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EP-0489308-B1	489,308	EP	B1	EN	19,980,902	1,992	20,100,220	new	C07H17	A61K31	A61P15, A61P31, A61K31, A61P33, A61P13, A61P3, C07H17	C07H 17/08G	Partricin derivatives	Derivatives of partricin and of its individual components, partricin A and B, wherein the mycosamine primary amino group forms an amide bond with the carboxy group of acids containing in addition a basic nitrogen group, the carboxy group at C-l8 of macrolide ring being either free or in form of ester or neutral amide or containing in the chain a basic nitrogen moiety, their pharmaceutically acceptable salts, a process for preparing the same and pharmaceutical formulations containing the same.	The present invention concerns derivatives of partricin and of its components, partricin A and B, their pharmaceutically acceptable salts, a process for preparing the same and pharmaceutical formulations containing the same.Partricin is a polyene macrolide of the heptaene group. Its structure is reported in Merck Index, 11° Ed., No. 6997. It was isolated from fermentative broths of Streptomyces aureofaciens, NRRL 3878 strain (GB-B-1 357 538), and consists of two components in a ratio of about 1:1, partricin A and partricin B, the only difference between them being a group -NHCH3 or -NH2, respectively, in para position of the aromatic ring at the side chain bound to C-37 of macrolide. The two components are separated according to conventional methods, such as, for example, preparative silica gel or reversed phase chromatography or Craig countercurrent distribution; alternatively, the components A and B can be obtained independently by fermentation.Partricin and its individual components A and B possess high antifungal and anti-protozoal activities. More recent studies have shown their potentiality also as anti-hypercholesterolemic, anti-hyperlipemic or antiviral agents and as therapeutic agents for curing the prostate benign hypertrophy. The pharmacological properties of partricin are to be ascribed to its bond and interaction capabilities with sterol compounds. However, owing to partricin high toxicity substantially due to its uncapability of discriminating between fungal cell wall ergosterol and human cell cholesterol, no practical application has been so far found for partricin in the therapeutic field.On the contrary, its methyl ester or mepartricin (see, e.g., U.S.-A-3 780 173 and Merck Index, ll° Ed., No. 5733),is widely used as an antifungal agent in topical and systemic formulations, and advantageously employed also in the treatment of prostate benign hypertrophy.However, although this less toxic and more active derivative represents a substantial improvement as compared to partricin, mepartricin still possesses a rather high toxicity, and is likely to give rise to emolysis and nephrotoxicity, especially on long--term treatments.Moreover, being mepartricin water-insoluble, the injectable solutions required for the treatment of serious systemic infections can be prepared only in the presence of surfacting agents, such as, for example, sodium lauryl sulfate (SLS). It must be appreciated, however, that this technique does not allow true solutions to be obtained, but only micellar dispersions, as indicated by both absorption maxima characteristically shifted to longer wavelengths and varied absorbance in UV spectra. It must also be taken into account that the presence of a surfacting agent, such as SLS, in the formulations can cause additional toxicity.The Journal of Antibiotics, vol. XXXV, n. 7, pages 911-914 (1982), Wright et al., discloses amide derivatives of polyene macrolides containing an aminoacyl group into the mycosamine moiety which show antimicrobial activity. Such derivatives are not easily bioavailable and show a certain toxicity.In consequence of the foregoing, and notwithstanding the presence of a number of functional groups in the molecule of partricin hindering univocal chemical transformations, a real request still exists of novel derivatives, which: a) possess lower toxicity and higher activity as compared to the natural antibiotic and mepartricin,b) can be transformed, by means of pharmaceutically acceptable agents, into water-soluble salts, suitable for preparing injectable forms and oral formulations endowed with better bio-availability.The object of the present invention is to provide derivatives of partricin and of its individual components A and B of the following general formula (I): wherein R' is a hydrogen atom (partricin B) or a methyl group (partricin A)R1 represents an aminoacyl radical -CO(CH2)mNR3R4, wherein m = 1, 2 or 3, R3 and R4, which can be the same or different, represent a C1-C3 alkyl group or form with the nitrogen atom to which they are bound, a five- or six-membered heterocyclic ring optionally containing another hetero atom selected from O, S and N, this latter being preferably methyl- or 2-hydroxyethyl-substituted;R2 represents a hydroxy, C1-C6 alkoxy, NR3R4 amino or -NH-(CH2)m-NR3R4 aminoalkylamino group, wherein m, R3 and R4 have the same meaning as above, or a substituted -NH-(CH2)m-R5 alkylamino group, wherein m has the same meaning as above and R5 represents a five- or six-membered nitrogen heterocyclic ring, optionally N-methyl- or N-ethyl - substituted.X represents the anion of a pharmaceutically acceptable, organic or inorganic acid, and n is 0, 1 or 2.From the foregoing it follows that the present derivatives are basic amides at the mycosamine amino group of partricin and partricin A and B or of their ester or amide derivatives at the C-18 carboxy group. The mycosamine amino group is therefore transformed into an amide derivative by reaction with the carboxy group of an acid containing a primary, secondary or tertiary amino group, in order to maintain a basic site in said molecular position. The C-18 carboxy group is either free or, alternatively, modified by formation of derivatives, such as esters or neutral or basic amides.Starting materials for the synthesis of the derivatives of the present invention are partricin, partricin A and B and their derivatives at the carboxy group, such as, for example, esters (U.S.-A-3 780 173) and amides. These latter can be easily synthesized by reacting the C-18 carboxy group with a primary or secondary amine, in the Dresence of diphenylphosphorazidate. The synthesis of the present derivatives involves the formation of an amide bond between the primary amino group at C-3' in the above starting materials (hereinafter only amines ) and the carboxy group of an amino acid of general formula (II): HOOC-(CH2)m-NR3R4 wherein m, R3 and R4 have the above indicated meanings. The preparation is carried out according to methods known in the field of chemical syntheses, such as, for example, the reaction between the amine and the acid chloride, preferably in the presence of an HCl acceptor, such as an inorganic or tertiary organic base; the reaction between the amine and an ester of the amino acid; the direct reaction between the amino and carboxy groups by means of dicyclohexylcarbodiimide (DCCD), in the presence or not of adjuvants, such as, for example, 4-dimethylaminopyridine (DMAP) or 1-hydroxybenzotriazole (HOBT); the reaction between the amine and an amino acid carboxy-activated derivative, such as, for example, hydroxysuccinimide ester, esters with mono-, dinitro- or polyhalophenols, the imidazolide prepared by reaction with carbonyl-diimidazole or the azide formed in situ with diphenylphosphorazidate (DPPA), optionally in the presence of tertiary organic bases; such as, for example, triethylamine.Especially advantageous is the use of DPPA; the starting amine derivative is dissolved in a mixture of chlorinated solvents and lower aliphatic alcohols or, preferably, in polar aprotic solvents, such as, for example, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. and then treated with equimolar amounts of DPPA and acid. The molar ratio of DPPA/acid to amine is in the range of 1 to 6, and the addition of reagents to amine is carried out either all at once or by slow dropping or portionwise, at appropriate intervals. The reaction times are in the range of 1 to 36 hours, preferably 3 to 12 hours. The temperature is in the range of 0° to 50°C, usually 15° to 25°C.The optimum conditions for preparing each individual product are selected according to preliminary experiments, the progress of the reaction being controlled by thin layer chromatography (TLC). When the reaction has been completed or an optimum ratio of the product to unreacted amine or by-products, if any, is achieved, as indicated by TLC, the reaction products are precipitated by suitable organic solvents and filtered off.The final purification is carried out according to various techniques, such as, for example, by dissolution and reprecipitation in solvents, crystallization, chromatography and Craig countercurrent distribution.Chromatrography and countercurrent distribution also allow the present partricin derivatives to be separated into the individual components A and B. These latter however, are preferably obtained according to the above described methods by using as starting materials the individual components of partricin A and B, their esters and amides.Alternatively, the present derivatives wherein the C-18 carboxy group is in form of ester or amide, are obtained by the already described condensation reaction of the primary amino (mycosamino) group of partricin A or B with amino acids of general formula (II), followed by the preparation of esters or amides at the carboxy group, according to the above-mentioned methods.The derivatives of the present invention are solids of deep yellow color, high and ill-defined melting point (gradual decomposition), soluble in polar aprotic solvents, such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, etc, poorly soluble in the most common organic solvents insoluble in water. The final control and characterization of the final products are carried out by the usual techniques: TLC, HPLC, elemental analysis, mass spectrometry, IR, UV. As far as UV spectra are concerned, it should be considered that the spectra of present derivatives and corresponding starting materials are qualitatively the same, because the chromophore is unchanged.The derivatives of the present invention are transformed into salts by reaction with pharmaceutically acceptable, inorganic or organic acids, such as, for example, hydrochloric, sulfuric, benzoic, glycolic, gluconic, glucuronic, ascorbic, aspartic, glutamic acid, etc.Said salts are obtained by adding 1-2 moles of acid to the aqueous suspension of the present derivatives. From the resulting solutions the salts are isolated according to usual methods, such as, for example, vacuum evaporation to dryness, freeze-drying, spray-drying, concentration and cooling, precipitation by water--miscible organic solvents, etc. Salts with organic acids are preferred because their aqueous solutions are usually neutral or only weakly acidic. The above-mentioned salts are enough soluble in water so as injectable pharmaceutical forms can be prepared. Moreover, the bioavailability of oral pharmaceutical forms, prepared with active ingredients in form of water-soluble salts, is usually higher.The derivatives of the present invention show antifungal and anti-protozoal activities comparable with, or even higher than, partricin and mepartricin, but lower both haemolytic power and local and systemic toxicity.These properties result in a more favourable therapeutic index, whereby these compounds are useful not only for the clinical therapy of fungal and protozoal infections, but also, and especially, for the cure of diseases requiring long-term treatments, such as, for example, hypercholesterolemia, hyperlipemia, prostate benign hypertrophy, etc. The lower toxicity of the present derivatives and of their salts also allows their utilization at high dosage rate, for example in controlling infections caused by potentially sensitive viruses, having lipidic envelope, such as the virus of the acquired immuno-deficiency syndrome (AIDS). For all therapeutic uses, the derivatives of the present invention and their salts can be diluted with appropriate amounts of a pharmaceutically acceptable, liquid or solid carrier. Formulations include, for example, tablets, effervescent tablets, powders, granules, capsules for oral administration as well as suspensions and solutions in suitable aqueous and oily carriers for oral administration. Slow-release oral forms and enteric-coated formulations are also produced. These latter are particularly suitable for obviating the reduced stability of some of the present derivatives in a medium at strongly acidic pH.Creams and ointments are prepared for use in dermatology and suppositories, bougies and vaginal suppositories or tablets for topical use.The present derivatives can be administered also parenterally in form of aqueous sterile solutions or, preferably, as freeze-dried powders dissolved at the time of usage. In the injectable formulations, even more than in other formulations, the compounds are employed in form of water-soluble salts.In case of necessity, combinations with other drugs are possible, depending on the pathological conditions to be subjected to the therapeutic treatment.The following examples are intended to illustrate the invention, but are not to be taken as limiting the scope thereof.The partricin derivatives described in the following examples have been checked by IR and UV spectrometry, elemental analysis, thin layer chromatography (TLC) and high-pressure liquid chromatography (HPLC). TLC was carried out on Silica gel 60, F254 Merck, plates using a CH2Cl2/MeOH/H2O/NH4OH, 85/15/1/1 v/v, mixture as eluant, and UV lamp, λ = 254 nm, as detector.HPLCs were carried out on an Hitachi-Merck instrument, consisting of L 6200 ternary gradient pump,L 4000 UV variable wavelenght detector and L 2000 integrator.Conditions: Merck Hibar Lichrocart 125 mm, ⊘ 4 mm, Column packed with Superspher 100 RP-18,4 µm; mixtures of 5 mM EDTA in H2O and acetonitrile as eluant; detection: UV, λ = 378 nm; flow rate 1 ml/min; room temperature. The following three types of gradient were used; EXAMPLE 1 - N-dimethylaminoacetyl-partricin A, methyl ester11.4 g (10 mmoles) of partricin A methyl ester (mepartricin A) were dissolved in 110 ml of dimethylacetamide. To this solution 5.15 g (50 mmoles) of dimethylaminoacetic acid (dimethylglycine), 5.05 g (50 mmoles) of triethylamine and 13.76 g (50 mmoles) of diphenylphosphorazidate were successively added under stirring and at room temperature. The solution was kept for 6 hours under stirring at room temperature its progress being checked by TLC (the procedure is detailed in the introduction to the examples). The reaction mixture was then treated with 1 l of ether/ethanol mixture (9:1), the precipitate was filtered off, washed with ether and dried under vacuum at 40°C. The resulting raw product (about 12 g) was purified preferably by medium-pressure preparative chromatography (MPLC) using silica gel in a weight ratio of 12:1 to the raw product. A CH2Cl2/CH3OH/H2O/NH4OH mixture, 85/15/1/1 v/v, was used as eluant. Alternatively, the raw product could be purified by Craig countercurrent distribution or column chromatography with silica gel, with the same eluant mixture used for MPLC.The MPLC fractions, pure according to TLC, are pooled and evaporated to dryness under vacuum. 7g of pure product are obtained in form of a deep yellow crystalline powder. TLCRf = 0.52HPLCretention time = 26.21' (gradient A)Elem. analysis for C64H95N3O20foundC 62.51%H 7.95%N 3.36%calc.C 62.67%H 7.81%N 3.43%Example 2 - N-dimethylaminoacetyl-partricin B methyl esterThe title product was prepared according to the procedure of Example 1, starting from mepartricin B. The product was in form of a deep yellow crystalline powder. TLCRf = 0.23HPLCRetention time = 19.32' (gradient A)Elem. analysis for C63H93N3O20foundC 62.30%H 7.79%N 3.39%calc.C 62.41%H 7.73%N 3.47%Example 3 - N-dimethylaminoacetyl-partricin methyl esterThe title product was prepared according to the procedure of Example 1, starting from mepartricin as A+B complex in a ratio of about 1:1. TLCRf = 0.52 (component A) and 0.23 (component B)HPLCRetention time = 26.21' (A) and 19.32' (B) (gradient A)Example 4The derivatives listed in the following Table 1 with their respective HPLC retention times and TLC Rf values were prepared by reacting the mycosamine amino group of the corresponding ester or amide derivatives at the carboxy group of partricin or partricin A and B with amino acids, such as 1-piperidine-propionic acid, 4-methyl-1-piperazine-acetic acid, 4-(2-hydroxy-ethyl)-1-piperazine-acetic acid, dimethylaminoacetic acid in the presence of triethylamine and diphenylphosphorazidate. Reaction conditions (temperature, molar ratios between partricin derivatives and reagents) and procedure were essentially the same as those of Example 1.The optimum reaction times for each preparation were determined by means of preliminarly reactions of 5 mmoles of starting derivatives of partricin, the reaction being stopped when the most favourable ratio of the conversion to final product to the formation of impurities and by-products was achieved. In each instance the times were in the range of between 4 and 8 hours.The so obtained derivatives, after purification by column chromatography with silica gel, were all in form of yellow crystalline powders and showed satisfactory C, H, N data of the elemental analysis.A few data on microbiological activity on C.albicans, on hemolytic activity and acute toxicity in mice are reported in Table 2. Example 5 - N-dimethylaminoacetyl-partricin A 2-dimethyl-amino-diaspartate.1,28 g of N-dimethylaminoacetyl-partricin A 2-dimethylaminoethylamide, prepared as described in Example 4, and 0,27 g of aspartic acid acid were added to 30 ml of distilled water and the resulting suspension was kept under stirring over a few minutes till total dissolution.The resulting yellow solution was evaporated under vacuum to dryness, the residue slurried with a little amount of ethanol, filtered and dried at 40°C under vacuum. The salt was a yellow crystalline powder, soluble in water with almost neutral reaction (pH 6), having the same TLC (Rf = 0.25) and HPLC (retention time = 25.16', gradient B) characteristics of the free base. Elem. analysis: for C75H117N7O27found %C 57.99%H 7.44%N 6.19%calc. %C 58.16%H 7.61%N 6.33%Alternatively, the diaspartate compound was isolated from the aqueous solution, prepared as above, according to the following techniques: a) freeze-dryingb) spray-dryingc) concentration under vacuum to half volume and precipitation by addition of about 12 volumes of ethanol or acetone.Whichever the isolation procedure may be, the salt showed in every instance satisfactory analytical data (C,H,N elemental analysis, TLC, HPLC). Example 6According to the procedure described in the previous Example, the following salts were prepared from the corresponding free bases described in Example 4.The salts showed the same TLC and HPLC characteristics of the free bases (see the Rf and retention time data reported in Table 1). N-dimethylaminoacetyl partricin A - 2-dimethylamino ethylamide diglutamate Elem. analysis: for C77H121N7O27found %C 58.72H 7.69N 6.25calc. %C 58.65H 7.74N 6.22N-dimethylaminoacetyl partricin A - 2-dimethylaminoethylamide di-gluconate Elem. analysis: for C79H127H5O33found %C 56.72H 7.55N 4.14calc. %C 56.65H 7.64N 4.18N-dimethylaminoacetyl partricin A - /4-(2-hydroxyethyl)/piperazide diaspartate Elem. analysis: for C77H119N7O28found %C 58.02H 7.48N 6.18calc. %C 58.13H 7.54N 6.16 N-dimethylaminoacetyl partricin A - (4-methyl)piperazide diglycolate Elem. analysis: for C72H111N5O25 found %C 59.85H 7.69N 4.87calc. %C 59.77H 7.73N 4.84N-dimethylaminoacetyl partricin A - (4-methyl)piperazide diglucuronate Elem. analysis: for C80H123N5O33found %C 57.15H 7.31N 4.20calc. %57.09H 7.37N 4.16N-dimethylaminoacetyl partricin A - (4-methyl)piperazide diascorbate Elem. analysis for: C80H119N5O31found %C 58.35H 7.31N. 4.29calc. %C 58.34H 7.28N. 4.25N-piperidinopropionyl partricin A - (4-methyl)piperazide diaspartate Elem. analysis for: C80H123N7O27found %C 59.54H 7.62N 6.1calc. %C 59.48H 7.68N 6.07N-4-methylpiperazinoacetyl partricin A - 2-dimethylamino ethylamide diaspartate Elem. analysis for: C78H122N8O27found %C 58.52H 7.71N 6.93calc. %C 58.41H 7.67N 6.99N-4-(2-hydroxyethyl)piperazinoacetyl partricin A - 2-dimethylamino ethylamide diaspartate Elem. analysis for: C79H124N8O28found %C 57.99H 7.73N 6.83calc. %C 58.07H 7.65N 6.86	Claims for the following Contracting States : AT, BE, CH, DE, FR, GB, IT, LU, NLDerivatives of partricin and of its individual components A and B of the following general formula (I): wherein R' is an hydrogen atom (partricin B) or a methyl group (partricin A);R1 represents a CO(CH2)mNR3R4 aminoacyl radical, wherein m = 1, 2 or 3, R3 and R4 which can be the same or different, represent a C1-C3 alkyl group or form with the nitrogen atom to which they are bound, a five or six-membered heterocyclic ring optionally containing an additional hetero atom selected from O, S and N;R2 represents a hydroxy, C1-C6 alkoxy,NR3R4 amino or -NH-(CH2)m-N-R3R4 aminoalkylamino group, wherein m, R3 and R4 have the same meaning as above, or a substituted -NH-(CH2)m-R5 alkylamino group, wherein m has the same meaning as above and R5 represents a five- or six-membered nitrogen heterocyclic ring, optionally N-methyl or N-ethyl-substituted.X represents the anion of a pharmaceutically acceptable, organic or inorganic acid, and n is 0, 1 or 2.Compound according to claim 1, wherein the additional hetero atom of the NR3R4 heterocycle is methyl or 2-hydroxyethyl-substituted nitrogen atom.Compound according to claim 1, wherein R1 represents one of the following groups: Compound according to claim 1, wherein R2 represents one of the following groups: Compound according to claim 1, wherein X represents the anion of aspartic, glutamic, glycolic, glucuronic, gluconic, ascorbic acid.Compound according to claim 1, which is N-dimethylaminoacetyl-partricin A dimethylamino-ethylamide.Compound according to claim 1, which is N-dimethylaminoacetyl-partricin A dimethylamino-ethylamide diaspartate.Compound according to claim 1, which is N- (4-methyl-1-piperazinoacetyl) partricin A 2-dimethylaminoethyl amide.Compound according to claim 1, which is N-(4-hydroxyethyl-1-piperazinoacetyl) partricin A 2-dimethylaminoethyl amide.Compound according to claim 1, which is N-dimethylaminoacetyl-partricin A 2-pyridylethyl amide.Compound according to claim 1, which is N-piperidinopropionyl-partricin A 2-pyridylethyl amide. Process for preparing the compounds according to claim 1, characterized in that a partricin or partricin A or B derivative is condensed at the mycosamine amino group with an R1-OH acid.Process according to claim 8, wherein the condensation reaction is carried out in the presence of diphenyl-phosphorazidate.Process according to claim 8, wherein the condensation reaction is carried out in the presence of diphenyl-phosphorazidate and triethylamine.Pharmaceutical formulations having activity against fungal and Protoza infections, hypercholesterolemic and hyperlipemic conditions, the prostate benign hypertrophy and viral infections, containing a therapeutically effective amount of a compound of formula (I) according to claim 1, in combination with appropriate pharmaceutical excipients and ausiliary substances.Claims for the following Contracting State : ESA process for preparing derivatives of partricin and its individual components A and B of the following formula (I) wherein R is an hydrogen atom (partricin B) or a methyl group (partricin A);R1 represents a -CO(CH2)mNR3R4 aminoacyl radical, wherein m = 1, 2 or 3, R3 and R4 which can be the same or different, represent a C1-C3 alkyl group or form with the nitrogen atom to which they are bound, a five or six-membered heterocyclic ring optionally containing an additional hetero atom selected from O, S and N; R2 represents a hydroxy, C1-C6 alkoxy, NR3R4 amino or -NH-(CH2)m-N-R3R4 aminoalkylamino group, wherein m, R3 and R4 have the same meaning as above, or asubstituted -NH-(CH2)m-R5 alkylamino group, wherein m has the same meaning as above andR5 represents a five- or six-membered nitrogen heterocyclic ring, optionally N-methyl or N-ethyl-substituted; X represents the anion of a pharmaceutically acceptable, organic or inorganic acid, and n is 0, 1 or 2, which comprises the condensation of a partricin or partricin A or B derivative at the mycosamine amino group with a R1-OH acid.A process as claimed in claim 1, wherein the condensation reaction is carried out in the presence of diphenyl-phosphorazidate.A process as claimed in claim 1, wherein the condensation reaction is carried out in the presence of diphenyl-phosphorazidate and triethylamine.A process as claimed in claim 1, wherein the additional hetero atom of the NR3R4 heterocycle is methyl or 2-hydroxyethyl-substituted nitrogen atom.A process as claimed in claim 1, wherein R1 represents one of the following groups: A process as claimed 1, wherein R2 represents one of the following groups: A process as claimed in claim 1, wherein X represents the anion of aspartic, glutamic, glycolic, glucuronic, gluconic, ascorbic acid.A process as claimed in claim 1, to obtain N-dimethylaminoacetyl-partricin A dimethylamino-ethylamide.A process as claimed in claim 1, to obtain N-dimethylaminoacetyl-partricin A dimethylamino-ethylamide diaspartate.A process as claimed in claim 1, to obtain N-(4-methyl-1-piperazino-acetyl) partricin A 2-dimethylaminoethyl amide.A process as claimed in claim 1, to obtain N-(4-hydroxyethyl-1-piperazinoacetyl) partricin A 2-dimethylaminoethyl amide.A process as claimed in claim 1, to obtain N-dimethylaminoacetyl-partricin A 2-pyridylethyl amide.A process as claimed in claim 1, to obtain N-piperidinopropionyl- partricin A 2-pyridylethyl amide.	PRODOTTI ANTIBIOTICI SPA; SPA SOCIETA' PRODOTTI ANTIBIOTICI S.P.A.	BRUZZESE TIBERIO; OTTONI FRANCO; SIGNORINI MASSIMO; BRUZZESE, TIBERIO; OTTONI, FRANCO; SIGNORINI, MASSIMO
EP-0489310-B1	489,310	EP	B1	EN	19,970,129	1,992	20,100,220	new	A47C27	A47C31	A47C27, G01L5, A47C7, G01N9, A61G7, B60N2, A47C31	A47C 27/10, K61G7:057K, B60N 2/44H, A47C 31/12	Feedback system for load bearing surface	An electronic system for adjusting a load bearing surface (12) such as a chair or bed to provide a desired level of comfort comprises an array of pressure sensors (14) located within the load bearing surface. The pressure sensors (14) generate data indicating the actual distribution of pressure exerted by a user on the load bearing surface. An electronic processor (40) processes the data generated by the array of pressure sensors (14). The processor (40) compares the fraction of total load exerted on each of a plurality of regions of the load bearing surface (12) with a desired range for each region. If the fraction of total load for any region is not within the desired range, a servo-mechanism (28) is activated to change the shape of the load bearing surface (12) so that the fraction of total load on each region is within the desired range, so as to provide a desired level of comfort to the user.	The present invention is directed to an electronic system for adjusting a load bearing surface to provide a desired level of comfort for a user according to the preamble of patent claim 1 and to a method for adjusting a load bearing surface to provide a desired level of comfort for an individual user according to the preamble of patent claim 11. US-A-4 797 962 discloses a system and a method including the features of the preambles of claims 1 and 11. According to this system a load bearing surface is divided into a plurality of sections. Each section contains one or more air sacs. When a user decides to use the load bearing surface, the user's height and weight, for example, are entered by a keyboard into a microprocessor. The microprocessor calculates the necessary internal pressure of each air sac. Once this pressure has been calculated and set, it is monitored by pressure transducers. If the air pressure in an air sac increases above or decreases below what was calculated to be optical, a servo valve in the air supply line for that air sac is adjusted by the microprocessor. US-A-3 982 786 teaches to divide a cushion into several cushion elements forming a grid and capable of being filled with a flowable medium, at least a number of which elements are capable of being connected exclusively with each other through pipes containing at least one valve. Means are provided which are responsive to the loading on the support surface for permitting reversible fluid flow between the elements upon predetermined positive or negative differences in the fluid pressures therebetween. These means are realized by valves between the elements. A patent application entitled Method and Apparatus for Evaluating a Load Bearing Surface filed for Clifford M. Gross on April 18, 1990, bearing Serial No. 07/510,653, now U.S. Patent No. 5,060,174, and assigned to the assignee hereof contains subject matter related to the subject matter of the present application. The above-identified related application is incorporated herein by reference. The above-identified patent application describes a system for measuring the pressure distribution on a load bearing surface such as a seat or bed. The system of the above-identified patent application comprises a two-dimensional array of pressure sensors located within the load bearing surface and a processor for processing the data generated by the pressure sensors. Using the data generated by the pressure sensors it is possible for the processor to evaluate certain attributes of the pressure distribution on the load bearing surface. For example, it is possible to divide the load bearing surface into regions and to determine the fraction of the total load on each region, the mean and median pressure of the various regions, and the pressure gradients between regions. By testing many different seats with many different human users, it is possible to statistically correlate subjective comfort sensations of the user with certain attributes of the objectively measured pressure distributions exerted on the seats by the users. For example, a seat pan may be divided into eight regions: left thigh, right thigh, left buttock, right buttock, two left bolsters and two right bolsters. Similarly, a seat back may be divided into eight regions: left bolster, right bolster, three lumbar regions and three thoracic regions. It is possible to statistically correlate the fraction of the total load on the seat which is exerted on each of these regions with a user's comfort. In this manner, it is possible to determine for each seat region a desired range for the fraction of the total load which is exerted on a region. A seat may then be objectively classified as comfortable for a user if the actual distribution of the load exerted by the user on the seat is such that the load fraction in each region falls into the corresponding desired range. Other attributes of the pressure distribution besides fraction of total load exerted on a region may also be statistically correlated with comfort. For example, small pressure gradients correlate with high comfort levels and large pressure gradients correlate with low comfort levels. One reason for this is that small gradient values indicate that the load is more evenly distributed over a greater surface area of a seat. It is an object of the present invention to utilize the above-described correlation between certain pressure distribution attributes and comfort to provide an electronic feedback system for automatically reconfiguring a load bearing surface such as a seat or bed to provide a user with a certain desired level of comfort. This object is achieved by an electronic system for adjusting a load bearing surface of the above-cited kind having the characterizing features of claim 1 The present invention is directed to an electronic feedback system for adjusting a load bearing surface such as a seat or bed to provide a desired level of comfort for a user. In an illustrative embodiment, a two-dimensional array of pressure sensors generates data indicating the actual distribution of pressure exerted by the user on the load bearing surface. The data generated by the array of pressure sensors is processed by an electronic processor. In an illustrative embodiment of the invention, the electronic processor determines, from the data generated by the pressure sensor array, the fraction of the total load exerted on each of a plurality of regions of the load bearing surface. The processor also compares the fraction of total load on each region of the load bearing surface with a predetermined load range. In the case of a load bearing device such as a seat, it is known that the seat is comfortable when the fraction of total load exerted on each of a plurality of regions is within a certain range. When the fraction of total load exerted on one or more of the regions of the load bearing surface is not within the corresponding desired range, the electronic processor activates a servo-mechanism which alters the shape of the load bearing surface to redistribute the pressure in such a way so as to bring the fraction of total load on each region into the desired range. This feedback system operates continuously and in real time. However, to avoid having the load bearing surface reconfigure itself for each small movement of the user, time averages of the load fraction exerted on each region of the load bearing surface are illustratively calculated and utilized by the processor to control the servo-mechanism. In this way the feedback system responds to larger longer term movements of the user rather than responding to every single small movement of the user. In an alternative embodiment of the invention, instead of comparing the actual load fraction exerted on each region with a range of desired values, other attributes of the actual pressure distribution on a load bearing surface may be utilized to determine if a seat or other load bearing surface is comfortable to a user. These other attributes include pressure gradients, mean pressures, median pressure, and the standard deviation of pressures in particular regions of a load bering surface. To change the shape of the load bearing surface, a plurality of air bladders may be located within the surface. In this case, the processor controls the amount of air in the individual bladders to regulate the shape of the load bearing surface. Alternatively, a plurality of plates may be located within the surface and the positions of the plates are changed under the control of the processor to change the shape of the load bearing surface. In short, the present invention provides a highly ergonomic interface between a user and a load bearing surface such as a vehicle seat, office seat or bed. Furthermore, the above-cited object is achieved by a method of the above-cited kind having the characterizing features of patent claim 11. In the following, the invention is described in detail by means of examples in connection with figures 1-5 FIG 1 schematically illustrates a feedback system for reconfiguring a load bearing surface in accordance with an illustrative embodiment of the present invention; FIG 2 and FIG 3 schematically illustrate a load bearing surface in the form of a seat which can be reconfigured in accordance with an illustrative embodiment of the present invention; FIG 4 is a flow chart which schematically illustrates an algorithm carried out by a processor in the system of FIG 1; and FIG 5 illustrates an alternative mechanism for reconfiguring a load bearing surface. FIG 1 schematically illustrates a load bearing device 10. Although the load bearing device 10 is shown in FIG 1 as being in the form of a rectangular solid, this geometry is intended to be illustrative only and the load bearing device 10 is intended to represent a seat, such as a vehicle or office seat, or a bed, for example. The load bearing device 10 includes a load bearing upper surface 12 which supports a load in the form of all or part of a human being. Located within and just beneath the surface 12 is a two-dimensional array of pressure sensors 14. Illustratively, each of the pressure sensors 14 is a Force Sensing Resistor available from Interlink Electronics, Santa Barbara, California. These devices are polymer thick film devices which exhibit a decreasing resistance when an increasing force is applied in a direction normal to the device surface. The sensors are arranged in strips 16 and connected so as to form a voltage divider network. The load bearing surface 12 is divided into a plurality of regions 1, 2, 3,4. Associated with each region 1, 2, 3, and 4 is a subset of the pressure sensors 14. In some embodiments of the invention, the different regions may overlap so that some of the sensors belong to more than one region. Located within the load bearing device 10 are a plurality of air bladders 20. In a preferred embodiment of the invention, there are one or more air bladders associated with each of the regions 1, 2, 3, 4 of the load bearing surface. Each of the air bladders 20 is connected to a source 22 of a pressure medium such as air by way of a conduit 24. A valve 26 is located in each conduit 24 to control the flow of air into and out of the associated bladder 20. Each valve 26 is controlled by a servo-mechanism illustratively in the form of a motor 28. By controlling the amount of air in each of the bladders 20, it is possible to control the shape of the load bearing surface 12 of the load bearing device 10. The present invention includes a feedback system 30 for changing the shape of the load bearing surface 12 to provide a desired level of comfort for a human being supported by the load bearing surface. In FIG 1, the feedback system 30 includes the multiplexer 32, the interface 34, the analog-to-digital converter 36, and the processor 40. The multiplexer 40 connects a signal from any one of the pressure sensors 14 to the interface 34. The sequence in which the pressure sensors are to be interrogated are transmitted from the processor 40 to the interface 34. Analog signals from the multiplexer are transmitted through the interface unit to the analog-to-digital converter 36 wherein the signals from the pressure sensors are converted to digital form and transmitted to the processor 40 which stores these signal values in memory. Thus, when there is a load in the form of a human being on the load bearing surface 12, the processor 40 receives from the array of pressure sensors 14 data representative of the actual distribution of pressure on the load bearing surface. This data is processed by the processor 40 and, in response to this data, the processor 40 outputs signals on the lines 42 to control the motors 28. In this manner, the processor 40 controls the shape of the load bearing surface 12. In particular, the processor 40 controls the shape of the load bearing surface 12 to achieve a desired level of comfort for the user. The algorithm utilized by the processor to change the shape of the load bearing surface is described in detail below. FIG 2 shows a partly perspective and partly cross-sectional view of a seat such as an automobile seat whose shape may be reconfigured in accordance with an illustrative embodiment of the present invention. The chair 50 is supported by a base 52. The chair 50 is divided into a plurality of sections including the headrest 54, the thoracic section 56, the lumbar section 58, the buttocks section 60 and the thigh section 62. Each section such as the buttocks section 60 includes a frame 64 for supporting the section. Each section such as the buttocks section 60 comprises a fabric outer surface 66 which is filled with the foam 68. The various sections 54, 56, 58, 60, 62 are movable with respect to each other through use of the actuators 70, 72, and 74. To implement the present invention, an array of pressure sensors 14 is embedded under the fabric surface for the thoracic, lumbar, buttocks, and thigh sections. In addition, the thoracic, lumbar, buttocks and thigh sections of the chair 50 include the bladders 20 which are illustratively located between the frame 64 and foam 68. In the illustrative embodiment of the invention shown in FIG 3, no bladders or pressure sensors are included in the headrest 54, although in other embodiments such bladders and pressure sensors may be incorporated. By using the feedback system described above in connection with FIG 1, air can be added or removed from the bladders 20 to change the shape of the load bearing surface formed by the seat 50. FIG 3 shows how air has been added to some of the bladders 20 in the thoracic, lumbar and thigh regions to change the shape of these regions. An illustrative algorithm utilized by the processor 40 of FIG 1 to control the shape of a load bearing surface is illustrated by the flow chart of FIG 4. Thus, as shown in FIG 4, the first step of the load bearing surface shape-changing process is to interrogate the pressure sensors 14 (box 70 of FIG 4) to obtain data representative of the actual distribution of pressure exerted by a user on a load bearing surface. Since the shape reconfiguration mechanism operates continuously, this data is time averaged (box 72 of FIG 4) to avoid changing the shape of the load bearing surface for each small movement by the user. Rather, the shape of the load bearing surface is preferably changed only in response to larger, longer term movement of the user. The processor 40 determines the fraction of total load exerted on each of a plurality of regions of the load bearing surface (box 74 of FIG 4). The processor then determines if the fraction of total load exerted on each region is within a desired range (box 76 of FIG 4). If the fraction of the total load in each region is within the desired range no action is taken. If the fraction of total load in each region is not within the desired range, a linear programming algorithm (box 78 of FIG 4) is executed to determine how to change the shape of the load bearing surface so that the fraction of total load exerted on each region is within the desired range. Once this is done the servo-mechanism such as the motors 28 of FIG 1 are activated to change the shape of the load bearing surface. Since a feedback system is utilized, after the change in shape of the load bearing surface, the pressure sensors are again interrogated to determine if the fraction of total load in each region is in the desired range and if further changes in shape are necessary for the load bearing surface. It should be noted that the desired range of load fraction for each region is determined experimentally by using conventional statistical techniques to statistically correlate the comfort of a statistically valid sample of users with the fraction of total load exerted on each region by these users. The linear programing algorithm utilized by the processor 40 of FIG 1 to determine how to change the shape of a load bearing surface in the case of a seat is as follows. An objective function: i=1N(Wi)(Xi-Ai)(Bi-Xi) is maximized subject to the following constraints i=1NXi = 100 Xi > Ai > O Xi < Bi > O where: Xi =the fraction of total load exerted on seat region i, for i = 1 to N Ai =lower limit of region i load fraction range of a very comfortable seat Bi =upper limit of region i load fraction range of a very comfortable seat Wi =priority (i.e. weighting) factor for region i Illustratively, there are N=16 regions in the seat. In the seat back there are three thoracic regions, three lumbar regions and left and right bolster regions. In the seat pan there are left and right buttocks regions, left and right thigh regions, and four bolster regions. Instead of using the foregoing algorithm, the processor 40 may evaluate a more complex algorithm. For example, an actual comfort level of a user may be set equal to a linear combination of a variety of attributes of the actual pressure distribution such as the standard deviation of the pressure distribution in particular regions, pressure gradients within or between particular regions, mean gradients in particular regions, maximum gradients in particular regions, median pressure in particular regions, fractions of total load in particular regions and sums of load fractions over several regions. When a linear combination of such attributes of the actual pressure distribution is obtained so as to obtain an actual comfort level of a user, the processor compares the actual comfort level to a desired comfort level range. If the actual comfort level is outside the desired range, the shape of the load bearing surface is altered until the actual comfort level is within the desired range. As has been indicated above, the shape of a load bearing surface can be changed by varying the quantity of air each of a plurality of air bladders within the surface. However, the shape change may be accomplished in other ways such as hydraulically or through the use of plates contained within the load bearing surface. FIG 5 shows a cross-section of a load bearing device 100 which has a load bearing surface 110. A plurality of plates 120 in the load bearing device are mounted on motor driven shafts (not shown) and repositioned under the control of a processor to change the shape of the load bearing surface. Finally, the above-described embodiments of the invention are intended to be illustrative only. Numerous alternative embodiments may be devised by those skilled in the art without departing from the spirit and scope of the following claims.	An electronic system for adjusting a load bearing surface (12) to provide a desired level of comfort for a user comprising pressure sensing means (14) for generating data indicating the actual distribution of pressure exerted by said user on said surface (12), electronic processing means (40) for processing said data generated by the said pressure sensing means (14) and servo-means responsive to said processing means (40) for reconfiguring said load bearing surface (12) so as to change the distribution of pressure exerted by the user on said load bearing surface (12) to achieve a desired level of comfort for the user, characterized in that (1) said pressure sensing means (14) generates data indicating a two-dimensional distribution of load exerted by an individual user on the load bearing surface (12), (2) said electronic processing means (40) determines an actual comfort level of the individual user from said two-dimensional distribution data and determines if the actual comfort level of the individual user is within a range of comfort levels predetermined to be desirable through a correlation of subjective comfort sensations with pressure distribution attributes of a statistically valid sample of users, and (3) said servo-means is activated by said electronic processing means (40) when said electronic processing means (40) determines that said actual comfort level is not within said predeterined range for reconfiguring in real time the load bearing surface (12) until said electronic processing means (40) determines that the actual comfort level of the individual user is within the predetermined range, (4) said actual comfort level of the individual user being a time average for preventing the load bearing surface (12) from being reconfigured for every small change in position of the individual user. The system according to claim 1, characterized in that said load bearing surface (12) forms part of a seat. The system according to claim 2, characterized in that said seat is a vehicle seat (50). The system according to claim 2, characterized in that said seat is an office seat. The system according to claim 1, characterized in that said load bearing surface (12) forms part of a bed. The system according to claim 1, characterized in that one or more air bladders (20) are contained within said load bearing surface (12) and said servo-means reconfigures said load bearing surface (12) by controlling the amount of air within said one or more bladders (20). The system according to claim 1, characterized in that a plurality of plates (120) is contained within said load bearing surface (12) and said servo-means comprises means for adjusting the position of said plates (120). The system according to claim 1, characterized in that said pressure sensing means (14) comprises a two-dimensional array of individual pressure sensors. The system according to claim 8, characterized in that said electronic processing means (40) determines the fraction of total load exerted on each of a plurality of regions (1 - 4) of said load bearing surface (12) and compares the fraction of total load for each region (1 -4) with a predetermined load range for each region (1 - 4). The system according to claim 9, characterized in that said servo-means reconfigures said load bearing surface (12) to change the distribution of load in said regions (1 - 4) so that the fraction of total load exerted on each region (1 - 4) is within the corresponding predetermined range for each region (1 - 4). A method for adjusting a load bearing surface (12) to provide a desired level of comfort for an individual user comprising the steps of: sensing the actual distribution of pressure exerted by said individual user on said load bearing surface (12) and generating data, processing the said data, and reconfiguring the shape of said load bearing surface, thereby achieving a desired level of comfort for the individual user, characterized by (1) sensing a current two-dimensional distribution of the load exerted on the load bearing surface by a particular individual user, (2) receiving data indicative of the two-dimensional distribution of the load exerted on load bearing surface, and (3) determining electronically a time-averaged actual level of comfort of the particular user based on the two-dimensional distribution of the load exerted on the load bearing surface and determining if the time-averaged actual level of comfort is a level of comfort predetermined to be desirable through a correlation of subjective comfort sensations and pressure distribution attributes of a statistically valid sample of users (4) whenever the position of the particular user is such that it is determined that the time-averaged actual level of comfort of the particular user is not a predetermined desired level of comfort, reconfiguring said load bearing surface so as to change the actual level of comfort so that it is a predetermined desired level of comfort, (5) the load bearing surface thereby being reconfigured over time in response to changes in position of the particular user of the load bearing surface to maintain the time-averaged actual level of comfort of the particular user at a desired comfort level.	AMERICA BIOMECHANICS CORP; BIOMECHANICS CORPORATION OF AMERICA	BANAAG JOSE; GOONETILLEKE RAVI; GROSS CLIFFORD; NAIR CHANDRA; BANAAG, JOSE; GOONETILLEKE, RAVI; GROSS, CLIFFORD; NAIR, CHANDRA
EP-0489326-B1	489,326	EP	B1	EN	19,990,526	1,992	20,100,220	new	G06F1	H05K7	G06F1, H05K7, F28D15	F28D 15/02E, G06F 1/20, G06F 1/20T, H05K 7/20S30	Cooling system of electronic computer	An electronic computer cooling system having a cooling apparatus to cool an electronic computer and cooling members (4, 41) for thermally connecting semiconductor devices (1) whose operating speeds are raised by cooling to a low temperature source of the cooling apparatus. Circuit boards (2) onto which the semiconductor devices (1) and the like constructing the electronic computer are mounted and the cooling apparatus such as a refrigerating apparatus and the like are compactly enclosed in a single casing (5). Or, the circuit boards (2) and the cooling apparatus are compactly enclosed in separate detachable casings, respectively. Thus, a structure in which desired semiconductor devices can be certainly cooled by using the cooling members (4, 41) is obtained.	The invention relates to a computer with a cooling system according to the preamble of claim 1. A conventional electronic apparatus has a construction in which one or a few fans are provided to cool a number of heat generating sources such as package, disk, power source, and the like which exist in a casing. A cooling air is blown by the fans and enters the casing through holes and flows in the casing along the package, disk, and power source and flows to the outside of the casing by the fans. In such a construction, an inflow temperature of the cooling air is equal to a room temperature. There is a case where, for instance, a temperature of the main portion of the package rises to about 50 to 100°C even when it is sufficiently cooled. As a method of improving the cooling of the package as mentioned above, there is an example in which channels are formed by surrounding the package by partition plates and fans are arranged before and after the channel as disclosed in JP-B-60-11830 (JP-A-53-145054). The publication also shows an example of coupling via heat pipe a cooling air inlet side with a heat source of very large heat capacity among various heat sources.In IEEE Transaction on Electron Devices , Vol. 36, No. 8 (1989), page 1404, a cooling system in which a board on which CMOS devices are mounted is dipped in liquid nitrogen is disclosed. As disclosed in JP-A-1-270296, there is a cooling system in which an inflow air is previously cooled by a refrigerating cycle.Among the above conventional techniques, in the case of the cooling system by the fans disclosed in JP-B-60-11830, to increase the cooling capacity in order to further reduce the temperature of semiconductor device, a flow rate of the air must be increased by increasing the number of fans, by increasing the size of fans, or the like. In such a case, there is a problem of an increase in fan noises. On the other hand, there is also a problem such that when the size of radiating fans is enlarged in order to enhance the cooling capability, a high installing density is not obtained. Further, the temperature of semiconductor device cannot be held to a temperature lower than the external air temperature and nothing is considered with respect to the realization of a high operating speed of the device due to the realization of a low temperature. On the other hand, according to the example in which the board on which the semiconductor device is mounted is dipped into liquid nitrogen, there are problems such that the size of refrigerator is large and another casing different from the casing to enclose the semiconductor device is needed, so that a large occupied area is necessary. According to the system disclosed in JP-A-1-270296, since all of the devices are uniformly cooled, nothing is considered with respect to the realization of a high operating speed of a special device and the dehumidification. US-A-4 546 619 discloses a cooler for cooling electronic equipment comprising a heat sink for attaching a plurality of electrical elements, a refrigeration system and pads for thermally connecting the refrigeration system with predetermined electrical elements. The pads are made of good thermal conductors such as aluminum or copper and are clamped to the heat sink by bolts, extending through the heat producing elements and the heat sink.The object of the invention is to provide an electronic computer of a high operating speed having a cooling system of a high reliability.This object is solved by a computer with a cooling system according to claim 1. According to one aspect of the invention, a flexible cooling member having a high heat conductivity is arranged between a special semiconductor device by which the whole operating speed of the computer is restricted and an evaporator of a refrigerator or a first cooling member which is thermally in contact with the evaporator, and such a semiconductor device is locally cooled by a cooling source which is generated from the refrigerator.A channel to lead the air cooled by the evaporator of the refrigerator is provided and the cooled air is blown out from holes formed in the channel and is allowed to collide with such a special semiconductor device, thereby cooling the device.A special semiconductor device and a cooling member having therein a group of liquid channels are thermally connected by a flexible member having a high heat conductivity. A liquid is circulated between the group of channels in the cooling member and a heat radiator provided on the outer wall of the casing by liquid pumps, thereby radiating the heat generated from the semiconductor device into the air on the outside of the casing. According to another aspect of the invention, a cooling member to thermally connect a special semiconductor device and an evaporator of a refrigerator is constructed by a plurality of heat pipes and an airtightness of each heat pipe is independently held.According to a further aspect of the invention, a refrigerator is constructed by refrigerating cycles of two or more stages and a dehumidifier is provided for an evaporator on the low temperature side.A water adsorption resin is attached to the evaporating portion in which a temperature decreases.According to a still another aspect of the invention, a temperature of a special semiconductor device is detected and a frequency of a reference clock generating section of the operation of the computer can be varied in accordance with the temperature value.According to a specific aspect of the present invention, there is provided an electronic computer and cooling system including a refrigerator contained with the computer in a casing, the refrigerator comprising an evaporator, a compressor, expansion valves, condensers, and the like, the computer including boards on which a plurality of semiconductor devices are mounted, wherein the semiconductor devices and the evaporator of the refrigerator are thermally connected by first and second cooling members; the first cooling member is formed by a block made of a material of a high heat conductivity or a group of a plurality of independent heat pipes; one end of the first cooling member is connected to the evaporator and the other end is arranged so as to face the board on which the semiconductor devices are mounted through the flexible second cooling member having a high heat conductivity; the heats which are generated from the semiconductor devices are transported to the evaporator through the second and first cooling members; the heat exchange with an operating refrigerant of the refrigerating cycle is performed by the evaporator; the heats are radiated to the outside of the casing by the condensers; whereby a heat path from the semiconductor devices to the evaporator of the refrigerator is assured, and a high cooling performance is obtained by a low temperature source by the refrigerator and the high speed operation of the computer can be accomplished.The electronic computer is constructed by a number of semiconductor devices whose functions and operating speeds are different and the operating speed of the whole computer is restricted by a device of the slow operating speed.First, a cooling source is generated by the refrigerator, and the evaporator of the refrigerator or the first cooling member which is thermally to come into contact with the evaporator and the special semiconductor device are thermally connected by arranging the flexible cooling member having a high heat conductivity between them. Therefore, for instance, when a special device such as a CMOS device or the like is set into a low temperature, the operating speed rises, so that the operating speed of the whole computer can be improved. In the above case, since the cooling member for connecting the semiconductor device and the evaporator of the refrigerator as a cooling source is constructed by a flexible material having a high heat conductivity, the gaps existing between the device surfaces and the cooling member surface due to a variation in heights of the devices can be connected by a small contact heat resistance, the heats of the semiconductor devices can be sufficiently radiated, and the operating temperatures can be reduced. On the other hand, since the temperature of the cooling source is held to be low by the refrigerator, a large temperature difference between the cooling source and the semiconductor device can be obtained, and a high cooling performance can be derived.The channel to lead the air cooled by the evaporator of the refrigerator is provided. The cooled air is allowed to collide with the special semiconductor device from the hole formed in the channel, thereby cooling the device. Therefore, the semiconductor device can be directly cooled by the jet air stream blown from the hole and the effective cooling of a high heat conductivity can be executed. Consequently, the special semiconductor device can be sufficiently cooled and the operating speed can be raised.The special semiconductor device and the cooling member having therein a group of liquid channels are thermally connected by the flexible member having a high heat conductivity. The liquid is circulated by the liquid pump between the group of channels in the cooling member and the radiator provided for the outer wall of the casing. Thus, the special device can be cooled and the high speed operation can be realized.Since the liquid is used as a cooling medium and is circulated in the casing, the high cooling performance can be realized by the cooling system of a small size and low noises.Second, the cooling member for thermally connecting the special semiconductor device and the evaporator of the refrigerator is constructed by a plurality of heat pipes and the airtightness of each heat pipe is independently held. Thus, the special semiconductor device can be cooled. Even when the airtightness of the heat pipe of a certain portion is not held, the heat transport can be executed by the remaining heat pipes and the cooling can be performed at a high reliability.Third, even when the semiconductor device is held to a low temperature, the dehumidifier is further provided for the cooling source of a low temperature, so that the moisture contained in the air in the casing is eliminated by the dehumidifier on the cooling source side. It is, therefore, avoided that the semiconductor device is wet with dew. An electrical malfunction does not occur.Fourth, the temperature of the semiconductor device is detected and the frequency of the reference clock can be varied in accordance with the temperature. Therefore, even in the case where the temperature of the cooling source is not immediately reduced by the refrigerator as in the case of the activation of the system, by reducing the clock frequency, the operating speed of the system is decreased. After the cooling source was reduced to a predetermined temperature and the enough cooling performance was derived, the clock frequency is raised and the high speed operation is allowed to be performed. Consequently, the normal operation can be executed even upon activation or starting of the system. Figs. 1 to 4 are diagrams showing an embodiment of the invention;Fig. 1 is a cross sectional perspective view of an electronic computer;Fig. 2 is a partial enlarged perspective view of a cooling member;Figs. 3 and 4 are perspective views of a first cooling member;Fig. 5 is a cross sectional perspective view of a computer system showing another embodiment;Figs. 6 to 10 are vertical sectional views of cooling member portions showing other embodiments of the invention, respectively;Fig. 11 is a cross sectional perspective view of an electronic computer showing another embodiment of the invention;Fig. 12 is a cycle constructional diagram showing another embodiment of the invention;Figs.13A to 13C are diagrams showing other embodiments of the invention, wherein Fig. 13A is a plan view showing the inside of an electronic computer, Fig. 13B is a cross sectional view of a refrigerator, Fig. 13C is a cross sectional view of a heat radiation fin;Fig. 14 is a diagram showing a construction of a reference clock generating section.An embodiment of the invention will be described with reference to Figs. 1 to 4. Fig. 1 is a diagram showing an electronic computer. Boards 2 and 16 on which a number of semiconductor devices 1 are mounted, a refrigerator, and cooling members 4 and 41 are enclosed in one casing 5. A number of semiconductor device groups having different functions for command processes, calculation, memory, input and output, operation control, and the like are installed on the boards 2 and 16. The computer is constructed by a plurality of boards as necessary. On the other hand, the refrigerator is constructed by a refrigerating cycle comprising evaporators 31 and 43, a condenser 32, an expansion valve 34, a compressor 33, refrigeration controller 15 and the like. Freon or the like is used as an operating refrigerant.The condenser 32 is constructed so as to form a part of or all of the portion of the casing 5 of the computer system. Although it is preferable to forcedly cool the condenser 32 by using a fan or the like, it is not always necessary to provide the fan when the condenser 32 has an enough large heat transfer area.In the embodiment shown in Fig. 1, both sides of the casing 5 are formed by the condensers 32. The evaporator is constructed by two portions of the evaporators 31 and 43. One end side of the first cooling member 4 made of a heat pipe or a heat conductive material having a high heat conductivity such as copper, aluminum, or the like is thermally to come into contact with the portion of the evaporator 31. The other end side of the first cooling member 4, that is, on the board 2 side is thermally to come into contact with the semiconductor devices 1 through the second cooling member 41 which has a high heat conductivity and is formed by a flexible material. In the embodiment shown in Fig. 1, although the boards 2 are arranged on both sides of the second cooling member 41, they can be also properly arranged at arbitrary positions. A fan 42 is attached to the portion of the evaporator 43. The cooled air is circulated in the casing 5 by the fan 42. A dehumidifier 6 can be arbitrarily provided; however, it is not always necessary to use it. When the dehumidifier 6 is provided, a construction similar to a refrigerating cycle shown in Fig. 12 can be applied.The heats which are generated from the semiconductor devices 1 mounted on the board 2 are transported to the first cooling member 4 through the second cooling member 41. Since the second cooling member 41 is flexible and has a high heat conductivity, even when there is a variation in heights of the semiconductor devices mounted on the board 2, the heats can be efficiently transported to the first cooling member 4. As a second cooling member 41, for instance, it is possible to use a member which is formed by sealing a perfluorocarbon liquid into a film which is molded in a sack shape. The heats transported to the first cooling member 4 are transferred to the evaporator 31 through the first cooling member. Channels are formed in the evaporator 31 connected to the first cooling member 4 and an operating refrigerant (for instance, freon) flows. When the refrigerant liquid is evaporated (at an evaporation temperature lower than a room temperature), the heat from the first cooling member 4 is received. In Fig. 1, the refrigerant liquid also flows in the evaporator 43. Fins are joined to refrigerant pipes of the evaporator 43. The air in the casing passes among the fins by the fan 42. For such a period of time, the refrigerant is evaporated and the heat exchange is performed between the air and the refrigerant, so that the air is set into a low temperature. The semiconductor devices in which the cooling performance is not particularly required like the semiconductor devices mounted on the boards 16 are cooled by the forced convection of the air of a low temperature. In the case where the forced convection is unnecessary, or in the case where all of the devices are cooled by the evaporator 31 by using the cooling members 4 and 41, the evaporator 43 and the fan 42 are unnecessary.The refrigerant evaporated by the evaporators 31 and 43 is compressed into a high pressure by the compressor 33 and is condensed and liquefied by the condensers 32. In such a processing step, the heat is radiated to the outside of the casing. The condenser 32 is, for instance, formed by directly joining a fin train to the pipes of the refrigerant. The refrigerant is again returned to the evaporator through the expansion valve 34.As mentioned above, the heats which are generated from the semiconductor devices are efficiently transported because a heat path from the semiconductor devices to the evaporator which constructs the refrigerating cycle and is held to a low temperature is assured by the cooling members. Further, the heats which are generated from all of the devices are transported to the evaporator and can be radiated in a lump to the outside of the casing by the refrigerating cycle by using the condenser attached by using a wide area of the casing wall, so that the cooling can be performed at a very high efficiency.In general, the operating speed of the computer differs depending on the function and the kind of device. The whole operating speed of the computer, mainly, the upper limit of the clock frequency is restricted by the lowest operating speed. On the other hand, it is known that an amount of heat generation increases as the operating speed of a certain kind of semiconductor device, for instance, a CMOS device rises or that the operating speed rises with a decrease in operating temperature. Therefore, by enhancing the cooling capability of the device, the operating speed of the device which specifies the operating speed of the whole computer is raised and the speed of the computer can be improved. In the embodiment, the semiconductor device 1 whose operating speed rises when the operating temperature is low is arranged so as to be cooled through the second cooling member 41.When the semiconductor devices are cooled, a group of special semiconductor devices such as CMOS devices or the like can be also cooled in a lump on a board unit basis as shown in Fig. 1. In such a case, the cooling efficiency to raise the calculating speed is improved and the devices which do not need to be cooled are also protected.For instance, as shown in Fig. 2, only special devices 1 can be also locally cooled. That is, it is possible to construct in a manner such that the first cooling member 4 is thermally to come into contact with only the special devices 1 through the second cooling member 41. Particularly, an electronic refrigerating device 44 or the like using a Peltier effect can be also used with respect to devices 11 which need a high operating speed of the computer.Although Figs. 1 and 2 show the case where the first cooling member 4 is made of a material having a high heat conductivity, there are also considered cases where the first cooling member 4 is formed by heat pipes as shown in Figs. 3 and 4.As shown in Fig. 3, the first cooling member is formed by the heat pipe 4. The heat pipe 4 is formed in a flat shape. The inside of the heat pipe 4 is separated to a plurality of independent chambers 45 each of which is connected from the evaporating portion near the board 2 to the condensing portion which is in contact with the evaporator 31. Fine grooves 46 and 47 are formed on the inner wall of each chamber 45 so as to perpendicularly cross each other and to be communicated by holes at intersecting points, respectively.For instance, as shown in an enlarged diagram of Fig. 3, the grooves 46 and 47 are formed on front and back surfaces of a plate 460 in the directions which cross perpendicularly each other in a manner such that the sum of depths of the grooves which are formed on the front and back surfaces is larger than a thickness of the plate 460. Thus, holes 461 which communicate the respective grooves are formed in the intersecting portions of the grooves 46 and 47. The plate 460 formed with the grooves is joined like a metal every chamber 45 to a wall 462 of the heat pipes in a region from the evaporating portion to the condensing portion. For instance, water is sealed as an operating liquid into each of the chambers 45 of the heat pipes. In the evaporating portions of the heat pipes which are thermally connected to the second cooling member, the operating liquid absorbs the heat from the second cooling member and is evaporated. The vapors are condensed and liquefied by the condensing portions and, at this time, the heat is transported to the evaporator 31. The liquefied operating liquid is again returned to the evaporating portion by the grooves 46. In the above case, the liquid also moves in the direction which perpendicularly crosses the grooves 46 through the grooves 47 which are communicated by the holes 461 and efficiently spreads into the whole region of the evaporating portion.Fig. 4 shows another example in which the first cooling member is formed by a plurality of heat pipes 4. A plurality of thin-pipe shaped heat pipes 48 are bound and are inserted into a flat block made of copper or the like in the evaporating portion and the condensing portion, thereby constructing the cooling member.The operation of the computer constructed as mentioned above will now be described.After the elapse of a predetermined time after the activation of the computer, or when a set time to activate the computer is set, the refrigerator is made operative before a predetermined time of such a set time. The refrigerant which has been set into a high pressure by the compressor 33 is cooled by the condensers 32 arranged on both sides of the casing 5. The cooled refrigerant is converged by the expansion valve 34 and becomes a liquid refrigerant of a low temperature and a low pressure. The liquid refrigerant receives the heats in the evaporators 31 and 43 and is evaporated. After that, it is returned to the compressor 33. In the case where the first cooling member 4 which is thermally in contact with the evaporator 31 is made of a material of a high heat conductivity such as copper, aluminum, or the like as shown in Figs. 1 and 2, the amount of heat which is generated by the semicodnuctor devices 1 is transferred to the first cooling member 4 through the second cooling member 41. The heat of the first cooling member 4 is transported to the evaporator 31 by the heat conduction and is exchanged by the evaporator 31 of a low temperature, so that the semiconductor devices 1 are cooled.Consequently, the first cooling member 4 is held at a low temperature because it is connected to the evaporator 31 by the heat pipe(s) or the block made of copper, aluminum, or the like having a high heat conductivity. Therefore, the semiconductor device is sufficiently cooled even in the case of any one of the device such that a heat generation amount is large to enable the computer to perform the high speed operation and it is necessary to obtain a high heat radiation amount by setting the temperature of the cooling source into a low temperature and the device such that the high speed operation can be performed by keeping a low temperature. The reason why the frist cooling member 4 is to come into contact with the semiconductor devices 1 through the second cooling member 41 having a high heat conductivity and made of a flexible material is to absorb a variation in heights of the device parts by the second cooling member 41 and to keep a small contact heat resistance. The other devices are cooled by the low temperature air by keeping the air temperature to a low temperature by allowing the air to pass in the fin portion provided for the evaporator 43 by the fan 42 or the like. The heat transferred from the semiconductor devices to the evaporating portion is finally radiated into the external air through the condensers 32 forming a part of or all of the casing 5 by the natural convection or the forced convection air cooling by the fan or the like. The dehumidifier 6 is assembled in the casing 5 and the external air is shut out by a rubber packing or the like, thereby preventing that the semiconductor devices 1 are wet with dew. In the embodiment, a water absorption resin is attached to the evaporating portion whose temperature decreases, the moisture contained in the air in the casing 5 is held in the water absorption resin. For instance, by properly exchanging the water absorption resin at the time of maintenance or the like, the moisture in the air can be eliminated.In the case where the heat pipe shown in Fig. 3 is used as a first cooling member, the condensed operating liquid flows along the grooves 46 and 47 and is returned to the evaporating portion. Also, by providing the grooves 46 and 47 which cross perpendicularly each other, the heat transfer area increases and the heat transfer performance in the evaporating portion can be increased. Even in the case where since the inside of the flat cooling member 4 is separated into a plurality of chambers 45, the airtightness of a certain chamber cannot be held and the heat transporting operation cannot be performed in such a chamber 45, the cooling functions are held in the other chambers 45, so that the operation as a heat pipe can be assured and the devices can be cooled at a high reliability.In the case of the first cooling member shown in Fig. 4, since the condensing portion is formed by a block, it can be closely adhered and attached by the evaporator 31 and the heat can be efficiently transferred to the evaporator 31 via the condensing portion. Even if the airthightness cannot be held at one portion, another heat pipe group operates, so that the heat can be transported and the high operation reliability is obtained.As mentioned above, according to the embodiment, the operating speed can be raised by setting the operating temperature of a special device such as a CMOS device to a low temperature. For instance, when such an operating temperature is held to 0°C or less, -50°C or less, or -100°C or less, it is also possible to obtain the operating speeds which are 1.5 times, 2 times, and 2.4 times as high as the operating speed at a room temperature or higher, respectively.Thus, the operating speed of the entire computer can be remarkably improved.Fig. 5 shows another embodiment of the invention. According to the embodiment shown in Fig. 5, the evaporator 31 which is held at a low temperature and constructs the refrigerator is arranged near the board 2 on which the device 1 in which a high operating speed is required is mounted, and the semiconductor device 1 is thermally to come into contact with the evaporator 31 by the cooling member 41 without using the second cooling member. The cooling member 41 is formed by a flexible material having a high heat conductivity in order to absorb a variation in heights of the semiconductor device parts. In the embodiment, since the evaporator 31 is directly arranged near the device 1 to be cooled, the heat path from the device 1 to the cooling source is reduced, so that a high cooling performance is derived. Thus, the device 1 can be maintained at a lower temperature. Therefore, the operating speed of the device which restricts the operating speed of the whole computer is raised and the speed of the computer can be improved. The cooling member 41 can be also formed by a grease of a high heat conductivity or the like. In such a case, the high cooling performance can be obtained by a smaller heat resistance. By interposing the electronic refrigerating device between the evaporator 31 and the semcionductor device 1 and by keeping the device at a further low temperature, the high speed can be also realized.Further other embodiments of the invention are shown in Figs. 6 to 10. In the embodiments, as shown in Fig. 6, a cooling member 9 is constructed along the board 2 on which the semiconductor devices 1 are mounted. Ducts are formed between the cooling member 9 and the semiconductor devices 1, thereby forming channels 50. Holes 51 are formed at the positions corresponding to the semiconductor devices 1.The cooling member 9 can be formed by any one of the heat pipe or block of a large heat conductivity, which is connected to the evaporator of the refrigerator provided in the casing, or the evaporator itself, and it is held at a low temperature. The air to cool introduced into channels 50 by fan 56 or like flows in parallel in the channels 50 along the cooling member 9. While the air flows in the channels 50, it is cooled by the cooling member 9 held at a low temperature. The cooled air is blown out of the holes 51 formed in the channels 50 and collides as jet air streams with the semiconductor devices 1. Generally, since the heat transfer performance at the surface of the semiconductor device in the case of using the jet air stream is very high, the semiconductor device can be effectively cooled. In such a jet stream method, since almost all of the cooling air which has passed the hole 51 directly collides with the semiconductor device 1, as compared with the case where the air flows in parallel with the board 2, the cooling air can be effectively used.An area of the hole 51 is determined in correspondence to each of the heat generation amount of the semiconductor device 1 and each of the special devices in which a low temperature is required, respectively. By setting as mentioned above, since the semiconductor device 1 can be sufficiently cooled and the operating speed can be raised, the operating speed of the computer can be improved.As shown in Fig. 7, a heat sink 52 can be also provided on the surface of the semiconductor device 1. Since the heat radiating area can be increased by providing the heat sink 52, the semiconductor device 1 can be more preferably cooled. Thus, the temperature of the whole semiconductor device 1 can be reduced or, in the case of the same semiconductor device temperature, a heat generation amount of the device can be increased. A speed when the cooling air is blown out of the hole can be reduced, there is an advantage such that the noises are small or the like. A shape of the heat sink 52 can be set into any one of the pin-fin shape, flat-plate shape, and the flat-plate shape having slits. It is possible to use a shape such that the heat radiating area can be enlarged.As shown in Figs. 8, 9, and 10, either one of a porous structure metal 53, thin metal wires 54, and a corrugated plate 55 formed with channels can be also inserted in the channel 50. By providing the metal body having spaces or channels in which the air flows into the channel 50, the heat exchange between the cooling air flowing in the channel 50 and the cooling member 9 held at a low temperature can be preferably executed. The semiconductor device 1 can be efficiently cooled.Fig. 11 shows another embodiment of the invention. In the embodiment, the semiconductor devices are cooled by circulating the cooling liquid by a liquid pump 7. The computer is constructed by: the boards 2 on which a number of semiconductor devices 1 are mounted; the liquid pump 7; the cooling members 4 and 41 to heat transfer the cooling liquid supplied from the liquid pump 7; and a heat radiating panel 71 which is formed in a part of the casing 5 and is used to cool the cooling liquid. The semiconductor devices 1 on the board 2 are special devices in which the high speed operation can be realized by cooling. By executing the high speed operations of the special devices, the operating speed of the computer can be improved. The first cooling member 4 and the second cooling member 41 are arranged near the board 2 on which the devices 1 in which the high speed operation is needed are mounted. The semiconductor devices 1 and the first cooling member 4 are thermally connected through the second flexible cooling member 41 having a high heat conductivity. The second cooling member 41 can use a heat conductive grease or the like in order to reduce the heat path from the semiconductor device 1 to the first cooling member 4. On the other hand, the first and second cooling members can be also arranged for only the individual devices on the board 2. A group of liquid flowing channels are provided in the first cooling member 4. The cooling liquid (heat medium liquid) flowing in the liquid channel group cools the semiconductor devices 1. The heat medium liquid is driven by the liquid pump 7. The cooling liquid which has absorbed the heat performs the heat exchange with the external air of the casing by the heat radiating panel 71 which forms a part of the casing 5. According to the embodiment, the generated heat is radiated and the device can be held at a low temperature. Therefore, the operating speed of the device which restricts the operating speed of the computer can be raised, so that the high speed operation of the computer can be realized.Fig. 12 shows further another embodiment of the invention. Although the embodiment can be also applied to the embodiment shown in Fig. 1 or 5, it is characterized by a cycle construction in which the system operates at two or more evaporation temperatures. In the embodiment, the refrigerating cycle is constructed by two evaporators 31 and 61, two expansion valves 63 and 64, the compressor 33, and the condensers 32. The evaporator 31 has a construction similar to that of the embodiment shown in Fig. 1 or 5 and cools the semiconductor devices through the cooling member. On the other hand, the evaporator 61 is operated at an evaporating temperature lower than that of the evaporator 31 and has the dehumidifier 6. The dehumidifier 6 is provided at a ventilation port of the casing. The dehumidified air is fed into the casing. It is consequently possible to prevent that the semiconductor device which has been cooled to the low temperature is wet with dew. The dehumidifier 6 may be also constructed by, for instance, a high water absorption resin or the like. It is also possible to construct in the following manner. That is, the inside of the casing is airtighted by using a rubber packing or the like, the expansion valve 63 which has the dehumidifier 6 and forms the refrigerating cycle on the low temperature side is made operative only in the initial operation after the external air entered the casing as in the case of the maintenance or the like, the air in the casing is dehumidified, and thereafter, the expansion valve 64 on the high temperature side is made operative, thereby cooling the semiconductor devices. Upon operation of the computer system, a humidity in the casing is detected, an opening degree of the expansion valve 63 on the low temperature side is changed as necessary, and it is possible to prevent that the semiconductor device is wet with dew.Further other embodiments of the invention will now be described with reference to Figs. 13A to 13C and 14.A computer system of the embodiment is constructed by: the boards 2 on which a temperature detecting circuit and a clock generating circuit comprising a frequency variable oscillator are mounted and which are enclosed in the casing 5; the first cooling member 4 which is constructed by the heat pipe to cool special devices, the block having a high heat conductivity, or the like; the second cooling member 41 which is formed by a flexible member having a high heat conductivity, a structure for allowing the air to collide with the semiconductor devices, or the like; and a refrigerator 90. As shown in Figs. 13A and 13B, the refrigerator 90 is provided as a separate unit and can be detached from the casing 5 of the computer main body. That is, in the connecting portion of the computer main body and the refrigerant unit, the first cooling member 4 of the computer main body and the evaporator 31 of the refrigerating unit are thermally physically connected by a small contact heat resistance by using an attachment structure 91. The semiconductor devices 1 are cooled through the first and second cooling members 4 and 41. When a high operating speed is not needed as a capability of the computer, the refrigerating unit is detached and the computer is operated in a state of only the computer main body or in a state in which radiating fins 92 shown in Fig. 13C are attached. At this time, the heat generated from the semiconductor devices 1 are radiated into the external air by the wall surface of the first cooling member 4 or the radiating fins 92 through the first and second cooling members 4 and 41. On the other hand, when a high operating speed is needed, by attaching the refrigerating unit, the semiconductor devices are set into a low temperature and the high speed operation can be performed.Fig. 14 shows the details of a reference clock generating section of the system operation in a computer in which a number of semiconductor devices, cooling members, and a refrigerator are enclosed in the casing and the operating speed of the whole system is raised by reducing temperatures of special semiconductor devices. The clock generating section is constructed by a frequency variable oscillator 8 whose frequency can be varied within a range from one time to two or three times in accordance with a signal from the outside and a temperature detecting circuit 80. The temperature detecting circuit 80 detects the temperature of the semiconductor device to be cooled or the temperature of the cooling members or the evaporator of the refrigerator and supplies signals corresponding to the temperatures to the frequency variable oscillator 8 and changes the clock frequency as a reference of the system operation. The frequency can be varied by means for switching clock signals generated from a plurality of quartz oscillators having different oscillating frequencies or means for frequency dividing one frequency into a plurality of frequencies or the like. Or, it is also possible to use a ring oscillator which is constructed by a CMOS device in which a delay time of a gate linearly changes in accordance with the temperature or the like. Upon activation of the computer, since the temperature of the evaporator of the refrigerator as a cooling source does not instantaneously decrease to a predetermined level, a predetermined operating speed is not obtained in the case of the semiconductor device which is thermally in contact with the cooling source. Therefore, the temperature at this time is detected and the clock frequency is reduced. As the temperature of the evaporator decreases and the temperature of the semiconductor device decreases to a predetermined temperature, the clock frequency is raised, so that a malfunction of the system can be avoided. By constructing as mentioned above, according to the computer of the embodiment, in the clock generating section, the temperature of the semiconductor device 1 or the cooling member 4 is detected and the clock frequency is set in accordance with the temperature. Therefore, in any cases, the computer can be operated without a malfunction at the speed corresponding to the cooling capability, namely, the temperature level of the semiconductor device without changing the device construction and circuit construction of the computer.By directly leading the operating refrigerant of the refrigerator to the semiconductor device cooling member and by evaporating the refrigerant by the surface of the cooling member or the inside thereof as necessary, the semiconductor device cooling member is cooled, and the semicoductor device can be also cooled by using the semiconductor device cooling member as a cooling source.On the other hand, in a computer which is constructed by wiring members such as a superconductive material or the like whose wiring resistance remarkably decreases by keeping the temperature to a low temperature, the substrate or both of the substrate and the special semiconductor devices may be also cooled to a critical temperature or lower.As mentioned above, according to the invention, first, the temperature of the special devices which restrict the operation of the whole system can be reduced by the cooling source which is generated by the refrigerator provided in the casing or a high radiation amount is derived and the operating speed of the special device can be raised, so that the operating speed of the electronic computer can be improved.Such special devices can be cooled at a temperature lower than room temperatures and with a highly improved cooling performance by thermally coupling the devices with a cold heat source via heat pipes or the like.On the other hand, since the liquid can be circulated in the casing, the high cooling performance can be realized by the cooling system of a small size and low noises.Second, since the cooling member for thermally connecting the special semiconductor device and the evaporating portion of the refrigerator is constructed by a plurality of heat pipes and the airtightness of each heat pipe is independently held, the special semiconductor device can be cooled. There is an effect such that even when the airtightness of the heat pipe of a certain portion cannot be held, the heat can be transported by the remaining heat pipes and the device can be cooled at a high reliability.Third, even when the temperature of the device is maintained at a low temperature, the portion of a temperature lower than the temperatures of the semiconductor devices can be realized and the air in the casing can be dehumidified, so that it is avoided that the semiconductor device is wet with dew.Fourth, since the clock frequency of the electronic computer can be varied in accordance with the temperature of the device, the computer can also normally operate upon activation of the computer.	A computer with a cooling system, comprising: means (2) for attaching circuit devices including a plurality of semiconductor devices (1) constructing the computer,a housing (5) for enclosing said attaching means (2), cooling means (7, 15, 31, 32, 33, 34, 43, 61) including a low temperature source (31) to cool said circuit devices, anda cooling member (4, 41) for thermally connecting said low temperature source (31) with predetermined semiconductor devices, characterized by said cooling member having at least one portion (41) made of a flexible material.A computer with a cooling system according to claim 1, wherein said cooling member comprises a connecting portion (4) arranged between the flexible portion (41) and said low temperature source (31).A computer with a cooling system according to claim 1 or 2, wherein said cooling means and said cooling members are enclosed in the housing (5).A computer with a cooling system according to claim 3, wherein said cooling means is formed by a refrigerator comprising a compressor (33), an evaporator (31, 43, 61) and condensers (32) for circulating an operating refrigerant. A computer with a cooling system according to claim 3, wherein said cooling means comprises a liquid pump (7) to circulate a cooling liquid serving as said low temperature source and a radiating panel (71) to cool the cooling liquid.A computer with a cooling system according to claim 4, wherein said evaporator (31) comprises a first portion which is thermally connected to the connecting portion (4) of said cooling member and a second portion including means (42) for cooling air in the housing (5) for circulating the cooled air.A computer with a cooling system according to claim 1, further having means for changing a frequency of a reference clock generating section (8) of the computer on the basis of a temperature detection value of a temperature detecting circuit (80) provided near the predetermined semiconductor devices (1).A computer with a cooling system according to claim 1, having another housing for enclosing said cooling means so as to be detachably coupled to said housing (5) enclosing the cooling member (4) therein.A computer with a cooling system according to claim 1, wherein said cooling means comprises a refrigerating apparatus including an evaporator (31), and the connecting portion (4) and the evaporator (31) are constructed by an attachment structure, and the refrigerating apparatus and the computer can be detached. A computer with a cooling system according to one of the claims 1 to 9, wherein said flexible material has a high heat conductivity.A computer with a cooling system according to one of the claims 1 to 10, wherein said connecting portion (4) is constructed by heat pipes (48) and is separated into a plurality of chambers (45) each having airtightness.A computer with a cooling system according to one of the claims 1 to 10, wherein the connecting member (4) is constructed by a bundle of a plurality of heat pipes (48) and an evaporating portion and a condensing portion of said heat pipes are constructed in a block shape.A computer with a cooling system according to one of the claims 1 to 12, wherein a water absorption resin is arranged near the evaporator (31).A computer with a cooling system according to claim 4 or 6, wherein said refrigerating apparatus has a second evaporator (61) which is set to an evaporation temperature lower than that of the evaporator (31), and moisture is dehumidified by the second evaporator (61).A computer with a cooling system according to one of the claims 1 to 14, wherein the temperatures of said predetermined semiconductor devices (1) are held to at least 0 °C or lower and the operating speeds of said predetermined semiconductor devices (1) are improved to an operating speed which is 1.5 or more times as high as the operating speed at a room temperature. A computer with a cooling system according to anyone of claims 1 to 14, wherein the temperatures of said predetermined semiconductor devices (1) are held to at least -50 °C or lower and the operation speeds of said predetermined semiconductor devices (1) are improved to an operating speed which is two or more times as high as the operating speed at a room temperature.A computer with a cooling system according to anyone of claims 1 to 14, wherein the temperatures of said predetermined semiconductor devices (1) are held to at least -100 °C or lower and the operating speeds of said predetermined semiconductor devices are improved to the operating speed which is 2.4 or more times as high as the operating speed at a room temperature.A computer with a cooling system according to claim 14, wherein a humidity in the casing (5) of the computer is detected and an opening degree of an expansion valve (63) on the low temperature side of the refrigerating apparatus is changed in accordance with the detected humidity.A computer with a cooling system according to anyone of the claims 1 to 18, wherein an electronic refrigerating device (44) is interposed between said predetermined semiconductor devices (1) and said cooling member.	HITACHI LTD; HITACHI, LTD.	HATADA TOSHIO; INOUYE HIROSHI; KUWAHARA HEIKICHI; MATSUSHIMA HITOSHI; NAKAJIMA TADAKATSU; OHASHI SHIGEO; OHBA TAKAO; SATO MOTOHIRO; YAMAGIWA AKIRA; HATADA, TOSHIO; INOUYE, HIROSHI; KUWAHARA, HEIKICHI; MATSUSHIMA, HITOSHI; NAKAJIMA, TADAKATSU; OHASHI, SHIGEO; OHBA, TAKAO; SATO, MOTOHIRO; YAMAGIWA, AKIRA
EP-0489328-B1	489,328	EP	B1	EN	19,950,621	1,992	20,100,220	new	C23C4	F02F3, B05B13	C23C4, B05B13, B05D1, F02F3, F02B3	L05D1:10, C23C 4/12, B05B 13/02B1, R02B3:06, B05D 1/00C2, F02F 3/12, L05D1:02	Method for spraying a coating on a disk	In a method to spray a coating of uniform thickness onto a spinning disk, a point is located spacially on the spinning disk at a distance from the center equal to about half of a spray stripe width plus half of the disk radius. The spray stream is moved in a ring-shaped pattern centered at the point and having a perimeter defined at the stripe mid-line. The perimeter diameter is equal to the disk radius. The spray stream is moved around the pattern with successive speeds, namely a base speed for a semicircular outer zone at the periphery of the disk and a smaller inner zone at the center, and lesser speeds for intermediate zones. For a concentrically contoured disk, between the above cycles the spray stream is affixed perpendicularly to a slanted surface of the spinning disk for a time period sufficient to compensate for a thickness deficiency.	This invention relates to a method of spraying a coating of uniform thickness onto a circular area of a substrate. BACKGROUND OF THE INVENTIONSpraying of a coating of uniform thickness onto a disk or other circular area of a substrate presents unusual difficulties, particularly if the area has concentrically contoured elevations instead of being flat. Spraying of a flat surface is relatively easy and common, being effected by linear passes of overlapping spray stripes. Spray coating of the outer surface of a shaft is similarly done by slowly moving the spray stream lengthwise along a spinning shaft. However, spraying onto a spinning disk ordinarily results in nonuniformity. If the spray stream is simply passed at constant speed over the spinning disk through the center, the coating will be much thicker at the center because the surface speed of the disk is slower there, being zero speed at the very center. The nonuniformity may be reduced by accelerating the movement of the stream from the edge toward the center, and decelerating from the center out. Very high speed, theoretically approaching infinite, is necessary but not very practical. The passes may be made slightly off-center, but the problem still is not solved, partly because spray gun manipulators such as robots are designed to operate in steps and are not generally capable of smooth accelerations and decelerations. Therefore, there is a need for a better method of making passes of a spray stream over a spinning disk. The need for spraying such surfaces particularly relates to the top domes of pistons for internal combustion engines. Advanced diesel engines are incorporating pistons with ceramic coatings for running hotter and enhanced performance. These coatings are being produced with the thermal spray process. Thermal spraying, also known as flame spraying, involves the heat softening of a heat fusible material such as metal or ceramic, and propelling the softened material in particulate form against a surface which is to be coated. The heated particles strike the surface where they are quenched and bonded thereto. A conventional thermal spray gun is used for the purpose of both heating and propelling the particles. In one type of thermal spray gun, the heat fusible material is supplied to the gun in powder form. Such powders are typically comprised of small particles, e.g., between 1⊘⊘ mesh U. S. Standard screen size (149 µm) and about 2 µm. The material alternatively may be fed into a heating zone in the form of a wire. A thermal spray gun normally utilizes a combustion flame, an arc plasma stream or an electrical arc to produce the heat for melting of the powder particles. SUMMARY OF THE INVENTIONThe object of the invention is to provide an improved method for spraying a coating of uniform thickness onto a selected circular area of a substrate such as an end of a cylindrical member. This object is achieved by the features as set forth in claim 1. The selected area is defined by a first center point and an area radius. A spray stream is generated with a spray coating device such that a spray pattern stripe is effected at the substrate upon relative lateral motion between the spray stream and the substrate, the stripe having a midline and an effective stripe width. The substrate is set spinning about an axis through the first center point normal to the selected area. The spray pattern is ring-shaped with a perimeter defined by the stripe midline. The pattern is spacially fixed with respect to the spinning substrate so that the center point is outside the spray pattern with the perimeter being spaced laterally from the center point by about one stripe width and the spray pattern having an outer portion located outside of the selected area. The spray device is manipulated so as to move the spray stream around a ring-shaped spray pattern on the spinning substrate. In a preferred embodiment the spray pattern is centered on a central radial line delineated so as to extend from the first center point along the spinning substrate to a spacially fixed point outside the selected area. The perimeter diameter and the radial location of the second center point are selected cooperatively so that the perimeter is spaced from the first center point by about half of the stripe width and the perimeter has a portion thereof outside of the selected area. The central line thereby has an inner line segment from the second center point to the first center point and an outer line segment from the second center point to the outside point. Further according to the preferred embodiment, the spray pattern is divided into arcuate zones consisting of a generally semicircular outer zone nominally centered on the outer line segment, an inner zone substantially smaller than the outer zone and encompassing the inner line segment, and two intermediate zones respectively separating the inner and outer zones at each side thereof. The spray device is manipulated so as to move the spray stream around the ring-shaped spray pattern with successive speeds for the zones relative to a selected base speed. The speeds for the outer and inner zones are substantially equal to the base speed, and the speeds for the intermediate zones are substantially less than the base speed. A further aspect of the invention is directed to the selected circular area of the substrate having concentrically contoured elevations therein providing a slanted surface component so as to cause a coating thickness deficiency with the preceding step of manipulating the spray device. Between the forgoing cycles of moving the spray stream around the spray pattern, the spray device is further manipulated in auxiliary steps comprising orienting the spray device to a slanted orientation, moving the spray device so that the spray stream is directed substantially perpendicular to the slanted surface component of the spinning substrate, and holding the spray device in the slanted orientation for a time period sufficient to compensate for the thickness deficiency. These steps are advantageously alternated with the cycles of moving the spray stream around the spray pattern, until a selected coating thickness is attained. BRIEF DESCRIPTION OF THE DRAWINGSFIG. 1 is a schematic drawing of an apparatus for carrying out the invention. Fig. 2 is a cross section of a spray pattern stripe effected with the apparatus of FIG. 1. FIG. 3 is a drawing of geometric patterns associated with the invention. FIG. 4 is a schematic drawing showing paths for a spray stream in carrying out the invention. FIG. 5 is a cross section of a portion of a substrate with contours, showing a spray device producing a coating thereon according to a further aspect of the invention. DETAILED DESCRIPTION OF THE INVENTION With reference to FIG. 1, a spray coating device 12 is mounted on arms 14 of a manipulator 16. The device may be any conventional spray coating gun suitable for producing the desired coating with a spray stream of definable width, for example a plasma or combustion type of thermal spray gun or a paint spray gun; the present example is directed to a thermal spray gun. The gun produces a spray stream 18 which is aimed substantially normally to a selected circular area 2⊘ of a substrate 22 to be coated such as an end of a cylindrical member. A particular useful application is the dome of a piston for an internal combustion engine where a very uniform coating of a ceramic such as zirconia is to be applied. A pattern stripe 24 is effected on the spinning substrate. The stripe will have a typical cross section as shown in FIG. 2. An effective width W of the stripe is not exact but is generaily considered to be that width which delineates the portion of coating stripe having at least half of the maximum stripe thickness T. This is subject to adjustment as indicated herein, and overspray 25 outside this region is to be utilized. A powder feeder 26 is provided for supplying ceramic powder to the gun, as well as gas supply lines 28 and gas sources 3⊘ as required for operation of the gun. The substrate is prepared conventionally such as with grit blasting and/or a metallic bond coat, and may be preheated prior to powder feed. The piston 22 (or other substrate) is mounted on a shaft 32 driven by a motor 34 for spinning the end-surface 2⊘ under the spray stream 18, about an axis 36 normal to the substrate surface area to be coated. The manipulator 16 such as a Metco Type AR1⊘⊘⊘ robot sold by the Perkin-Elmer Corporation is computerized and programmed to move the gun so that the spray pattern is moved with varying positions and velocities over the coating surface according to the invention in a manner described below. Programming of a conventional robot is readily done with a pendent 38 or computer keyboard as supplied or recommended by the manufacturer of the robot. FIG. 3 shows geometric patterns 4⊘ associated with the invention. The selected circular area 2⊘ or disk-shaped substrate for coating is in the plane of the drawing. The selected area is defined by a first center point 44 and an area radius R. This radius is about 6 cm in the present example. The spray device (not shown in FIG. 3) is above this plane by the desired spray distance, e.g. by about 1⊘ cm. Relative lateral motion between the spray stream and the substrate produces a spray pattern on the substrate which, for a stationary gun over the spinning area, is a circular stripe such as stripe 24 with a mid-line 48 and an effective width W. In the present example the area to be coated has a radius R of about 6 1/2 (six and one half) such pattern widths, delineated in the drawing with five concentric circles 5⊘. The innermost circle should have a radius W' about 1 1/2 (one and one half) times the width W. A hypothetical central radial line 52 is delineated fixed in space as extending from the first center point 44 along the spinning substrate 22 to a spacially fixed point 54 outside the selected area 2⊘. A second center point 56 is located on the central line 52 at a distance D from the first center point 44 substantiatly equal to the width W plus half of the area radius R. The center line 52 is conveniently described as having an inner line segment 58 between the second center point 56 and the first center point 44, and an outer line segment 6⊘ between the second center point 56 and the outside point 54; the exact location of the outside point 54 is not important, and may provide a starting point for the spraying operation. The spray device 12 (FIG. 1) is firstly manipulated so that the spray stream 18 is moved in a ring-shaped spray pattern 62 (delineated with dashed-line circles in FIG. 3) centered at the second point 56. The spray pattern 62 is defined by a spray pattern stripe with its stripe width W (as if the disk were stationary) and has a perimeter 64 defined by the stripe mid-line and further has a perimeter diameter P substantially equal to the radius R of the selected area 2⊘. This geometry places a portion 63 (less than about half) of the spray pattern 62 outside of the selected area. In a broad aspect of the invention, the spray pattern 62 is divided arcuately into zones. An outer zone 66 (shown in FIG. 3 by the arc of the zone) is generally semicircular and is nominally centered on (i.e. bisected by) the outer line segment 6⊘. An inner zone 68 is substantially smaller than the outer zone and encompasses the inner line segment 58. The full circle of the pattern is completed with each of two intermediate zones 7⊘,72 respectively separating the inner and outer zones at each side. Preferably, as indicated in FIG. 3, the outer zone 66 is skewed in an arcuate direction 74 from being bisected by the outer line segment 6⊘. This skewing is shown as counter-clockwise in the figure. Similarly the inner zone 68 is skewed in an opposite direction 76 from the arcuate direction, from being bisected by the inner line segment 58. The opposite skewing is clockwise in the present example. An objective of the skewings, and a result, is a narrowing of the left intermediate zone 7⊘ and a corresponding broadening of the right intermediate zone 72. During the coating process, simultaneously with being moved around in the ring-shaped spray pattern 62, the spray device 12 is secondly manipulated so that the spray stream 18 (FIG. 1) moves around in the spray pattern with successive speeds relative to a selected base speed. Broadly, the speeds are substantially equal to a selected base speed for the outer and inner zones 66,68, and substantially less than the base speed for the intermediate zones 7⊘,72. The combination of the herein specified size and location of the ring-shaped spray pattern, and this selection of speeds, should result in a sprayed coating that has a relatively uniform thickness across the selected coating area 2⊘. Although the disk center 44 is just outside the edge of the pattern 62, fringe spray is sufficient to coat the center region without excess thickness. The exact location of the pattern center 56 may be adjusted and fine tuned as necessary to effect this result. For further precision the zones are more specifically divided into sectors that arcuately divide the spray pattern. The number of sectors will depend on the radius R of the coating area relative to the pattern width W. For a radius of about 4 to 1⊘ such widths the following sector arrangement should be quite suitable. A larger area in terms of a radius of a greater number of pattern widths should have more sectors. Considering the sectors in detail for the present example of a six-width area radius R as shown, the arrangement is as follows: A first sector T1 extends from the outer line segment 6⊘ through an angle AA marginally greater than 9⊘°. A second sector T2 extends from the first sector by an angle BB equal to about half of an angle LL between the first sector and the inner line segment 58. A sixth sector T6 extends in the opposite direction from the first sector starting at the outer line segment 6⊘ through an angle FF about equal to or marginally less than 9⊘°. A fifth sector T5 extends from the sixth sector by an angle EE about equal to or marginally greater than the angle BB. A fourth sector T4 extends from the fifth sector by an angle DD about equal to the angle EE. Lastly, a third sector T3 fills in between the second and fourth sectors through an angle CC such that about one third of the third sector is between the inner line segment 58 and the fourth sector. The term marginally as used herein and in the claims generally refers to an angle increment of up to about 2⊘% of the referenced angle. Most preferably for this arrangement, angle AA is about 1⊘⊘°, angle BB is about 35°, angle CC is about 7⊘°, angle DD is about 35°, angle EE is about 4⊘°, and angle FF is about 8⊘°. All sector angles add up to 36⊘°, the sectors being non-overlapping. It may be seen that the first and sixth sectors together form the outer zone 66. The second sector constitutes the left intermediate zone 7⊘, and the fourth and fifth sectors constitute the right intermediate zone 72. For preferable speeds, the first, third and sixth sectors each has substantially the base speed, the second sector has between about 25% and 3⊘% of base speed, the fourth sector has about twice the second sector speed, and the fifth sector has between about 3⊘% and 4⊘% of base speed. Most preferably the second sector speed is about 28% of base speed, the fourth sector speed is about 6⊘% of base speed, and the fifth sector speed is about 36% of base speed. With a significantly larger coating area having more sectors, speeds for the additional sectors will be selected between these speeds so as to provide a grading of the speeds. The sectors are advantageously described further in terms of hypothetical concentric circles nominally separated by the spray pattern widths on the selected coating area. These are illustrated in FIG. 3 as five such circles designated C1, C2, C3, C4 and C5 consecutively from the center. The circles have separations nominally equal to the stripe width W. It should be recognized that the cross section of a pattern stripe has a profile as shown in FIG. 2, so that selection of a spray pattern width is not exact. Therefore, the width as used herein is generally selected so that the circles fit evenly over the area, with the width otherwise being as closely as practical to about half of the maximum thickness of a single-pass stripe. The concentric circles include an outermost circle C5 with a radius of one stripe width less than the area radius. An adjacently outer circle C4 is adjacent to the outmost circle. An innermost circle C1 has a radius of about 1 1/2 stripe widths, and an adjacently inner circle C2 is adjacent to the innermost circle. In the present example there is one middle circle C3. In other cases for other circular spray radii R relative to a pattern width W, there may be other middle circles, or even no middle circle. The concentric circles intersect the pattern perimeter 64 to define points of intersection therewith. These points of intersection are used to define a series of radial lines extending from the second center point 56 through the intersection points. One boundary for the first sector T1 is the outer line segment 52. The other boundary is a first radial line 8⊘ through a point of intersection 9⊘ of the pattern perimeter 64 with circle C4. This also is a boundary for the second sector T2. The other boundary for the second sector is a fourth radial line 82 through a point of intersection 92 of the pattern perimeter with the circle C2, which also is a boundary for the third sector T3. The other boundary for the third sector is a third radial line 84 through a point of intersection 94 of the pattern perimeter with the circle C1 such that the third sector encompasses the inner line segment 58. The latter boundary 84 is also for the fourth sector T4, which has as its other boundary a radial line 86 through a point of intersection 96 of the pattern circle and circle C3. The latter radial line 86 is also a boundary for the fifth sector T5 which has as its other boundary a second radial line 88 through a point of intersection 98 of the pattern circle with circle C5. The latter boundary 88 also is for the sixth sector T6 which completes the pattern of sectors to the outer line segment 52. It will be appreciated that there are two points of intersection of the pattern perimeter 64 with each concentric circle. However any apparent ambiguity in defining intersection points for the radial lines is removed herein and in the claims by the more fundamental definitions for the sectors set forth. The radial lines merely fine tune these definitions. Specifically, in its direction of skewing, the outer zone is bounded by the first radial line 8⊘; and, in the opposite direction, by the second radial line 88. Similarly, in its direction of skewing, the inner zone is bounded by the third radial line 82; and in the opposite direction, by the fourth radial line 84. More generally, for other ratios of coating radius to pattern width, each of the intermediate zones is divided into at least one intermediate sector, each such sector having an arc width of nominally twice a minimum width defined between radial lines through points of intersection of the pattern perimeter with adjacent concentric circles. To determine specific speeds for these sectors, a preliminary speed is first estimated for each intermediate sector relative to the base speed. A coating is then produced on a disk with the selected area according to the steps described above, coating thickness is next measured such as with a micrometer at various locations across the selected area, and any excess or deficiency in thickness is correlated to concentric circles associated with an intermediate sector at the pattern perimeter. A new speed is then selected for the associated sector, namely a faster speed if the thickness was excessive, or a slower speed for a deficient thickness. A further coating is sprayed with the adjusted speed or speeds, so as to produce the further coating with a more uniform thickness on the selected area. Thickness measurements on the new coating may be made, leading to still further adjustments to the speeds, in a limited iterative process. Only one or two repetitions should be necessary, so that such experimenting will not be excessive. The concentric circles of the pattern widths provide a useful way to visualize the action of the spray stream through each sector of the circular pattern stripe. Skewing the sectors or zones by essentially one pattern width from symmetry about the central line provides for effectively overlapping coating depositions at the different surface speeds from the center on the spinning disk, so as to smooth out coating thickness differences at different distances from the first center point. The spinning of the substrate should be at a constant rotational rate. Also the selected base speed (i.e. the speeds for the outer and inner zones) should be much less than the surface velocity (from the spinning) of the periphery of the selected area at its area radius R, preferably at least an order of magnitude less. Fig. 4 illustrates supplementary steps of moving the spray stream into and out of the spray pattern on the selected area. These steps, also programmed into the robot, make use of the fact that the ring-shaped spray pattern 62 has the portion 63 outside of the selected area 2⊘. A reference point 1⊘2 is selected well away from the substrate (and may coincide with the outside point 54, FIG. 3). At the start of a cycle, the spray gun is lit at a starting point 1⊘4 and moved (1) to the reference point 1⊘2 where feeding of powder (or other material form) is turned on so that the spray stream is operative at the reference point. The spraying gun is then moved (2) so that the spray stream is taken to pattern 62 at a point of intersection 1⊘6 of the central radial line 52 with the pattern perimeter 64 outside of the selected area 2⊘. The manipulation of the gun to move (3) the spray stream around the pattern at the selected speeds is effected as set forth above, and the spray stream is exited from the spray pattern at said point of intersection 1⊘6 after at least one cycle of the spray stream around the spray pattern, and moved (4) back to the reference point 1⊘2. The number of continuous cycles may be whatever is necessary for buildup of a coating of desired thickness, e.g. 1 mm, or other steps may be interjected between cycles as described above. A particular case for further manipulating the spray device in auxiliary steps in the method is where the substrate 22 such as a piston dome has concentrically contoured elevations therein providing a slanted component 112 in the surface. An example is shown in FIG. 5. A nearly vertical slant 112 will cause a coating thickness deficiency in the associated area when sprayed normal to the (mean) surface. Also, a coating sprayed at only low angle to a surface may be of poor quality. To solve these problems, the method further comprises, between cycles of the spray stream abound the spray pattern, thirdly manipulating the spray device in a set of auxiliary steps presented next below. Referring back to FIG. 4, after a cycle as described above, the gun is (optionally) moved (5) from the reference point to a convenient nearby point 1⊘8. There the spray device is oriented from its normal (perpendicular) direction to a slanted orientation. The spray device is then moved (6) into a position (7) selected so that the spray stream 18 is directed so as to be substantially perpendicular to the slanted surface component of the spinning substrate, as shown in FIG. 5. The spray device 12 is held in the slanted orientation for a time period sufficient to add to the slanted coating 114 to compensate for the thickness deficiency, the time being generally less than for one normal cycle of spraying. The device again is moved (8) so that the spray stream is withdrawn out of the selected area and back to the convenient point 1⊘8. Advantageously there is continuously alternating between the auxiliary steps and cycle of the spray stream around the spray pattern until a selected thickness for a coating 114 is reached. At this stage, at or near the reference point, powder feeding is stopped and the gun is shut down or moved (9) back into an idle mode position 1⊘4. This total sequence of steps produces a particularly uniform, high quality coating 116 on a circularly contoured surface such as that of FIG. 5. As an example the dome of a 12.5 cm diameter piston having a configuration as in FIG. 5 was thermal spray coated with Metco 2⊘2 zirconium oxide powder to a thickness of about 1 mm using the geometry of FIG. 3. A Metco Type 7MB plasma spray gun with a G4 nozzle was used with a Type AR1⊘⊘⊘ robot. The zirconia was sprayed at 12.5 cm spray distance with nitrogen plasma gas using standard parameters. The piston was spinning at 65⊘ rpm and the base speed was 75 cm/sec. While the invention has been described above in detail with reference to specific embodiments, various changes and modifications which fall within scope of the appended claims will become apparent to those skilled in this art. The invention is therefore only intended to be limited by the appended claims.	A method of spraying a coating of uniform thickness onto a selected circular area (20) of a substrate (22), the selected area being defined by a first centre point (44) and an area radius (R), comprising: generating a spray stream (18), substantially normal to the selected area (20) with a spray coating device such that a spray pattern stripe is effected at the substrate (22) upon relative lateral motion between the spray stream (18) and the substrate, the stripe having a mid-line (48) and an effective stripe width (W); spinning the substrate (22) about an axis (36) through the first center point (44) normal to the substrate (22); delineating a central radial line (52) extending from the first center point (44) along the spinning substrate (22) to a spacially fixed point (54) outside the selected area (20); establishing a ring-shaped spray pattern (62) with the spray stream (18) over the spinning substrate (22), the spray pattern (62) being centered at a second center point (56) located on the center line (52) in the selected area (20), the spray pattern (62) having a perimeter defined by the stripe mid-line (64), the perimeter having a perimeter diameter (P) selected cooperatively with the location of the second center point (56) so that the center point (56) is located outside the spray pattern with the perimeter being spaced laterally from the first center point (44) by about one stripe width (W) and the spray pattern having a portion thereof located outside of the selected area (20), the central line (52) thereby having an inner line segment (58) extending between the second center point (56) and the first center point (44) and an outer line segment (60) extending between the second center point (56) and the outside point (54), dividing the spray pattern into arcuate zones consisting of a generally semicircular outer zone (66) nominally centered on the outer line segment (60), an inner zone (68) substantially smaller than the outer zone (66) and encompassing the inner line segment (58), and two intermediate zones (70, 72) respectively separating the inner and outer zones at each side thereof; and manipulating the spray device so as to move the spray stream (18) around the ring-shaped spray pattern (62) on the spinning substrate (22) with successive speeds for the zones relative to a selected base speed, the speeds for the outer (66) and inner zones (68) being substantially equal to the base speed, and the speeds for the intermediate zones (70, 72) being substantially less than the base speed. The method according to claim 1 wherein the outer zone is skewed in an arcuate direction from being bisected by the outer line segment (60), and the inner zone is skewed oppositely from the arcuate direction from being bisected by the inner line segment (58). The method according to claim 2 wherein the second center point (56) is located on the central line (52) at a distance from the first center point (44) substantially equal to the stripe width (W) plus half of the area radius (R), and the perimeter diameter (P) is substantially equal to the area radius (R). The method according to claim 3 wherein the step of dividing comprises: forming concentric circles (C1-C5) within and concentric to the selected area (20) and having separations nominally equal to the stripe width (W), the concentric circles including an outermost circle (C5) with a radius of one stripe width (W) less than the area radius (R), an adjacently outer circle (C4) adjacent to the outmost circle (C5), an innermost circle (C1) with a radius of about 1 1/2 stripe widths (W), and an adjacently inner circle (C2) adjacent to the innermost circle (C1), the concentric circles (C1-C5) intersecting the pattern perimeter (64) to define points of intersection (90, 92, 94, 96, 98) therewith; forming first and second radial lines extending from the second center point (56), the first radial line (80) being defined to extend through a point of intersection (90) for the adjacently outer circle (C4), and the second radial line (88) being defined to extend through a point of intersection (88) for the outermost circle (C5), the first and second radial lines providing respective boundaries for the outer zone; and forming third and fourth radial lines extending from the second center point (50), the third radial line (84) being defined to extend through a point of intersection (94) for the innermost circle (C1), and the fourth radial line (82) being defined to extend through a point of intersection (92) for the adjacently inner circle (C2), the third and fourth radial lines providing respective boundaries for the inner zone. The method according to claim 4 wherein the step of dividing further comprises dividing each of the intermediate zones (70, 72) into at least one intermediate sector (T2, T4, T5), each such sector having an angular width of nominally twice a minimum angular width defined between radial lines extending through adjacent points of intersection of the pattern perimeter (64) with adjacent concentric circles (C1-C5), and the method further comprises, in sequence, estimating a preliminary speed for each intermediate sector (T2, T4, T5) relative to the base speed, producing a coating on the selected area (20) with each preliminary speed according to the step of manipulating, measuring coating thickness across the selected area, correlating any excess or deficiency in thickness to concentric circles associated with an intermediate sector at the pattern perimeter (64), selecting for the associated sector a faster speed for an excess thickness or a slower speed for a deficient thickness, and producing a further coating with the faster or slower speed according to the step of manipulating, so as to produce the further coating with a more uniform thickness on the selected area (20). The method according to claim 1 wherein the step of dividing comprises dividing the spray pattern into non-overlapping sectors, a first sector (T1) extending from the outer line segment (60) through an angle A marginally greater than 90°, a sixth sector (T6) extending from the outer line segment (60) oppositely from the first sector through an angle F marginally less than 90°, a second sector (T2) extending from the first sector (T1) by an angle B marginally less than half of an angle between the first sector (T1) and the inner line segment (58), a fifth sector (T5) extending from the sixth sector (T6) by an angle E about equal to or marginally greater than the angle B, a fourth sector (T4) extending from the fifth sector (T5) by an angle D about equal to the angle B, and a third sector (T3) extending between the second and fourth sectors by an angle C such that about one third of the third sector is between the inner line segment and the fourth sector, whereby the outer zone (66) consists of the first and sixth sectors, the inner zone (68) consists of the third sector, and the intermediate zones (70, 72) consist of the second, fourth and fifth sectors; and wherein the speed for each of the first, third and sixth sectors is substantially equal to the base speed, the speed for the second sector is between about 25% and 30% of the base speed, the speed for the fourth sector is about twice the second sector speed, and the speed for the fifth sector is between about 30% and 40% of the base speed. The method according to claim 6 wherein angle A is about 100°, angle B is about 35°, angle C is about 70°, angle D is about 35°, angle E is about 40°, and angle F is about 80°. The method according to claim 7 wherein the speed for the second sector is about 28% of base speed, the speed for the fourth sector is about 60% of base speed, and the speed for the fifth sector is about 36% of base speed. The method according to claim 1 wherein the spinning of the substrate (22) is at a constant rotational rate. The method according to claim 1 wherein the spinning of the substrate (22) effects a surface speed of the selected area (20) at the area radius (R), and the base speed is at least an order of magnitude less than the surface speed. The method according to claim 1 further comprising supplementary steps of first entering the spray stream (18) into the ring-shaped spray pattern (62) at a point of intersection (106) of the central radial line (52) with the pattern perimeter (64) outside of the selected area (20) and subsequently exiting the spray stream out of the spray pattern (62) at said point of intersection (106) after at least one cycle of the spray stream around the spray pattern. The method according to claim 1 wherein the selected area (20) of the substrate has concentrically contoured elevations therein providing a slanted surface component (112) so as to cause a localized coating thickness deficiency upon effecting the step of manipulating, and the method further comprises, separately from the step of manipulating, further manipulating the spray device (12) in auxiliary steps comprising orienting the spray device to a slanted orientation, moving the spray device so that the spray stream is directed substantially perpendicular to the slanted surface component (112) of the spinning substrate (22), and holding the spray device in the slanted orientation for a time period sufficient to compensate for the thickness deficiency. The method according to claim 12 further comprising continuously alternating between the auxiliary steps and the cycles of moving the spray stream (18) around the spray pattern until a selected coating thickness is attained. The method according to claim 1 wherein the spray device (12) is a thermal spray gun. The method according to claim 1 wherein the substrate (22) is a cylindrical member with an end constituting the substrate and having the selected circular area (20). The method according to claim 15 wherein the cylindrical member is an internal combustion engine piston with a dome constituting the selected area, the spray device (12) is a thermal spray gun, and the spray stream (18) comprises a ceramic spray material.	PERKIN ELMER CORP; THE PERKIN-ELMER CORPORATION	LAMBERT RICHARD W; LAMBERT, RICHARD W.
EP-0489334-B1	489,334	EP	B1	EN	19,960,207	1,992	20,100,220	new	G21C3	null	G21C3	G21C 3/356F, S21C3:356F, S21Y2:302, S21Y4:30, G21C 3/344, S21C3:344	Self locating springs for ferrule spacer	The spacer consists of a matrix of ferrules (20) defining the spacing pitch of the fuel rods. The ferrules (20) comprise stops against which the fuel rods are biased by springs (44). The springs are loop springs (44) positioned between two ferrules in corresponding cut-outs (60). Tabs are integrally formed on the springs so as to project into the interstitial space (82) between the ferrules (20). The cooperation of tabs (204) and ferrule walls the loop springs are captured and centered.	BACKGROUND OF THE INVENTIONThis invention relates to spacers for use in nuclear fuel bundles for maintaining individual fuel rods or tubes containing fissionable materials in their designed spaced apart relation. More particularly, a spacer is disclosed which has both an improved spring for biasing fuel rods to their correct designed location as well as an improved self-centering spring mounting to the spacer. Summary of the Prior ArtModern boiling water nuclear reactors typically include a core composed of many discrete fuel bundles. Water circulates from the bottom of the each fuel bundle of the core, is heated in passing upward through each fuel bundle, and passes out the top of each fuel bundle in the form of heated water and steam. The fuel bundles are composed of discrete groups of fuel rods - sealed tubes which contain nuclear fuel. Typically, the fuel rods are supported upon a lower tie plate and held in side-by-side vertical relation by an upper tie plate. Water flow is confined within a fuel bundle channel extending from the lower tie plate to the upper tie plate. In addition to supporting the fuel rods, the lower tie plate admits water into the interior of the fuel bundle. The upper tie plate - in addition to maintaining the fuel rods upright-permits the heated water and generated steam to exit the fuel bundle. The fuel bundles are elongate - typically being in the rang of 4,064m (160 inches) in length. Consequently, the individual fuel rods within the fuel bundles are flexible along the length of the fuel bundle. If unsupported, the individual fuel rods could easily wander out of their intended side-by-side spacing. Preservation of the intended side-by-side spacing of fuel rods within a fuel bundle is important. Specifically, if the fuel rods are not maintained within their desired side-by-side spacing, the required designed nuclear reaction and concurrent heat generation with steam production does not efficiently occur. Further, vibration of the fuel rods is undesirable; fuel rods become heated pressure vessels during nuclear reaction. Maintaining these heated pressure vessels sealed is vital to reactor operation. To maintain the required spacing between the individual fuel rods and to prevent unwanted vibration, it has long been the practice of the nuclear industry to incorporate spacers along the length of the fuel bundles. Typically, anywhere from five to ten spacers - usually seven - are placed within the each fuel bundle. The spacers are preferably placed at varying elevations along the length of the fuel bundle to brace the contained fuel rods in their designed location. Spacer construction is easily understood. Each spacer has the task of maintaining the precise designed spacing of the particular matrix of fuel rods present at its particular elevation within a fuel bundle. Consequently, it has been a common practice to provide each spacer with a matrix of ferrules for surrounding each fuel rod of the corresponding matrix of fuel rods. Each ferrule is provided with at least one stop. The fuel rods when biased into the stop(s) of their ferrules have their precise designed side-by-side spacing preserved. The necessary biasing of the fuel rods within the spacers has been accomplished by individual springs. In the prior art it has been a common practice to have two side-by-side ferrules share the same spring at a common aperture defined between the ferrules. Typically the shared spring is of the loop configuration having two spring legs joined together at the top and at the bottom to form a continuous and elongated loop spring. One spring leg protrudes through the common aperture into a first ferrule of a ferrule pair and biases the fuel rod in the ferrule against the stops of the first ferrule of the ferrule pair. The other spring leg protrudes through the common aperture into the other ferrule of the ferrule pair and biases the other fuel rod in the second ferrule against the stops of the second ferrule of the ferrule pair. Maintaining the loop springs of the prior art within the side-by-side ferrule pairs has been difficult. The common aperture between adjacent ferrules has been defined by configuring an aperture in each ferrule and confronting the ferrules at these defined apertures. The confronted apertures define the common aperture. These confronted apertures have been configured with irregular shapes having protruding internal surfaces - for example apertures of the E variety have been used. By the expedient of either overlapping or confronting protruding portions of the confronted apertures between the loops of the prior art springs, capturing of the springs into the common aperture between the spacers has resulted. With the loop springs confined into the common aperture between the metal walls of a ferrule pair, it has been possible to effect the required spring biasing in two ferrules with a single confined loop spring. Unfortunately, modern fuel bundle design has complicated the design of spacer springs and spacers. Fuel bundles have become more densely packed with smaller diameter fuel rods. As a consequence, the space available for both spring movement and capturing of the spring to the spacer has become vastly reduced. As fuel bundles have become more dense, the number of springs required across a spacer has increased. Unfortunately, the required movement of the springs in either maintaining the fuel rods in alignment or permitting assembly of the fuel bundle in the first instance has remained unchanged. The practical effect of having denser fuel bundles has resulted in the need for redesign of the springs within fuel bundle spacers. Further, assembly of fuel bundles has further complicated this problem. Specifically, the biasing springs of individual spacers have a tendency to scratch fuel rods when fuel rods are inserted to the spacers. These scratches can possibly be the location for the commencement of corrosion of the fuel rods during their in service life. This being the case, it is desirable to encase fuel rods in protective plastic sheaths during their insertion into spacers. Once insertion is complete, the plastic sheaths are removed. The use of the plastic sheaths prevents scratches. Unfortunately, the use of plastic sheaths requires additional spring flexure during fuel bundle assembly. This additional flexure is necessary to permit the plastic protective coating to be temporarily inserted with the fuel rods into the fuel bundle. In some fuel bundles requiring initial insertion of the fuel rods with plastic coatings, it has not been possible to have existing spring flexure within design tolerances where two plastic covered fuel rods are placed simultaneously within the ferrules of a ferrule pair. As a consequence, construction of some fuel bundles has required a complex procedure for inserting the fuel rod. Considering a ferrule pair and spring, a first fuel rod with a plastic sheath is inserted into one ferrule of the pair, and the sheath is removed. Then a second fuel rod with a plastic sheath is inserted into the remaining ferrule and its sheath is removed. This procedure is required because the prior art springs cannot deflect far enough to accommodate both fuel rods and both plastic sheaths. When it is realized that this alternating insertion procedure must be followed over a 9 by 9, 10 by 10, 11 by 11 or 12 by 12 matrix in a carefully controlled sequence, it can be understood that a spring design which permits simultaneous insertion of rod pairs, each with a plastic sheath, is desirable. Finally, those familiar with mechanical design and mechanical design tolerances will realize that exact dimensions and perfect alignment are never as a practical measure achieved. Instead, a tolerance range is specified. The cost of manufacture increases as the tolerance range is narrowed. In the prior art spacers, and to a greater degree in new designs, a very tight tolerance range is required for the springs and ferrules. If a spring can be designed with greater flexibility, and a mounting method which allows more spring deflection, the tolerances can be less restrictive. Because of at least the above design considerations, the providing of springs in spacers having improved flexibility has become a high priority. A standard method for providing increased flexibility is to vary the width of the spring, using a lesser width in regions of low stress. Unfortunately, the width of the current loop spring is not easily varied. The loop spring starts out as a continuous circular loop of constant width and is then bent into its final shape. The circular loop, or the final spring could be machined to a varying width, but the cost would be high. According to the invention, there is provided a fuel bundle spacer for placement within a fuel bundle channel between upper and lower tie plates around fuel rods for maintaining said fuel rods in designed side-by-side spacing, said spacer comprising a matrix of ferrules coextensive with the construction of said spacer for placement within the fuel bundle channel; each said spacer matrix of ferrules including at least first and second side-by-side ferrules mounted in combination with a loop spring forming a ferrule pair for fitting around respective side-by-side fuel rods to maintain said fuel rods spaced apart one from another; each said ferrule of said ferrule pair having at least one internal stop for permitting said fuel rod internal of said ferrule to be biased against said stop to a position of designed side-by-side alignment with respect to said fuel bundle at said spacer within said ferrule; each said ferrule of said ferrule pair further defining an aperture for confrontation with a corresponding aperture of said adjacent ferrule of said ferrule pair to define a common aperture between said ferrule pair for receiving the loop spring between said ferrules CHARACTERIZED IN THAT said common aperture is regular in section without any protruding tabs, said common aperture further defining tap receiving slots at the sides of said common aperture between said ferrules for confining said spring at protruding tabs to said common aperture between said ferrule pair; each said loop spring having first and second legs, each leg including a rod contacting portion; said first spring leg biasing a fuel rod interior of said first ferrule of said ferrule pair and a second spring leg for biasing a fuel rod interior of said second ferrule of said ferrule pair; at least first and second tabs protruding from at least one of said spring legs, said first tab protruding from a first side of said spring and said second tab protruding from a second side of said spring, said tabs for maintaining said loop spring in said common aperture at said tab receiving slots; and, said first and second ferrules confronted at said apertures with a main body of said loop spring confined in said common aperture and said tabs protruding into said tab receiving slots to maintain said loop spring in said aperture whereby said respective spring legs of said loop spring can bias respective fuel rods in each said ferrule of said ferrule pair against said stops to maintain said fuel rods in designed side-by-side spacing. In an illustrative fuel bundle having a matrix of parallel side-by-side fuel rods supported within a fuel channel between a supporting lower tie place and a holding upper tie plate, the spacers maintain the fuel rods in their required precise side-by-side alignment for efficient nuclear reaction. Spacers are placed at preselected and typically regular intervals along the elevation of the elongate fuel bundle to prevent the otherwise flexible discrete fuel rods from moving out of their required precise side-by-side relation. The spacers each have a corresponding matrix of individual ferrules each surrounding the discrete fuel rods to be spaced within the matrix of fuel rods at any given elevation within the fuel bundle. Each of the individual ferrules surrounding the individual fuel rods is provided with stops against which the fuel rods are biased to ensure the required side-by-side spacing. Consequently, each ferrule must have at least one spring for forcing the fuel rods against the stops of its spacer ferrule to enable the spacer to assure required side-by-side alignment of the fuel rods. In illustrative embodiments of the present invention, the prior art practice of having two side-by-side ferrules share the same biasing spring for two adjacent fuel rods is followed. Paired ferrules are each provided with apertures for capturing a single spring between the ferrules. In accordance with an embodiment of the invention, the springs are provided with a continuously looping main body having protruding tabs on opposite sides of the springs. The paired ferrules are confronted at their respective apertures for the capture of the springs at their main body and to provide a defined space between the confronted apertures on either side of the apertures for permitting protrusion of spring tabs for holding the springs within the confronted apertures. Before the ferrules are confronted, the springs are placed so as to be trapped by and be confined within the respective confronted apertures of the ferrules. When confrontation of the ferrules has occurred, the springs at their protruding tabs extend into a small interstitial space defined by the apertures between the confronted ferrules. The springs as trapped between the apertures at their main body and confined within the apertures by the tabs become self centering to the ferrule pair and do not have the metal of the ferrules invading the interstitial space between the springs. As a result, greater relative movement between the legs of the springs is permitted enabling the design of this invention to be utilized in modern dense fuel rod arrays requiring greater relative spring movement both for assembly and operation under normal production tolerances. Three exemplary types of springs are illustrated. A first spring has a simple looping main body with two simple intermediate protruding tab pairs on either side of the main body, one tab pair at the top of the entrapping aperture and the remaining tab pair at the bottom of the entrapping aperture for holding the spring to the entrapping aperture. A second spring is disclosed in which the tab portions are located near the ends of the spring, midway between the two sides of the spring. This spring consists of two identical halves which are welded together. A third spring is disclosed in which the tab portions are included at either end of the spring and are used for entrapping the springs within their respective ferrule apertures, and are incorporated into the spring legs to produce a spring having longer spring legs with a resulting lesser range of spring force over the designed range of spring deflection. The manufacture of all three springs begins with flat strip material. A punching operation provides the variation in width required for optimum spring design and provides the locating tabs. An embodiment of this invention mounts a loop type spring between a ferrule pair of a spacer without having the material of the ferrules intrude within the loop of the spring. According to this embodiment of the invention, paired ferrules are provided with confronting apertures. These apertures when confronted provide two functions. First, they trap between the ferrules the main body of the loop type spring. Second, they provide confining slots defined between the respective ferrule pairs. To mate with these confining slots, tabs protrude from the main body of the loop springs on either side of the loop springs. The tabs extend from the trapped main body of the loop spring within the confronted apertures into the confining slots. As a result, the loop springs are held to the confronted apertures of the ferrule pair by the tabs. An advantage of the spring of this embodiment is that it is self centering with respect to the ferrule pair. Under the forces of compression exerted on the fuel rods, the spring seeks and maintains its designed position with respect to the ferrule pair. An additional advantage of the spring is that the material of the ferrules is no longer required to penetrate in between the discrete legs of the loop springs. This being the case, the spring legs are permitted a relatively greater movement - this compression permitting movement of each leg toward the remaining leg until contact of one spring leg with its opposed spring leg occurs. No longer is spring leg movement limited by the structure of portions of the ferrules invading the interstitial space between the discrete spring legs of the loop spring. A further advantage of spring and ferrule construction is that assembly of the spacers is simplified. Specifically, in the past the loop springs have had to be individually threaded to portions of the ferrules - and thereafter trapped in place by manipulation of the confronting ferrules. With the design here disclosed, simple trapping of the spring between confronted ferrules is all that is required. An additional advantage of the greater flexibility of the spring construction is that the insertion of fuel rods covered with protective plastic sheaths is possible simultaneously on both sides of confronted ferrules. It is not required to insert the plastic sheath covered fuel rods on an alternating basis to avoid over stressing of the springs. An additional embodiment of this invention utilizes the projecting tabs required for locating the spring as additional portions of the spring. According to this embodiment of the invention, a loop spring has upper and lower protruding tabs which form portions of the body of the loop spring. These respective portions of the loop spring give the main spring body a longer effective length. As a result, spring compression can occur with a more uniform compression acting. A softer spring results. The width of the spring may be varied over its span without an increase in cost, giving a more efficient spring design. Another advantage of this invention is the additional flexibility of the spring enabling greater design tolerances in the spacer and spring. Accordingly, manufacturing costs can be saved. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a perspective view of a broken away fuel bundle having contained side-by-side fuel rods illustrating a bottom tie plate for the support of fuel rods and the inflow of coolant, a top tie plate for maintaining individual fuel rods in side-by-side vertical upstanding relation and permitting the outflow of heated coolant, and a typical spacer positioned therebetween for maintaining the fuel rods in their designed spaced apart relation. Figs. 2A and 2B are respective plan and elevation views of a prior art ferrule having an irregular shaped aperture with protruding portions utilized in a prior art spacer; Figs. 2C and 2D are respective views of prior art paired ferrules such as that shown in Figs. 2A and 2B, the ferrules here illustrated confronted one to another at irregular shaped apertures and trapping therebetween at protruding portions of the irregular apertures a loop spring, the loop spring here shown biasing two discrete fuel rods against stops of the ferrules for maintaining the fuel rods in their designed spaced apart relation; Figs. 3A and 3B are respective plan and elevation views of an additional prior art ferrule having an irregular shaped aperture with a protruding portion of the aperture bent out of the plane of the ferrule material for use within a prior art spacer; Figs. 3C and 3D are respective plan and elevation views of the ferrule construction of Figs. 3A and 3B, the ferrules here shown confronted one to another at their irregularly shaped apertures and trapping therebetween at the protruding portion of their apertures a leaf spring for biasing two fuel rods against respective stops; Figs. 4A and 4B are respective plan and elevation views of the altered ferrule of this invention, this ferrule designed for confronting and entrapping the improved loop spring of this invention; Fig. 5 is a perspective view of the improved loop spring of this invention; Figs. 6A, 6B and 6C are respective detailed sections taken through the improved spring of Fig. 5 illustrating in detail the spring construction; Fig. 7 illustrates the improved spring of Fig. 5 entrapped between paired ferrules of the construction of Figs. 4A and 4B; Fig. 8 is a perspective view of a second embodiment of the improved loop spring of this invention; Figs. 9A and 9B are respective detailed sections taken through the improved spring of Fig. 8 illustrating the construction in detail; Fig. 10 illustrates the spring of Fig. 8 entrapped between paired ferrules of the construction of Figs. 4A and 4B; Figs. 11A and 11B are respective plan and side elevations of an alternate ferrule construction with the ferrule here illustrating a I profile aperture; Fig. 12 is a plan view of spring material before formation into an alternate embodiment of the loop spring of this invention; Fig. 13 is a perspective view of the loop spring of Fig. 12; Fig. 14 is a cross section at the mid-height of the loop spring of Fig. 13 showing how the spring is located between two adjacent ferrules; Figs. 15A-15C are respective front elevation, top plan and side elevation of an alternate embodiment of the spring of this invention, this embodiment including C-shaped loops at the ends of the upper loop tab structure of the invention for keying the springs to confronted ferrules; Fig 16 is a top plan view of two ferrules with the spring of Figs. 15A-15C captured therebetween; and, Fig. 17 is a perspective view of the spring and ferrules of Fig. 16. Referring to Fig. 1, a typical prior art fuel bundle is illustrated in perspective with the major sections between the top and bottom of the bundle removed. The fuel bundle has a lower tie plate 14, an upper tie plate 16, and a plurality of fuel rods F. Fuel rods F extend vertically the length of the fuel bundle from a position of support on lower tie plate 14 to the upper tie plate 16. Unlike the illustration here shown, the fuel bundle is elongated. Typically, it is in the order of 4,064m (160 inches) long with approximately a 127x127mm (5 x5 ) cross-section. This being the case, it will be appreciated that the fuel rods within the bundle assembly are flexible in the longitudinal direction. In the particular case here shown, a 9x9 array of fuel rods is illustrated. Arrays of 10x10, 11x11, and 12x12 are known. It goes without saying that as the arrays become more dense, fuel rod diameter decreases and longitudinal flexibility increases. A word of explanation about the term fuel rods. Typically, fuel pellets are placed within tubular metallic cladding. The metallic cladding is thereafter sealed at both ends. So-called fuel rods F become sealed pressure vessels. It will be appreciated that each of these individual fuel rods F because of its 4,064m (160 ) length is individually flexible. It is well known that in the nuclear operation of the fuel bundle the spacing between discrete fuel rods F is important. Specifically, this spacing is important both for efficiency of the nuclear reaction as well as the generation of steam. Furthermore, any vibration on the fuel rods F is undesirable as such vibration can induce either rod abrading or cracking with resultant leakage of the contained radioactive materials interior of the fuel rods. To assure the proper spacing and a lack of vibration a plurality of spacers S are placed along the length of the fuel bundle F. Typically, 5 to 10 such spacers are utilized with 7 spacers being the ordinary number utilized. The spacers are placed at individual preselected elevations along the length of the fuel bundle. Referring to the illustrated spacer S in the 9x9 array of Fig. 1 it will be seen that each spacer consists of a grid of ferrules. These ferrules are illustrated in ferrule pairs in the prior art illustrations of Figs. 2A-2D and 3A-3D. Referring to Fig. 2A, a typical ferrule 20 as described in US-A-4 508 679 is illustrated. The ferrule is bent at its upper and lower portions to form stops 28. As will be pointed out with respect to Fig. 2C, it is the function of the stops 28 to enable the individual fuel rods 26 to be biased against the stops to assume their desired side-by-side spacing. Referring to Fig. 2B, an aperture 30 is illustrated cut within the side of the ferrule. The aperture includes two indentations 32, which indentations 32 define a protruding ear 34. As will be seen with respect to Fig. 2D, when the respective ears 34 are overlapped one to another, they can entrap a loop spring. Referring to Fig. 2D, two ferrules are abutted. When they are abutted, they define a common aperture 40 which aperture 40 surrounds a loop spring 44. In the particular embodiment illustrated in Fig. 2D, the double protrusions 34 are opposed and form a double wall thickness interior of the loop spring 44. This double wall thickness holds the loop spring in place. Referring to Fig. 2C, loop spring 44 is shared between the paired ferrules 20. The loop spring contacts the contained fuel rods 26, and biases rods 26. As biased the rods are pushed against their respective stops 28 within the ferrules 20. When the rods are pushed against the respective stops 28, they assume their designed side-by-side spacing. As has been previously emphasized, when the rod arrays become dense, the space between the rods 26 is reduced and the movement of the legs 48 of the spring 44 responsive to the compression of the rods is limited. Specifically the rod contacting portions 46 of the spring comes into contact with the walls 34 between the respective ferrules 20. Spring motion is limited. A further problem exists. Specifically, when the fuel bundles are assembled, rod contacting portions 46 of the spring have been known to scratch the sides of the fuel rods 26. Such scratches can be points where corrosion commences. Accordingly, it is desirable to cover the respective rods 26 with a thin plastic layer before insertion. Upon insertion, the plastic layer is removed and the problem of the rod contacting portions 46 of the spring scratching the sides of the fuel rods 26 are avoided. Unfortunately, space for spring movement has become so limited that it is not possible to insert two plastic covered fuel rods into a ferrule pair. It has become necessary to insert a first coated rod 26, and remove its cover before inserting a second coated rod 26 and removing its cover. In an effort to provide more spring flexure, the prior art has tried to reduce the wall thickness between the respective springs. Referring to Fig. 3A, a ferrule with paired stops 28 is illustrated. Unlike the ferrule 20 of the Fig. 2A, ferrule 20 of Fig. 3A has a protruding ear member 54. Ear member 54 is bent out slightly from the wall of the ferrule. Referring to Fig. 3B, aperture 50 is illustrated. The aperture 50 includes two protruding tabs 54, which tabs 54 impart to the aperture an overall E-type configuration. For stress relief and to provide ease of bending, two apertures 51 are provided. It will be seen in the view of Fig. 3A that tabs 54 are bent outwardly from the walls of the ferrule 20. As bent outwardly from the walls of the ferrule 20, they protrude outwardly approximately one-half of a wall thickness. Referring to Figs. 3C and 3D, the respective ferrules are confronted to one another. They are confronted with their tabs 54 opposed. The tabs as opposed come into abutment one with another. When the tabs are in abutment they serve to trap the spring members 44 therebetween. The trapped spring members contact the respective fuel rods 26 and urge the fuel rods against the respective stops 28. It can be seen with this prior art design additional flexure can be imparted to the legs 48 of the spring 44. Specifically with a single thickness of metal 54 in between the respective legs 48 of the spring, greater flexibility of the spring is present. Nevertheless, it has been found that the ferrule mounting herein disclosed can and does cause restricted movement of the spring. Additionally, and with respect to the prior art of Figs. 3C and 3D, assembly can be complicated. The process of positioning spring 44 and threading the respective tabs 54 into abutment is only accomplished with some difficulty. Accordingly, it is a major feature of this invention to simplify the construction. Referring to Figs. 4A and 4B, a ferrule 20 for incorporation into the matrix of a spacer according to this invention is illustrated. Ferrule 20 includes a single aperture 60 which aperture 60 is rectangular and therefore regular in section. Aperture 60 is typically as long as the loop spring. As will be hereinafter set forth, the loop spring fits interior of the aperture 60. At the same time, the width of aperture 60 is carefully selected. The width, defined in terms of degrees from the central axis of the ferrule 20, is approximately 35 . With such a dimension, two things can occur when two such ferrules 20 are confronted. First, a spring can fit within the aperture 60. Secondly, and at the sides of the aperture, there are defined tab receiving slots. These slots are defined in the interstices between two confronted ferrules 20. By the expedient of providing a spring with tabs to fit within these slots, confinement of a spring can result. Referring to Fig. 5, a spring for confrontation between the respective ferrules 20 of Fig. 4 is illustrated. The spring, like the prior art, includes two rod confronting portions 46 with respective spring legs 48 therebetween. Typically, the spring is welded at one C-shaped end at a weld 50 and is continuously bent to a C-shaped configuration at the other end in a loop configuration. Unlike the prior art, the spring includes four protruding tabs 70. Tabs 70 protrude on the respective opposite sides of spring legs 48A. Two tabs 70 protrude at the bottom of the spring, two tabs 70 protrude at the top of the spring. As will hereinafter be made more clear, these tabs locate the spring between two adjacent ferrules. The tabs project into regions between two confronted ferrules, and limit motion of the spring in the direction normal to the axes of the ferrules. Each spring is held in place at the common aperture defined between the opposed ferrules. The width of the spring legs 48 varies over their length, being widest at the top and bottom of the spring and at the middle of the spring. The central part of each leg has a reduced width, as can be more clearly seen in Fig. 6b. Referring to Fig. 6A, a section of the spring construction here illustrated is shown. Referring to Fig. 6A, it can be seen that half of a loop spring 44 is illustrated. The loop spring includes rod contacting portions 46 and respective legs 48, 48A. The respective legs 48, 48A are adjoined to a C-sectioned end 49 here shown welded with a weld 50. It will be observed that the spring at the C-sectioned end 49 has an extremely narrow clearance between the sections of the C. Specifically, clearance here is so narrow (especially under states of compression), that mounting of the spring around metal sections as in the prior art of Figs. 2A-2D and 3A-3D is not possible. Referring to Fig. 6B, the respective tabs 70 can be seen. These respective tabs 70 protrude outwardly into and engage tab receiving slots at the respective upper and lower ends of the apertures. By such engagement, the spring is held within the common aperture between the respective ferrules 20, as will be set forth in more detail with respect to Fig. 7. Fig. 6B also shows the regions of reduced spring width 43. Referring to Fig. 6C, it can be seen that the respective tabs 70 are bent out of the plane of the spring legs 48A. Such bending occurs so that the tabs 70 have the function of centering the spring. Referring to Fig. 7, the spring 44 is illustrated between the two ferrules 20. A cross section is shown at the elevation of the upper tabs. Each of the ferrules 20 has been confronted at its respective aperture 60. A discussion of the function of the confronted aperture 60 is instructive. When the ferrules 20 are confronted at their respective apertures 60, two classes of openings are defined between the respective ferrules 20. The first of these apertures is a common aperture 80. Common aperture 80 has a dimension slightly exceeding the height and width of the loop spring. Thus the loop spring is capable of being received within the common aperture 80 defined by the confronted apertures 60 of the confronted ferrules 20. The apertures also serve to define tab receiving slots 82. Specifically, openings into the interstitial area between the respective ferrules are tab receiving slots 82. It is into these tab receiving slots 82 that the tabs 70 of the spring fit. Assembly is easy to visualize. Specifically, ferrule pairs of ferrules 20 are confronted at their slots 60. They are confronted so as to define a common slot 80 and opposed tab receiving slots 82 along their respective sides. The common rectangular aperture 80 restricts displacement of the spring in the direction perpendicular to the axis x-x, and in the direction perpendicular to the plane of the figure. The tabs 82 restrict displacement of the spring along the axis x-x. In this way, the spring is completely captured between a pair of ferrules. Before the respective ferrule portions 20 are confronted, a spring is inserted between the respective ferrules. The spring 44 is captured within the common aperture 80. At the same time, the springs are held by the tab receiving slots 82. Referring to Fig. 8, a perspective view of a second embodiment of this invention is shown. In this embodiment, the spring is composed of two identical halves 202a and 202b, where the part on the right is inverted with respect to the part on the left. Locating tab 204a and 204b are located at the lower and upper ends of the spring halves 202a and 202b, respectively, and the springs are joined by welds 206 at top and bottom. Except for the locating tabs and the two-piece construction, this spring is similar to the first embodiment shown on Fig. 5. Rod contacting portions 46 urge the fuel rods against their respective stops. Referring to Figs. 9A and 9B, an end view and a side view of the spring of Fig. 8 are shown. The locating tabs 204a and 204b are formed as extensions of the ends of the spring halves 202a and 202b, respectively. These tabs lie midway between the two sides of the spring. Fig. 9b shows the variation in width of the spring with the narrow portion 43. Fig. 10 shows the spring of Fig. 8 captured between two ferrules. A cross section through the upper locating tabs is shown. The locating method is the same as that of the first embodiment of the spring, shown in Fig. 6C. Referring to Figs. 11A and 11B, an additional embodiment of this invention is illustrated. Specifically, a ferrule 20 has an I shaped aperture 90 configured therein. Aperture 90 includes upper and lower rectangular sections 92 which sections form the respective upper and lower bars of the I section of the aperture 90. As before, respective stops 28 form the points against which fuel rods are biased. Fabrication of the spring can be easily understood. Specifically, spring metal, typically formed of Inconel, is stamped in the shape of the side elevation section view of Fig. 12. The view of Fig. 12 includes upper and lower bars 102 with spring legs 48 and rod contracting portions 46 formed therebetween. As will hereinafter be understood, this spring is bent about an axis 104. Referring to Fig. 13, the bent and configured spring can be easily understood. Referring to Fig. 13, the respective portions of the spring have been bent about an axis 104, and the ends 106 are welded together. Such bending causes upper and lower bars 102 to bend in loop configuration back upon themselves. These members are integral with the spring legs 48 and expand the effective length of the spring. The rod contacting portions 46 act as before. Such a spring with an expanded effective length requires greater compression at the rod contacting portions 46 before appreciable change in the force required for the compression occurs. Such springs with an expanded effective length can be referred to as softer springs. Trapping of the spring into the apertures 90, 92 is easily understood with respect to Fig. 14. Specifically, apertures 90-as before-capture the main spring body. Apertures 92-both above and below aperture 90-capture arms 102. Since arms 102 are a part of the spring, these arms are required to extend into the tab receiving slots 112 defined by confronted aperture portions 92 in each of the ferrules. Construction is as illustrated before. The ferrules 20 are confronted with the spring of Fig. 13 trapped therebetween. When the ferrules are brought together-and fastened together-self-centering trapping of the spring occurs. Referring to Figs 15A-15C, an embodiment of the spring is disclosed in which the respective loop portions of the spring are integral with the tabs, and the tabs include C-shaped sections at their respective ends. These respective C-shaped ends at the tab loops are for retaining the springs to rectangular apertures in the side walls of the ferrules. As can be seen, opposed rod contacting portions 246 extend outwardly on either side of the spring. These respective portions 246 connect at spring leg members 248 to upper and lower tab loops 302. The respective ends of the tab loops 302 contain the respective C-shaped loops 320. Two of these loops 320 are welded on one side to close the construction of the spring. Referring to Figs 16 and 17, the trapping of the spring between two confronted ferrules can be understood. Two identical ferrules 330 are confronted at common rectilinear apertures 332. As before, these apertures when confronted define a common aperture between the ferrules and define at the sides of the spring trapping volume loop receiving apertures into which the (tab) loops protrude. Here the loop receiving slot receives the C-shaped loops 320. These respective C-shaped loops have a dimension that cause the retention and centering of the spring with respect to the ferrules. Were it not for this retention, the rod contacting portions of the spring 246 would cause retention - but at the same time permit undesirable excursion of the spring between the ferrules.	A fuel bundle spacer (S) for placement within a fuel bundle channel between upper (16) and lower (14) tie plates around fuel rods (F) for maintaining said fuel rods (F) in designed side-by-side spacing, said spacer comprising a matrix of ferrules (20) coextensive with the construction of said spacer (S) for placement within the fuel bundle channel; each said spacer matrix of ferrules including at least first and second side-by-side ferrules mounted in combination with a loop spring (44) forming a ferrule pair for fitting around respective side-by-side fuel rods to maintain said fuel rods spaced apart one from another; each said ferrule (20) of said ferrule pair having at least one internal stop (28) for permitting said fuel rod internal of said ferrule to be biased against said stop to a position of designed side-by-side alignment with respect to said fuel bundle at said spacer within said ferrule; each said ferrule of said ferrule pair further defining an aperture (60) for confrontation with a corresponding aperture of said adjacent ferrule of said ferrule pair to define a common aperture (80) between said ferrule pair for receiving the loop spring between said ferrules CHARACTERIZED IN THAT said common aperture is regular in section without any protruding tabs, said common aperture (80) further defining tap receiving slots (82) at the sides of said common aperture (80) between said ferrules for confining said spring at protruding tabs (70) to said common aperture (80) between said ferrule pair; each said loop spring having first and second legs (48), each leg including a rod contacting portion (46); said first spring leg biasing a fuel rod interior of said first ferrule of said ferrule pair and a second spring leg for biasing a fuel rod interior of said second ferrule of said ferrule pair; at least first and second tabs (70) protruding from at least one of said spring legs, said first tab protruding from a first side of said spring and said second tab protruding from a second side of said spring, said tabs for maintaining said loop spring in said common aperture (80) at said tab receiving slots; and, said first and second ferrules confronted at said apertures (60) with a main body of said loop spring confined in said common aperture (80) and said tabs protruding into said tab receiving slots (82) to maintain said loop spring in said aperture (80) whereby said respective spring legs (48) of said loop spring can bias respective fuel rods (F) in each said ferrule (20) of said ferrule pair against said stops (28) to maintain said fuel rods in designed side-by-side spacing. The spacer of claim 1 CHARACTERIZED BY said common aperture (80) having a rectangular shaped section. The spacer of claim 1 CHARACTERIZED BY said loop spring (44) including said first and second tabs (204b) protruding from the top side of said loop spring; and said loop spring includes at least third and fourth tabs (204a) protruding from the bottom side of said loop spring at at least one of said spring legs, said third tab protruding from a first side of said spring and said forth tab protruding from a second side of said spring, said tabs for maintaining said loop spring in said common aperture at said tab receiving slots; said first and second tabs (204a) engaging the top side of said tab receiving slots and said third and forth tabs (204a) engaging the bottom of said tab receiving slots. The spacer of claim 3 CHARACTERIZED BY said tabs forming an integral portion of said loop of said loop spring. The spacer of claim 1 CHARACTERIZED BY said common aperture (80) between said ferrules has an I shaped section. The fuel bundle spacer recited in claim 1 wherein said fuel rods (F) are vertical and further CHARACTERIZED BY said loop spring first and second legs (248) being vertical and a first horizontal loop (302) integral with and connecting the upper ends of the first spring legs and a second horizontal loop (302) integral with and connecting the lower ends of the second spring legs, said loops for maintaining said loop spring (244) in said common aperture (80) at said loop receiving slots (unnumbered); and said first and second ferrules (20) confronted at said apertures (60) whereby said respective spring legs (248) of said loop spring can bias respective fuel rods in each said ferrule of said ferrule pair against said stops (28) to maintain said fuel rods (F) in designed side-by-side spacing. The spacer of claim 6 CHARACTERIZED BY said loops (302) having respective C-shaped ends (320) and said loops protrude outwardly of said loop receiving slots at a dimension that exceeds the dimension of said slots whereby said C-shaped ends center said spring (244) in said common aperture. The spacer of claim 7 wherein each said aperture of said ferrule pair is rectilinear. The spacer of claim 7 wherein each said aperture of said ferrule pair is I shaped.	GEN ELECTRIC; GENERAL ELECTRIC COMPANY	JOHANSSON ERIC BERTIL; KING HAROLD BLECKLEY; JOHANSSON, ERIC BERTIL; KING, HAROLD BLECKLEY
EP-0489336-B1	489,336	EP	B1	EN	19,950,510	1,992	20,100,220	new	B42C9	null	B42C9, B32B37	B42C 9/00C, B32B 37/18A4	Combination binding and laminating machine	A device for simultaneously or sequentially edge binding a sheaf of papers (20) and separately laminating single sheets (15). A heat applying assembly includes a body (25,26,27,28) of heat conducting material having a generally horizontal elongated slot (29) extending through the body and two pairs of rollers (23,24;30,31), one at an input end of the slot and the other at an output end thereof for feeding a document (15) between two thermoplastic sheets (16,17) through the slot. Upper and lower imbedded heating coils (25b,28b) apply heat above and below the slot for fusing the thermoplastic sheets to effect lamination of the document. The body of heat conducting material provides an upper surface (28a) slanted at an acute angle with respect to the horizontal. A rigid guide surface (18,19) oriented by an equal angle with respect to the vertical provides for gravity retention of a sheaf of paper (20) to be edge bound against the aforementioned upper surface, a heat setting adhesive being introduced along the common end of the sheaf of papers thereby binding the papers along a spine.	BACKGROUND OF THE INVENTIONThe invention relates to multipage document binding and to single sheet document lamination in a common machine. In the prior art, both of those technologies are known separately. Thus, separate machines have been required to accomplish both functions sequentially or contemporaneously. The disadvantages of separate machines both physically and economically are obvious. These disadvantages are addressed by the unique structure of the invention as described hereinafter. Typical of prior art binding machines is that of U.S. Patent 4,367,116. In that disclosure a sheaf of paper to be edge-bound is inserted between guides vertically (on edge). The guide comprises two panels, one movable to hold the sheaf of papers in compression. The hot plate which sets the adhesive material is essentially horizontal in that reference. This device is relatively slow in operation because of the mechanical adjustment required. However, it does define the basic prior art of edge binding of a sheaf of papers. U.S. Patent 4,818,168 discloses another form for the basic binding device with converging guides which narrow at a lower apex to compress the multi-page document at the spine during the thermal binding operation. Separate laminating machines are extant in the prior art. Basically these machines rely on heating of a document sandwiched between sheets of a thermoplastic material - polyethelene, for example. Temperatures on the order of 300 degrees F. produce enough softening of the thermoplastic to produce fusion. The manner in which the invention advances the state of this art will be understood as this description proceeds. SUMMARY OF THE INVENTIONThe invention relates to a novel combination and certain novel features taken alone. A particularly novel aspect of the combination is the gravity loading of the binding portion of the machine. A plurality of sheets (sheaf) to be edge-bound stacks at an angle with respect to the vertical and lies against an angled rigid guide panel. To accomodate this loading arrangement, the top surface of the underlying heat applying (edge-heating) assembly is angled so that its planar surface is normal to the angled guide panel such that the spine of the bindable edge rests against the heated surface as fully as in the prior art case when the sheaf of papers stack vertically on a horizontal hotplate. For the laminating function, the body of the heating assembly includes an elongated slot through the body from an input to an output. An input pair of rollers grips the document to be laminated which is sandwiched between thermoplastic sheets and advances it through the slot thereby subjecting it to heating which softens the thermoplastic. Imbedded in the body are upper and lower electrical heating coils. The upper heating coils are the main source of heating at the top (angled) surface of the heat-applying assembly for the binding function. The heating assembly may be one piece above the slot or may be two pieces. If two pieces are employed, the portion containing the upper heating coils may be very similar to the lower piece (below the slot). An additional elongated piece of trapezoidal cross-section is closely mated to the upper heating coil-containing piece for enhancement of heat conduction to the upper (angled) surface of the trapezoidal piece. The input roller pair effects advancement of the document to be laminated until it disappears within the slot. Subsequently the output roller pair pulls the document through the slot and at the same time affords same forging action against the softened thermoplastic. The details of a typical embodiment of the invention with certain variations described will be understood from the detailed description hereinafter taken with the drawings. BRIEF DESCRIPTION OF THE DRAWINGSFIG.1 is pictorial showing the general form of a typical machine embodiment according to the invention. FIG.2 is a sectional view taken along the lines 2-2 of FIG.1. FIG.3 is a sectional view of the heat applying assembly of FIG.2. FIG.4 is a variation of FIG.3 in which the upper planar member and the trapezoidal heat sink are combined as a single monolithic piece. Referring now to FIG.1, the typical unit according to the invention is depicted at 10. A housing 11 includes a bottom panel 11a, and deck sections 11b and 11c and a bonnet 12 (see also FIG.2). Switches 13 and 14 conventionally control the power to the heating coils and roller drive motor,, respectively. A document 15 sandwiched between thermoplastic sheets 16 and 17 of polyethelene, for example, has a width of 279,4 mm (11inches) in typical case and the width of the gap L in the same direction is approximately 304,8 mm (12 inches) in a typical embodiment. FIG.2 affords a view of the internal structure of the apparatus of FIG.1. The input for a document to be laminated is at 22 where document 15 and thermoplastic sheet 16 and 17 are inserted and are picked up between rollers 23 and 24 and moved inward (left in FIG.2) to the aperture defined by chamfers 25a and 26a on elongated planar members 25 and 26, respectively, and through gap 29. Reference to FIG.3 is desirable at this point in the description. As the document passes beyond the grip of rollers 23 and 24, its passage within gap (slot) 29 is continued by the grip of rollers 30 and 31 until exited over deck section 11c. During its time passing through gap 29, the thermoplastic sheets are softened by the heat of members 25 and 26 and rollers 30 and 31 have some forging effect on the still soft plastic although cooling occurs quickly thereafter and the laminated document exits over deck section 11c. Referring to FIG.3, heating of members 25 and 26 is effected by resistance coils 25b and 26b so that gap 29 is heated from above and below. A typical temperature for polyethelene plastic lamination is on the order of 149 degrees C (300 degrees F). Electrical connections for heating coils 25b and 26b are at 25c, 25d, 26c and 26d and are typical and may be anywhere as long as there is no interference with the operation of the device. The heat sink 27 is in thermal contact with member 26 along an interface 27b. A variation in the structure of the elongated planar members is depicted in FIG.4. The elements 26 and 27 of FIG.3 are combined into a single monolithic element 28 with a corresponding imbedded upper resistance heating coil 28b and comparable electrical connections. It should be understood that the structures of FIG.3 and FIG.4 are elongated in the L direction as identified on FIG.1. Referring back to FIG.2, the guide panels 18 and 19 are seen tilted at an acute angle with respect to the vertical. A sheaf of papers to be edge-bound 20 is inserted betwen panels 18 and 19 so as to lie against panel 18 and abut top surface 27A (or 28A if the FIG.4 variation is used). Guide panel 19 is spaced from panel 18 to conform to a predetermined maximum thickness of the sheaf of papers to be bound but may in fact be eliminated in the general case since the angle of panel 18 provides the support needed. As is conventional in this art, a tape with a layer of thermally curable adhesive is inserted against surface 27A (or 28A) and the heat of that surface effects the binding operation. The electric motor drive for the rollers 23,24, 30 and 31 is conventional and the related electrical connections are similarly conventional and are, therefore, not specifically described.	A thermal binding device (10) comprising: a heat applying assembly (27) and guide means (18, 19) for directing a sheaf (20) of papers to be bound along a common edge to direct said common edge against a top surface (27a) of said heat applying assembly (27), characterized in that it is arranged as a combination laminating and thermal binding device (10), the heat applying assembly (27) being formed by upper and lower blocks of solid heat conducting material, said blocks having spaced facing surfaces forming a generally horizontal enlongated uniform gap (29) therebetween; with upper and lower heating coils (26b, 25b), associated with said upper and lower blocks, respectively, for applying heat above and below said gap (29); with feed means including at least one pair of counter-rotating rollers (23, 24) for conveying a document (15) sandwiched between two thermoplastic sheets (16, 17) through said gap (29) to effect fusion of said thermoplastic sheets (16, 17) to thereby laminate said document (15). Combination according to claim 1, characterized by a second pair of rollers (30, 31) at the exit end of said gap (29) to pull the laminated document (15) therethrough. Combination according to claim 1, characterized in that said conductive material of said heat applying assembly (27) is aluminum. Combination according to claim 1, characterized in that said guide means (18, 19) includes at least one rigid planar surface (18) parallel to said sheaf (20) of papers to tend to hold said sheaf (20) of papers such that said common edge seats against said heat applying top surface (27a). Combination according to one of the preceding claims, characterized in that the heat applying assembly has a heat sink member (27) of generally trapezoidal cross-section, said heat sink member (27) having a lower surface (27b) in thermal contact with an upper surface of said upper block and having an upper planar top surface (27a), making a first acute angle with respect to the upper surface of said upper block; and said guide means (18, 19) being oriented such as said common edge of said sheaf (20) of papers lies against said heat sink member upper surface (27a). Combination according to claim 5, characterized in that said guide means (18, 19) holds said sheaf (20) of papers to be bound at a second acute angle with respect to the vertical, said first and second acute angles being equal. Combination according to claim 5, characterized in that said planar members and said heat sink member are aluminum. Combination according to claim 6, characterized in that said planar members and said heat sink member are aluminum. Combination according to claim 5, characterized in that said feed means includes a first pair of rollers (23, 24) for feeding said document (15) and thermoplastic sheets (16, 17) into said gap (29) and a second pair of roller (30, 31) at the exit of said gap (29) for exiting said document (15) from said gap (29) in laminated condition, said second pair of rollers (30, 31) rotating to pull said laminated document (15) through said gap (29). Combination according to claim 5, characterized in that said guide means comprises a rigid sheet (18), said sheaf (20) of papers to be bound resting against said rigid sheet (18) and thereby edge abutting said heat sink upper surface. Combination according to claim 9, characterized in that the aperture of said gap (29) adjacent said first pair of rollers (23, 24) is chamfered adjacent said first pair of rollers (23, 24) to provide ease of guidance for said document (15) and thermoplastic sheets (16, 17) into said gap (29). Combination according to one of the preceding claims, characterized by first and second electric coil heating elements (26b, 25b) imbedded in said assembly above and below said gap (29) respectively to apply heat from above and below said gap (29). Combination according to claim 12, characterized in that said first electric coil heating element (26b, 28b) is proximate to said heat applying assembly top surface (27a, 28a) thereby heating said top surface (27a, 28a) by conduction. Combination according to claim 12, characterized in that said heat applying assembly (27, 28) is fabricated of highly conductive metal. Combination according to claim 13, characterized in that said heat applying assembly (27, 28) is fabricated of aluminum. Combination according to claim 12, characterized in that said feed means comprises first and second pairs of rotating rollers (23, 24; 30, 31) for gripping and feeding said document (15) and said thermoplastic sheets (16, 17) through said gap (29), said first pair of rollers (23, 24) being adjacent an input end of said gap (29) and said second pair of rollers (30, 31) being adjacent the output end of said gap (29).	BANNER AMERICAN PROD INC; BANNER AMERICAN PRODUCTS, INC.	COOK ROY P; PARKHILL ALAN J; COOK, ROY P.; PARKHILL, ALAN J.
EP-0489339-B1	489,339	EP	B1	EN	19,960,417	1,992	20,100,220	new	C23F3	null	C23F3	C23F 3/06	Brightening chemical polishing solution for hardened steel article and method of using it	A brightening chemical polishing solution for a hardened steel article (e.g., a carburized and quenched gear) comprises hydrofluoric acid having a molar concentration of from 0.2 to 2 mol/ℓ, hydrogen peroxide having a molar concentration of from 0.4 to 4 mol/ℓ, and water, a molar ratio of the hydrofluoric acid to the hydrogen peroxide being from 1:1.5 to 1:2.8. The steel article is quench hardened and is chemically polished in the solution. A shot-peening is additionally performed, prior to the polishing.	BACKGROUND OF THE INVENTIONField of the InventionThe present invention relates to a (brightening) chemical polishing solution for a hardened steel article, and a method of chemically polishing the hardened steel article by using the solution. The present invention can be applied to hardened steel articles having a complicated shape, e.g., hardened gears used in a transmission gear, a differential gear and the like, to improve the properties of these articles, such as the surface roughness, fatigue strength, and wear resistance thereof. Description of the Related ArtSteel articles requiring a high strength, e.g., transmission gears of automobiles, are subjected to a case-hardening heat-treatment, particularly, a carburizing and quench hardening treatment, and a carburized and quench hardened layer formed in the surface portion of the steel article (gear) has a high hardness and a residual compressive stress which improve the fatigue strength and wear resistance of the article. Recently, as the power output by automobile engines is increased, a greater fatigue strength is required of such articles. A carburized and hardened steel article, however, has an abnormal layer, regarded as an oxidized and non-martensitic layer, having a depth of from 5 to 50 µm from the surface thereof, and as such an abnormal layer has a hardness lower than that of the normal hardened layer existing thereunder, and thus lowers the residual compressive stress at the top surface, the abnormal layer is a factor in the lowering of the fatigue strength; a large surface roughness is another factor in the lowering of the fatigue strength, whether or not the abnormal layer exists. To improve the fatigue strength of steel articles, shot-peening has been adopted as an additional process giving a relatively high compressive stress to a surface layer having a depth of from 200 to 400 µm from the top surface thereof. The residual compressive stress caused by the shot-peening has a peak value at from 10 to 100 µm from the top surface which is lower than the peak value thereof at a portion above the former-mentioned position. According to the shot-peening process, the steel articles are bombarded with hard particles at a high speed, and thus surface damage is liable to occur. Furthermore, the abnormal layer of the carburized and hardened steel article is hardly removed by the shot-peening, and thus a portion thereof remains. Such damage and the remaining abnormal layer portion are liable to become initiation points of fatigue crack, and hinder a stable and marked improvement of the fatigue strength. A mechanical polishing process for removing this abnormal layer has been proposed in, e.g., A Process for Producing a High Strength Gear (Japanese Unexamined Patent Publication (Kokai) No. 01-264727, published on October 23, 1989), in which a steel article (gear) is subjected to a carburizing and quench hardening treatment, and shot-peening, and is then ground with a grinding wheel of cubic boron nitride. The high hardness of the hardened article, however, lowers the grinding efficiency of the mechanical grinding. In particular, articles with a complicated shape, such as tooth-roots of a gear required a fatigue strength can not be precisely ground, with high efficiency. On the other hand, electrolytic polishing has been proposed in, e.g., Japanese Unexamined Patent Publication (Kokai) Nos. 62-24000 (published on January 31, 1987), 02-129421 (published on May 17, 1990), and 02-129422 (published on May 17, 1990). According to the above Publication No. 62-24000 (Electrolytic Polishing Process of Gears), electrodes are arranged near the tooth-bottom of a carburized and hardened gear, and an electrolytic polishing solution is sprayed toward the tooth-bottom, to thereby etch the tooth-bottom only. In this case, it is necessary to change the position of the electrodes, depending on the shape of the steel article, to ensure a dimensional accuracy, and thus this electrolytic polishing device has a complicated structure. Furthermore, according to the above Publication Nos. 02-129421 and 02-129422 (High Strength Coil Spring and Method of Producing the Same), a spring of chromium-vanadium steel is quench-hardened, tempered and shot-peened, and then subjected to an electrolytic polishing treatment. In this case, surface damages are removed to attain a surface roughness (Rmax) of 5 µm or less, but the accuracy of the spring is not so severe. If the methods of these publications apply to articles (e.g., gears) required of a strict accuracy, the problem pointed out in the above Publication No. 62-24000 also occurs. Taking the above-mentioned conventional processes and disadvantages into consideration, the present inventors though investigated the use of chemical polishing process for polishing a hardened steel article. A chemical polishing process for steel articles was proposed by, e.g., U.S. Patent No. 3369914 (Method of Chemically Polishing Iron, Zinc and Alloys thereof). USP' 914 uses an aqueous solution of hydrogen fluoride and hydrogen peroxide, a molecular ratio of hydrogen peroxide to hydrogen fluoride being between about 3:1 and 7:1, and states that a metal component part is immersed in this solution bath for 1 minute to obtain a shining surface of the component part. It is possible to apply this polishing process to a pretreatment for plating, a treatment for improving a corrosion resistance, and a brightening treatment, without considering the polishing rate or polishing amount, but if this process is applied to a precision polishing of articles such as hardened gears, requiring a precise dimensional accuracy, since USP' 914 does not disclose suitable conditions for such a precision polishing treatment, a person skilled in the art cannot apply this process to a final polishing of parts. Furthermore, since the molar ratio of hydrogen peroxide to hydrogen fluoride is large (3 to 7), the hydrogen peroxide in the solution is liable to decompose during its solution is not used with the result that expensive hydrogen peroxide is wasted and the polishing solution is not suitable for an industrial polishing treatment, from the viewpoint of solution stability. Furthermore, regarding the shot-peening, a Method of Treating a Surface of a Carburized and Hardened Layer (Japanese Unexamined Patent Publication (Kokai) No. 62-203766 (published on September 8, 1987) was proposed, in which a steel article (e.g., a gear) is carburized and hardened, an abnormal layer is removed by a chemical dissolving (etching treatment, and the article surface is then shot-peened. In this case, the chemical dissolution (etching) produces a surface roughness (Rmax) of several tens of micrometers, and the shot-peening reduces this roughness. Nevertheless, although the abnormal layer is removed, the shot-peening damages the article surface, and thus no remarkable improvement of the fatigue strength is obtained. SUMMARY OF THE INVENTIONAn object of the present invention is to provide a solution suitable for brightly and chemically polishing a hardened steel article with a complicated shape, to thereby improve the properties, such as fatigue strength, surface roughness and luster, of the article. Another object of the present invention is to provide a method of chemically polishing and brightening a hardened steel article at a high accuracy and a high efficiency without a special polishing device. These and other objects of the present invention are attained by providing a brightening chemical polishing solution for a hardened steel article, which solution consisting essentially of hydrofluoric acid having a molar concentration of from 0.2 to 2 mol/ℓ, hydrogen peroxide having a molar concentration of from 0.4 to 4 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being in the range of from 1:1.5 to 1:2.8, with the proviso that the solution does not contain sulfuric acid. The above-mentioned and other objects are also attained by a method of bright-chemical-polishing a hardened steel article, the method comprising the steps of: hardening the steel article, and thereafter, polishing the hardened steel article with the above-mentioned brightening chemical polishing solution. preferably, the method further comprises a shot-peening step carried out between the hardening step and the chemical polishing step. In general, a chemical polishing solution comprises an acid and an oxidizer. According to the present invention, the hydrofluoric acid (solution of hydrogen fluoride (HF)) is adopted as the acid for dissolving (chemically attacking) a hardened steel article, since iron (Fe) ions eluted from the article are stabilized as complex ions of FeF6 3- or the like in the solution bath. As a result, a catalytic action of complex ions is reduced, and thus this solution can be used industrially for such a treatment. The hydrofluoric acid used in the present invention can be prepared as hydrogen fluoride (99% or more) or diluted hydrofluoric acid. Preferably the diluted hydrofluoric acid is in a concentration of about 50%, from the viewpoint of easy handling thereof in preparation of a polishing solution, and the commercially availability thereof. According to the present invention, a concentration of the hydrofluoric acid ranges from 0.2 to 2 mol/ℓ, preferably from 0.3 to 1.5 mol/ℓ. The hydrofluoric acid concentration influences the polishing rate (i.e., metal dissolution rate) in connection with a bath (solution) temperature. At a constant bath temperature, the higher the hydrofluoric acid concentration, the higher the polish rate. During the polishing step, the bath temperature is remarkably elevated due to the reaction heat and thus the polishing rate is inevitably increased. Where the concentration is more than 2 mol/ℓ, it is difficult to suitably control the polishing rate, but if the concentration is less than 0.2 mol/ℓ, the polishing rate is less than 1 µm/min, and thus the polishing efficiency is too low. It is industrially preferable that the polishing rate is from 1 to 100 µm/min, and the hydrofluoric acid concentration is determined to be from 0.2 to 2 mol/ℓ, to obtain the preferable polishing rate. Where the hydrofluoric acid has a concentration of from 0.3 to 1.5 mol/ℓ, a practical polishing rate of 2 to 50 µm/min is obtained, and a control and maintenance of the polishing rate is facilitated. BRIEF DESCRIPTION OF THE DRAWINGThe present invention will be more apparent from the description of the preferred embodiments set forth below, with reference to the accompanying drawing, in which: Fig. 1 is an S-N diagram showing a relationship between the relative stress amplitude and the number of cycles to failure. DESCRIPTION OF THE PREFERRED EMBODIMENTSAccording to the present invention, the hydrogen peroxide (H₂O₂) is adopted as the oxidizer accelerating dissolution of Fe and has a micro-smoothing (i.e., brightening) action, since the hydrogen peroxide has a strong oxidizing power and forms by-products of water (H₂O) and oxygen gas (O₂) after the polishing reaction. Such by-products do not hinder the polishing step even over a long operation time, and are favorable for a waste solution treatment. It is preferable to use a hydrogen peroxide having a concentration of from 30 to 60%, which is commercially available as an industrial chemical. According to the present invention, a concentration of the hydrogen peroxide ranges from 0.4 to 4 mol/ℓ, preferably from 0.6 to 3 mol/ℓ. At less than 0.4 mol/ℓ of the hydrogen peroxide concentration will degrade a luster of the polished surface, and at more than 4 mol/ℓ, will cause a remarkable decomposition due to reaction heat, thereby making it difficult to control the polishing solution. Furthermore, a hydrogen peroxide concentration of 0.6 mol/ℓ or more stably provides a satisfactory glossy surface, and that of 3.0 mol/ℓ or less almost eliminates the hydrogen peroxide decomposition based on reaction heat. The suitable concentration of the hydrogen peroxide depends mainly on the hydrofluoric acid concentration. The chemical polishing solution according to the present invention comprises the hydrofluoric acid and the hydrogen peroxide at a suitable mixing ratio, to thereby polish and brighten a hardened steel article at a practical polishing rate. According to the present invention, the molar ratio of the hydrofluoric acid to the hydrogen peroxide ranges from 1:1.5 to 1:2.8, preferably from 1:1.6 to 1:2.4. In an electrochemical model of an acid dissolution of metal, where the hydrogen peroxide and the hydrofluoric acid coexist in the solution, the hydrogen peroxide is decomposed at a surface of the steel article, to thus generate oxygen, and the nascent oxygen exhibits a strong oxidation power to promote a transpassive dissolution of the article surface. With such a transpassive dissolution, it is possible to prevent a nonuniform dissolution of the article surface, based on a metal structure or the like, to thereby form an evenly brightened surface. The formation of the transpassivity substantially depends on the dissolution power of the hydrofluoric acid and oxidation power of the hydrogen peroxide, and is stably maintained in the above-mentioned molar ratio range. Such a chemical dissolution action (i.e., transpassivity) of the chemical polishing solution according to the present invention promotes a uniform polishing of the steel article, regardless of the shape or hardness of the hardened steel article. A molar ratio of less than 1:1.5 will degrade the luster of the article surface, since the micro-smoothing action is insufficient, and a molar ratio of more than 1:2.8 will have no advantage over the claimed molar ratio range, although it will not degrade the luster, wastes the expensive hydrogen peroxide, and easily causes variations in the bath (solution) composition. A molar ratio of 1.6 mol/ℓ or more provides a more satisfactory glossy surface, despite concentration variations caused by additional supply for consumed hydrofluoric acid and hydrogen peroxide in a continuous operation, and a molar ratio of 2.4 mol/ℓ or less suitably suppresses variations in the composition of the solution and effectively prevents waste of the expensive hydrogen peroxide. When preparing the chemical polishing solution having a predetermined composition, it is preferable to weigh or measure by volume the diluted hydrofluoric acid and the hydrogen peroxide aqueous solution, as commercial chemicals, mix same, and add water to the mixed solution to control the component concentrations. Such a preparation method is most usual, but it is possible to adopt other preparation methods. Namely, it is possible to use these chemicals and diluting water containing impurities, as long as the polishing is not hindered. Preferably, the chemicals are a reagent first grade or better, and the water is a deionized water. Preferably, the chemical polishing solution further comprises one of purine alkaloid compounds, as a stabilizer for the hydrogen peroxide. The addition of the purine alkaloid compound contributes to a further stabilizing of the chemical polishing solution, and enables the solution to be used despite an accumulation of metal ions at a high concentration during the polishing step, and thus the stabilizer extends the service life of the solution when used on an industrial scale. Since the effect of the stabilizer is unchanged by heat, an activation of the chemical reaction due to the raising of the bath (solution) temperature is utilized for increasing a process capability (i.e., raising the polishing rate under a suitable control), and thus the stabilizer can lower the cost and raise the production efficiency of the chemical polishing treatment. Since the purine alkaloid compounds are a vegetable matter widely found in nature, they are not harmful to workers' health. The compounds are water-soluble basic organic compounds, such as caffeine, theophylline and theobromine, having a prime structure shown in the following formula. Preferably, the compound has a concentration of from 0.1 to 30 g/ℓ in the polishing solution. A concentration of less than 0.1 g/ℓ will weaken the effect of suppressing the decomposition of the hydrogen peroxide, and that of more than 30 g/ℓ will not obtain an effect corresponding to the addition amount and is not economical. The quench hardening method used for the hardened steel article may be a carburizing and quenching method, an induction hardening method, a flame hardening method, or the like. After the quench hardening, a usual tempering may be performed. Preferably, most of the hardened metal structure is composed of martensite. The hardened steel includes carbon steel, chromium steel, chromium-molybdenum steel, nickel-chromium-molybdenum steel and the like, which can be easily dissolved by an acid solution Since some steels, such as stainless steel, having a very strong resistance to acid does not substantially chemically dissolvable, the present invention is not applied to such steels. Where a steel has precipitate particles stable to acid, such as various carbides, a grain size of the precipitate particles should be small. Furthermore, it is preferable to minimize non-metallic inclusions contained in the matrix, since the inclusions are liable to serve as initiation points of fatigue crack. The steel article can have any shape, as long as a surface to be polished of the article comes sufficiently into contact with the chemical polishing solution in a bath, and the solution runs on the surface. Therefore, it is undesirable that the article has a very narrow gap portion or a cavity portion. If the article has such undesirable portions, it is necessary to change the solution application conditions, e.g., to make a jet of the solution impinge on such portions. Where the heat-treated steel article has a clean surface, the article may be directly subjected to the chemical polishing, but usually dirt, oil and the like adhere to the article, and thus this should be removed by a cleaning treatment prior to the chemical polishing. The cleaning treatment can be carried out in a usual way using, e.g., a cleaning agent such as an organic solvent and an alkaline cleaner. Where the hardened steel article has an oxide scale on the surface thereof, it is unnecessary to remove the normal scale, but it is preferable to remove very thick scale strongly adhering to the surface, by a mechanical stripping method (e.g., a shot-blasting method) or an etching method. The hardened steel article, after such a pretreatment as required, is immersed in the chemical polishing solution having the predetermined concentrations of the hydrofluoric acid and hydrogen peroxide in accordance with the present invention. The chemical polishing treatment proceeds together with a generation of an oxygen gas naturally causing strong stirring of the solution, and thus it is unnecessary to additionally fit a stirring means to a solution bath. Furthermore, a heat generated by a chemical reaction raises the bath temperature, which raises the polishing rate. To ensure the precision of the size and surface condition of the article, it is preferable to maintain the bath temperature at a constant value. Such an immersing treatment is performed for a certain time, to obtain the desired polishing amount, and thereafter, the article is taken out of the bath, washed and dried. Under certain circumstances the polished surface becomes discolored (rust-colored) during such an after-treatment, and such surface is not desirable for special use. In this case, the discoloration can be prevented by adding a pickling step using a dilute acid (e.g., a hydrochloric acid ranging from 2 to 3% in concentration) and then an alkaline neutralizing step, prior to the washing step. In the chemical polishing step, according to another embodiment of the present invention, the hardened steel article is mainly polished in a (first) chemical polishing solution having relatively high concentrations of the hydrofluoric acid and hydrogen peroxide, and then additionally polished in another (second) chemical polishing solution having relatively low concentrations. For example, it is preferable to carry out the chemical polishing step in two stages, i.e., a first stage of mainly polishing the hardened steel article in a first chemical polishing solution consisting essentially of hydrofluoric acid having a molar concentration of from 0.8 to 1.5 mol/ℓ, hydrogen peroxide having a molar concentration of from 1.6 to 3 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being from 1:1.6 to 1:2.4, and then a second stage of additionally polishing the article in a second chemical polishing solution consisting essentially of hydrofluoric acid having a molar concentration of from 0.2 to 0.8 mol/ℓ, hydrogen peroxide having a molar concentration of from 0.4 to 1.6 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being from 1:1.5 to 1:2.8. When the washing step is performed a certain time after the end of the first polishing stage using the (first) high concentration chemical polishing solution, the remaining solution adhering to the article surface further reacts (over-reacts) therewith, prior to the washing, to deteriorate the luster of the article surface. In this case, the polished article is repolished by using the (second) low concentration chemical polishing solution, to restore the glossy surface. The low concentration solution adhering to the surface chemically reacts with the article surface at a low reaction rate, and thus the glossy surface is maintained. Therefore, the two stage polishing process is suitable for an industrial, i.e., continuous and/or mass operation. According to the other embodiment of the present invention, prior to the chemical polishing step, the hardened steel article is subjected to shot-peening, to further improve the fatigue strength. Such shot-peening usually generates a residual compressive stress extending in the article to a depth of 200 to 400 µm from the surface thereof. The residual stress has a peak value at a depth of 10 to 100 µm from the surface. The shot-peening has an effect of suppressing a a growth of fatigue crack. The shot-peening is performed by striking shots (hard particles) against the article surface (i.e., by bombarding the surface with the shots) with a commercial shooting device under conditions similar to those for treating ordinary steel articles. For providing a large peening effect, the shot material has a relatively high density and a high hardness, and is, e.g., steel having an HV450 to HV1000 (preferably, HV600 to HV1000). The larger the shot size, the deeper the effective depth of the peening effect, but the smaller the number of the shots, the more extended the peening time. Preferably, the shot size is in the range of 0.2 to 1 mm. Where the steel article, e.g., a gear, has fillet portions (tooth-roots or tooth-bottom), the shots are smaller than one-half of the smallest fillet radius, for providing an effective peening of the fillet portions, and should be near such a size. A strength of the shot-peening is larger than 0.1 mm in arc height. If the strength is smaller than 0.1 mm in arc height, it is difficult to attain a suitable peening effect. Preferably, a speed of the shot jet is in the range of 30 to 70 m/sec, which is obtained by accelerating the shots with an impeller or a compressed air. Preferably, the shot time is from 0.5 to 10 minutes. A conventional shot-peening is carefully performed (under limited conditions), to thus prevent surface damage, but the surface damage caused by the shot-peening is easily removed by the following chemical polishing according to the present invention, with the result that the shot-peening conditions are more freely determined. Moreover, the chemical polishing treatment chemically dissolves and removes a surface layer including the shot-peening surface damage and the abnormal layer caused by the carburizing and quenching treatment, as mentioned above. Since a thickness of 5 to 50 µm is removed in accordance with the chemical polishing process of the present invention, such a harmful surface layer is completely removed, to thereby expose the surface with the residual compressive stress at the peak value or in the vicinity thereof. Therefore, the finally obtained steel article has a defect-free smooth surface having a high residual compressive stress, and thus the surface dependence of the fatigue failure is greatly lowered to thereby remarkably increase the fatigue strength. As mentioned above, the chemical polishing method according to the present invention is widely applied to hardened steel articles, especially those with complicated shapes which are difficult to polish by a mechanical polishing method and an electrolytic polishing method. The chemical polishing method improves the polishing finish, fatigue strength, friction property, and wear-resistance. Furthermore, the addition of the shot-peening further improves the fatigue strength. Example 1Samples having a size of 15 mm x 10 mm x 50 mm were made of a chromium steel (JIS SCr 420H) and were finished at a surface roughness Rz of 3 to 4 µm by cutting. Then the samples were carburized, quench hardened and tempered under the conditions shown in Table 1. Treatment Condition Carburizing930-950°C x 150-240 min Quenching850°C x 30-60 min Holding and then Oil Cooling Tempering130-160°C x 60-120 min Holding and then Air Cooling Chemical polishing solutions (500 ml) were prepared by mixing a commercial reagent grade hydrofluoric acid (47%), a commercial reagent grade hydrogen peroxide aqueous solution (30%), and deionized water to attain predetermined compositions shown in Table 2. The solutions for sample Nos. 1 to 15 had compositions according to the present invention, and the solutions for sample Nos. C1 to C6 were comparative examples. After the samples were degreased with an alkaline cleaner, the samples were immersed in the chemical polishing solutions for 2 minutes, and then were washed, drained, and dried. The surfaces of the samples were checked to determine whether or not a good luster had appeared, and a polished depth of the samples was measured to thereby calculate the polishing rate. The results are shown in Table 2. Sample No. Solution Composition Solution Temp. (°C) Ability Estimation Hydrofluoric Acid (Mol/ℓ) Hydrogen Peroxide (Mol/ℓ) Molar Ratio HF:H₂O₂ Surface Luster Polishing Rate (µm/min) Present Invention10.20.41:2.040Yes1.2 21.02.01:2.040Yes12.0 31.53.01:2.040Yes46.0 42.04.01:2.040Yes98.0 51.01.51:1.540Yes11.0 61.02.51:2.540Yes13.5 71.02.81:2.840Yes14.5 81.02.01:2.050Yes13.8 91.02.01:2.030Yes8.4 101.02.01:2.020Yes5.9 110.40.81:2.040Yes4.0 121.01.71:1.740Yes11.6 131.02.31:2.340Yes13.2 141.22.81:2.340Yes19.9 151.42.41:1.740No21.4 Comparative ExampleC10.10.281:2.840No0.3 C20.14.0 1:4040Yes0.4 C3 2.5 2.5 1:2.040Yes248 C42.52.51:1.040No159 C51.01.21:1.240No10.2 C61.01.21:5.040Yes18.5 As is obvious from Table 2, the samples Nos. 1 to 15 polished with the solution having a hydrofluoric acid concentration of 0.2 to 2 mol/ℓ and a hydrogen peroxide concentration of 0.4 to 4 mol/ℓ, a molar ratio of the hydrofluoric acid to the hydrogen peroxide being from 1:1.5 to 1:2.8, according to the present invention, had a luster (glossy surface) and a polishing rate of from 1.2 to 98.5 µm/min. Among the samples Nos. C1 to C6 were treated with the solutions outside the present invention, the sample No. C1 had no luster and a low polishing rate of 1 µm/min or less, similar to that of the sample No. C2; a polishing rate of the sample No. C3 was greatly increased, so that the polishing treatment was not controlled; the sample Nos. C4 and C5 had a nonglossy, satin-like surface; and in the sample No. C6, although the glossy surface was obtained and the polishing rate was similar to that of the present invention, the solution was quickly and severely decomposed, and thus the polishing rate was rapidly lowered. Example 2Samples Nos. 16 and 17 (rods) having a diameter of 15 mm and a length of 100 mm were made of chromium-molybdenum steel (JIS SCM 420H) and nickel-chromium-molybdenum steel (JIS SNCM 420H), respectively, and the samples were carburized, quench hardened and tempered under the conditions shown in Table 1 of Example 1. A sample No. 18 having the same dimensions as the samples Nos. 16 and 17 was made of carbon steel (JIS S55C) and was hardened by an induction hardening treatment at a frequency of 150 kHz, to form a hardened layer having an effective hardened depth of 1 to 2 mm. Then, these three hardened samples were ground to a surface roughness Rz of about 4 µm. The commercial hydrofluoric acid, the commercial hydrogen peroxide aqueous solution, and an deionized water were mixed to prepare a chemical polishing solution having a composition having a hydrofluoric acid concentration of 1 mol/ℓ, a hydrogen peroxide concentration of 2 mol/ℓ, and a molar ratio of the hydrofluoric acid to the hydrogen peroxide of 1:2, according to the present invention. After the samples were degreased with an alkaline cleaner, the samples were immersed for 3 minutes in the chemical polishing solutions kept at 40°C, and were washed, drained, and dried. The surfaces of the samples had mirror-likely brightened good luster. A polished depth of the samples was measured, to thereby calculate the polishing rate. A surface roughness of the samples was measured before and after the polishing treatment. The results are shown in Table 3. Sample No. Roughness (µmRz) Polished Depth (µm) Polishing Rate (µm/min) Before After 164.20.623511.7 173.80.493712.7 183.20.553511.7 As obvious from Table 3, the surface roughness was remarkably reduced by a chemical polishing treatment for 3 minutes. Furthermore, regardless of the kind of steel, the polished depth and polishing rate were almost the same, respectively, and thus a highly efficient polishing rate was obtained. Example 3Two samples were prepared in the same manner as Example 1, namely, the samples of chromium steel (JIS SCr 420H) having the same dimensions and roughness, were heat treated under the same conditions, and were degreased with the same alkaline cleaner as in Example 1. Two chemical polishing solutions were prepared in the same manner as Example 1. A first (high concentration solution) of the two solutions had the same composition as that of the solution for the sample No. 2, and a second (low concentration solution) had the same composition as that of the solution for the sample No. 1 in Table 2. One of the samples was immersed in the first chemical polishing solution (40°C) for 3 minutes, taken out, kept for 20 seconds, immersed in the second chemical polishing solution (40°C) for 10 seconds, and then kept for 20 seconds. Then, the polished sample was washed, drained and dried in the same manner as Example 1. The sample had a good luster (glossy surface). For a comparison with the above-mentioned sample, the other sample was immersed in the first (high concentration) solution (40°C) for 3 minutes, taken out, kept for 20 seconds, and washed, drained and dried, thus omitting the second solution treatment. This sample had a dull luster surface, since the chemical reaction of the solution adhering to the sample surface further proceeded during the holding before the washing. Example 4A gear sample (module: 2.75, pitch circle radius: 85 mm, tooth number: 28) was made of a chromium steel (JIS SCr 420H) and carburized, quench hardened and tempered under the conditions shown in Table 1 of Example 1. The polishing solution used in Example 2 was prepared as a chemical polishing solution. After the gear sample was cleaned in the same manner as that of Example 1, the gear was immersed for 2.5 minutes in the chemical polishing solutions kept at 40°C. Then, the gear sample was washed, drained and dried, and the gear sample had a bright finished. To examine changes in the dimensions of the gear, the polished depths of the sample were measured at a tooth-root, a tooth-face and a tooth-tip, to calculate the polishing rates. The results are shown in Table 4. Measurement Position Polished Depth (µm) Polishing Rate (µm/min) Tooth-Root2811.2 Tooth-Face2911.6 Tooth-Tip3112.4 As is obvious from Table 4, the polished depths and polishing rates at the tooth-root, tooth-face and tooth-tip were almost the same values, and thus a hardened steel article with a complicated shape (e.g., gear) was polished at a high accuracy. Example 5The chemical polishing solution containing a hydrofluoric acid 1 mol/ℓ in concentration and a hydrogen peroxide 2 mol/ℓ in concentration was prepared by mixing a commercial hydrofluoric acid, a commercial hydrogen peroxide aqueous solution, and a deionized water, as described in Example 2. Hardened steel article samples of a chromium steel (JIS SCr 420H) were polished by immersing same in the solution, with the result that metal ions were accumulated to 40 g/ℓ. Then, the solution was supplemented with the commercial hydrofluoric acid and the commercial hydrogen peroxide aqueous solution, to control the concentrations to the initial values, respectively. During such preparation, a stabilizer of caffeine, theophylline or theobromine was also added in amounts shown in Table 5, to obtain solution samples A to H. For comparison with these solution samples, a well-known stabilizer of uric acid, orthoaminobenzoic acid or polyoxyethyleneoctylphenylether was added in amounts shown in Table 5, to obtain comparative solution samples I to M. Then, the solution samples were maintained at 40°C and the concentration of the hydrogen peroxide thereof was analyzed. The concentration gradually dropped with the lapse of time to 1.5 mol/ℓ, for a certain time, and this time was determined as a stabilizing time. The results are shown in Table 5. Note that the analysis of the hydrogen peroxide concentration was performed by the permanganate titration method. As is obvious from Table 5, the use of a purine alkaloid compound stabilizer stabilized the hydrogen peroxide for a long time, to thus extend a service life of the chemical polishing solution. Solution Sample Stabilizer Added Amount (g/ℓ) Stabilizing Time (hr) Present InventionACaffeine0.13 BCaffeine0.36 CCaffeine1.015 DCaffeine3.032 ECaffeine10.070 FCaffeine30.0> 100 GTheophylline3.015 HTheobromine3.013 Comparative ExampleIOrthoaminobenzoic Acid0.11 JOrthoaminobenzoic Acid0.32 KOrthoaminobenzoic Acid3.06.5 LUric Acid3.03 MPolyoxyethyleneoctylphenylether3.03.5 Example 6Test pieces (fillet-notched specimens) having a test portion 6 mm thick and 10 mm wide, and a notch 1 mm in radius were prepared from a round chromium steel 30 mm in diameter (JIS SCr 420H) and then were carburized, quench hardened and tempered under conditions shown in Table 6. After the heat treatment, the test pieces were degreased with an alkaline cleaner. Treatment Condition Carburizing950°C x 150 min Quenching850°C x 30 min Holding then Oil Cooling Tempering150°C x 60 min Holding then Air Cooling Next, in accordance with processes and conditions shown in Table 7, sample Nos. 21 and 22 of the heat treated test pieces were subjected to a shot-peening step and a chemical polishing step (according to the present invention). In the shot-peening step, shots (steel particles) having on average hardness of HV 800 or HV590 and an average diameter of 0.66 mm collided with the sample Nos. 21 and 22 at a rate of 50 to 70 m/sec for 1 minute. In the chemical polishing step, the sample Nos. 21 and 22 were immersed in the chemical polishing solution used in Example 2 and kept at 40°C, for 1.5 to 2.5 minutes, to give a glossy finish to the surface thereof (i.e., remove a surface layer having a thickness of 20 to 30 µm). Then the surface roughnesses and residual compressive stress at the surface and at a depth of 50 µm of the polished samples were measured. The results are shown in Table 8. As comparative examples, a sample No. C11 of the heat treated test pieces was not subjected to the shot-peening and chemical polishing, sample Nos. C12 and C13 were subjected to the shot-peening using the shots (HV 800 or HV 590), and a sample No. C14 was subjected to etching using an aqueous solution of HNO₃ to remove (chemically dissolve) a surface layer having a thickness of 20 to 30 µm, and to the shot-peening with HV 800 shots. The sample Nos. C12, C13 and C14 were not chemically polished. The surface roughness and residual compressive stress at the surface and at a depth of 50 µm of these comparative samples were then measured, and the results are shown in Table 8. Sample No. Process Present Invention21Carburizing Hardening → Shot-Peening (Shot HV590) → Chemical Polishing (20-30 µm) 22Carburizing Hardening → Shot-Peening (Shot HV800) → Chemical Polishing (20-30 µm) Comparative ExampleC11Carburizing and Hardening Only C12Carburizing Hardening → Shot-Peening (Shot HV590) C13Carburizing Hardening → Shot-Peening (Shot HV800) C14Carburizing Hardening → HNO₃ Etching (30 µm) → Shot-Peening (Shot HV800) Sample No. Residual Stress (kg/mm²) Roughness (µmRz) Surface 50 µm depth Present Invention21-115-1252 22-140-1653 Comparative ExampleC110-252 C12-40-1257 C13-50-16510 C14-110-1557 To examine the fatigue strength thereof, all of the samples of the test pieces were subjected to a pulsating bending fatigue test to obtain a relationship between a stress amplitude and a number of cycles to failure. The results are shown in Fig. 1. In Fig. 1, the abscissa indicates a number of cycles (repetition) of the bending, and the ordinate indicates a repeated stress (stress amplitude) which are values relative to the fatigue limit (corresponding to a horizontal line portion) of the sample No. C11 as 1.0. As obvious from Fig. 1, compared to the comparative carburized and hardened only steel article (sample No. C11), the fatigue limit of the sample Nos. C12 and C13 is improved by 7 to 30% by the shot-peening, that of the sample No. C14 is improved by about 37% by the etching and shot-peening, and that of the sample Nos. 21 and 22 is remarkably improved by 44 to 63% by the shot-peening and chemical polishing according to the present invention. Thus, the hardened steel article produced in accordance with the treating process of the present invention has a high fatigue strength, since the article has higher residual compressive stresses at the surface and at the 50 µm depth and a smoother surface than the hardened steel articles treated by conventional processes, as shown in Table 8. Example 7Test pieces (fillet-notched specimens) having a test portion 6 mm thick and 10 mm wide, and a notch 0.5, 1 or 2 mm in radius, were prepared from a round chromium steel 30 mm in diameter (JIS SCr 420H), and then carburized, quench hardened and tempered under the conditions shown in Table 6 of Example 6. Then, the heat treated test pieces were subjected to a shot-peening step and a chemical polishing step in accordance with the process of the present invention, to obtain samples Nos. 23, 24 and 25. In the shot-peening step, shots (steel particles) having an average hardness of HV 800 and an average diameter of 0.66 mm collided with these samples at a velocity of 50 to 70 m/sec for 1 minute. In the chemical polishing step, these samples were immersed in the chemical polishing solution used in Example 2 and kept at 40°C, for 1.5 to 2.5 minutes, to give a bright polish to the surface thereof (i.e., remove a surface layer having a thickness of 20 to 30 µm). As comparative samples, the heat-treated test pieces having different notches were used as sample Nos. C15, C16 and C17, respectively, as they were. All of the samples of the test pieces were subjected to a pulsating bending fatigue test in the same manner as Example 6, to obtain a relationship between a stress amplitude and a number of cycles before failure. The results for the fatigue limit (corresponding to a horizontal line portion of S-N curve) are shown in Table 9. In Table 9, the fatigue limits are relative values to those of comparative samples, with the same size notch regarded as 100. Sample No. Notch Radius (mm) Fatigue Limit 230.5180 C15100 241.0163 C16100 252.0155 C17100 As is obvious from Table 9, the fatigue limits of the samples with different notch radiuses treated by the shot-peening and chemical polishing are improved by 55% or more, compared with those of the comparative samples. Thus, according to the present invention, it is unnecessary to use a special electrode and device used in a conventional electrolyte polishing process for a complicated shape article with, e.g., notched portions, and it is possible to attain a high fatigue strength by a convenient process (shot-peening and chemical polishing steps without special devices). Example 8Helical gear samples (module: 2.25, pitch circle diameter: 117 mm, tooth number: 46) were made of three kinds of steels (JIS SCr 420H, JIS SCM 420H and JIS SNCM 420H) and carburized, quench hardened and tempered under the conditions shown in Table 6 of Example 6. Then, three of the heat treated gears were subjected to a shot-peening step and a chemical polishing step in the same manner as Example 7 to obtain samples Nos. 27, 28 and 29, except that the shot-peening step was performed for 3 minutes. As comparative samples, three other of the heat treated gears were used as sample Nos. C18, C19 and C20, respectively, as they were. All of the samples of the helical gears were subjected to a pulsating type tooth-root bending fatigue test, to estimate a tooth-root fatigue strength. The results are shown in Table 10. In Table 10, the tooth-root fatigue strengths of the sample Nos. 27, 28 and 29 are relative values to those of the comparative sample Nos. C18, C19 and C20 of the same steel, regarded as 100. Sample No. Gear Material Fatigue Strength 27SCr 420H170 C18100 28SCM 420H170 C19100 29SNCM 420H178 C20100 As is obvious from Table 10, the fatigue strengths of the gears treated by the shot-peening and chemical polishing are improved by 70% or more, compared with those of the comparative samples, regardless of the steel used. Thus, the improvement proportion of Example 8 is remarkably increased compared with Examples 6 and 7, since an initial surface roughness (about 10 µm Rz) of a tooth-root important for fatigue strength of the gear is larger than the surface roughness in Examples 6 and 7, and is remarkably improved by several micro-meters (µm) by the shot-peening and chemical polishing, to largely increase the fatigue strength. It will be obvious that the present invention is not restricted to the above-mentioned embodiments and that may variations are possible for persons skilled in the art without departing from the scope of the invention.	A brightening chemical polishing solution for brightening a hardened steel article consisting essentially of hydrofluoric acid having a molar concentration of from 0.2 to 2 mol/ℓ, hydrogen peroxide having a molar concentration of from 0.4 to 4 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being from 1:1.5 to 1:2.8, with the proviso that the solution does not contain sulfuric acid. A brightening chemical polishing solution according to claim 1, wherein the molar concentration of said hydrofluoric acid is from 0.3 to 1.5 mol/ℓ, the molar concentration of said hydrogen peroxide is from 0.6 to 3.0 mol/ℓ, and said molar ratio is from 1:1.6 to 1:2.4. A brightening chemical polishing solution according to claim 1, wherein said water is a deionized water. A brightening chemical polishing solution according to claim 1, further comprising a stabilizer of a purine alkaloid compound. A method of bright-chemical-polishing a hardened steel article comprising the steps of: quench hardening the steel article; and chemically polishing said hardened steel article in a brightening chemical polishing solution according to any of claims 1-4. A method of bright-chemical-polishing a hardened steel article comprising the steps of: quench hardening the steel article; shot-peening the surface of said hardened steel article, and chemically polishing said hardened steel article in a brightening chemical polishing solution according to any of claims 1-4. A method according to claim 5 or 6, wherein said water is deionized water. A method according to claim 5 or 6, wherein said quench hardening step comprises the steps of: carburizing said steel article; quenching said carburized steel article; and tempering said quenched steel article. A method according to claim 5 or 6, wherein said quench hardening step is performed by an induction hardening process. A method according to claim 5 or 6, wherein said chemical polishing step comprises he steps of mainly polishing said hardened steel article in a first chemical polishing solution consisting essentially of hydrofluoric acid having a molar concentration of from 0.8 to 1.5 mol/ℓ, hydrogen peroxide having a molar concentration of from 1.6 to 3 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being from 1:1.6 to 1:2.4, and then additionally polishing said hardened steel article in a second chemical polishing solution consisting essentially of hydrofluoric acid having a molar concentration of from 0.2 to 0.8 mol/ℓ, hydrogen peroxide having a molar concentration of from 0.4 to 1.6 mol/ℓ, and water, a molar ratio of said hydrofluoric acid to said hydrogen peroxide being from 1:1.5 to 1:2.8.	TOYODA CHUO KENKYUSHO KK; TOYOTA MOTOR CO LTD; KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO; TOYOTA JIDOSHA KABUSHIKI KAISHA	AIHARA HIDEO; ASANO TAKASHI; KAJINO MASAKI; OGAWA KAZUYOSHI; OGINO MINEO; ONISHI MASAZUMI; SHIMIZU FUMIO NAGAKUTE-SHATAKU; SUZUKI KENICHI; SUZUKI YASUYUKI; AIHARA, HIDEO; ASANO, TAKASHI; KAJINO, MASAKI; OGAWA, KAZUYOSHI; OGINO, MINEO; ONISHI, MASAZUMI; SHIMIZU, FUMIO,; SUZUKI, KENICHI; SUZUKI, YASUYUKI; SHIMIZU, FUMIO, NAGAKUTE-SHATAKU 304
EP-0489348-B1	489,348	EP	B1	EN	19,950,201	1,992	20,100,220	new	B22D11	B22D11	B22D11	B22D 11/06E, B22D 11/06L2D1, B22D 11/115	Method for continuous casting of steel and apparatus therefor	The invention relates to a method and an apparatus for continuous casting of steel. The melt is feed with a nozzle (1) to the mould (2). A high-frequency magnetic field is generated to the place where nozzle, mould and melt (5) contact each other, to improve the surface quality of the cast product.	The present invention relates to a method for continuous casting of steel wherein molten steel is solidified by cooling means and produced solidified shells are successively withdrawn and an apparatus therefor, and more particularly to a method for continuous casting of steel by the use of cooling means such as a cooled roll, a cooled mold and the like and an apparatus therefor. Various methods for continuous casting of steel using a cooled roll and a cooled mold have been reported. Japanese Patent Application Laid Open No. 284469/89 discloses a method for continuous casting of steel wherein a refractory nozzle and a cooled mold connected to said refractory nozzle are used. In this method, the refractory nozzle is means for feeding molten steel and the mold is cooling means. Japanese Patent Application Laid Open No. 210154/89 discloses a method for continuously manufacturing a steel sheet by solidifying molten steel on a circumferential surface of a rotating cooled roll. In this method, a refractory dam is placed near an end face of said cooled roll to hold molten steel on the surface of said roll, and the refractory dam is means for feeding molten steel, and the cooled roll is means for cooling molten steel. Problems are generally raised that a solidified shell is generated at a zone where cooling means such as a cooled mold and a cooled roll, means for feeding molten steel such as a refractory nozzle and a refractory dam and molten steel contact each other, which gives rise to a great deterioration of surface properties of a cast product. It is an object of both the prior art methods in the Japanese Patent Application Laid Open No. 284469/89 and the Japanese Patent Application Laid Open No. 210154/89 not to cause defects in a cast porduct. The prior art methods are methods wherein a solidified shell is not generated at a zone where means for cooling molten steel and means for feeding molten steel and molten steel contact each other. The method for continuous casting of steel disclosed in the Japanese Patent Application Laid Open No. 284469/89 will now be described with specific reference to Figure 4. Figure 4 is a partially sectional view illustrating a zone adjacent to a connectig portion where a refractory nozzle for feeding molten steel to a cooled mold is connected to the cooled mold. A coil 4 is placed near the connecting portion where the refractory nozzle 1 is connected to the cooled mold 2. That is, the coil 4 is positioned inside the refractory nozzle 1 just in front of an inlet port of the cooled mold 2. A high-frequency electric current is flowed through the coil 4, thereby generating a magnetic field . A magnetic pressure is generated on the part of molten steel near by a zone where the refractory nozzle 1, cooled mold 2 and molten steel contact each other by interaction between said magnetic field and said molten steel. Molten steel 5 at said zone is pressed toward inside, whereby a space 7 is formed. A solidified shell 6 is hard to be generated at the zone where the refractory nozzle 1 and the cooled mold 5 and molten steel contact each other due to formation of the space 7. The molten steel 5 begins to be solidified from a position adjacent to the space 7 on the inner surface of the mold 2. There is no surface defect such as a draw mark referred to as a cold shut in a withdrawn billet and the billet with good surface properties can be obtained. The method disclosed in the Japanese Patent Application Laid Open No.210154 will now be described with specific reference to Figure 5. Figure 5 is a partially sectional view illustrating a zone adjacent to a cooled roll and a refractory dam placed near an end face of said cooled roll. The cooled roll 20 is immersed into molten steel 5. The refractory dam 21 is positioned along both the end faces of said cooled rolls 20 so that the molten steel 5 cannot penetrate between the dam 21 and the side of said roll 20. A coil 4 is positioned outside the refractory dam 21. A high-frequency electric current is flowed through the coil 4 whereby a magnetic pressure is generated. The molten steel 5 at a zone adjacent to the end face of the cooled roll 20 and adjacent to the refractory dam 21 is pressed to the inside, thereby a space 7 is formed. A solidified shell is hard to be generated at the zone adjacent to the end face of the cooled roll 20 and adjacent to the refractory dam 21 due to formation of the space 7, which solves a problem of deterioration of surface properties of a steel sheet. That is, there cannot be a problem that the solidified shells generated at the zone adjacent to the cooled roll 20 and adjacent to the refarctory dam 21 stick to each other and is connected to each other, that a connecting portion of the solidified shells is broken by rotation of the cooled roll 20, and that end faces of the steel sheet in the direction of the breadth of the steel sheet are made zigzag by repeated sticking and breaking of the solidified shells. However, since a magnetic field is only generated by simply flowing an electric current through the coil 4, the magnetic field generated is scattered. Therefore, an effective magnetic pressure cannot be caused to act on the zone where cooling means such as the cooled roll 20 and cooled mold 2 and feeding means such as the refractory nozzle 1, refractory dam 21 and the molten steel 5 contact each other. In order to generate a magnetic pressure strong enough to be able to form a space 7 where there is no molten steel at the zone where the cooling means, feeding means and the molten steel 5 contact each other, a great high-frequency electric current shoud be flowed through the coil 4, which requires a high-frequency power source of large capacity. It is an object of the present invention to provide a method for continuous casting of steel wherein a steel cast with good surface properties can be produced without any high-frequency power source of large capacity. To attain the above-mentioned object, the present invention provides a method for continuous casting of steel comprising the steps of: feeding molten steel to cooling means for cooling molten steel by use of feeding means for feeding molten steel, said feeding means being followed by said cooling means; cooling fed molten steel by said cooling means; generating a high-frequency magnetic field near a zone where said feeding means, said cooling means and molten steel contact each other; and converging said high-frequency magnetic field on the zone where said feeding means, said cooling means and molten steel contact each other. Further, the present invention provides an apparatus for continuous casting of steel, comprising: feeding means for feeding molten steel; cooling means for cooling molten steel fed by said feeding means, said feeding means being followed by said cooling means; generating means for generating a high-frequency magnetic field near a zone where said feeding means, said cooling means and molten steel contact each other; and converging means for converging the magnetic field on the zone where said feeding means, said cooling means and molten steel contact each other. The above objects and other objects and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the appended drawings. Figure 1 is a partially sectional view illustrating an apparatus to be used for executing a method for continuous casting of steel according to the present invention; Figure 2 is a partially sectional view illustrating another apparatus for executing the method for continuous casting of steel according to the present invention; Figure 3 is a graphical representation showing a magnetic pressure generated at a connecting portion where a refractory nozzle is connected to a mold during casting of a billet according to the present invention; Figure 4 is an explanatory view of a method for continuous casting of a billet according to the prior art method; Figure 5 is an explanatory view of another method for continuous casting of a billet according to the prior art method; and Figure 6 is a partially sectional view illustrating another apparatus for executing the method for continuous casting of steel according to the present invention. In the present invention, a high-frequency magnetic field is generated near a zone where feeding means for feeding molten steel, cooling means for cooling molten steel and molten steel contact each other, and the high-frequency magnetic field thus generated is converged on the zone where the feeding means, the cooling means and molten steel contact each other. To converge the high-frequency magnetic field, a magnetic field convergence plate is used. A magnetic pressure generated by the high-frequency magnetic field acts concentratedly on molten steel at the zone where the feeding means, the cooling means and molten steel contact each other. The magnetic field convergence plate is desired to be made of a soft magnetic material having a high magnetic permeability, a large saturation magnetic flux density and a small hysterisis loss. Silicon steel, pure iron, permalloy and the like are desired as the soft magnetic material. When a magnetic field is generated near the magnetic field convergence plate, the magnetic field is converged, passing through the magnetic field convergence plate without scattering. Accordingly, when the magnetic field convergence plate is arranged near the zone of generation of the high-frequency magnetic field on the occasion of generating the high-frequency magnetic field near the zone where the feeding means, the cooling means and molten steel contact each other, the generated high-frequency magnetic field is converged on the magnetic filed convergence plate whereby a high magnetic pressure acts concentratedly on the zone where the feeding means, the cooling means and molten steel contact each other. A space is effectively formed by said concentratedly acting magnetic pressure at the zone where the feeding means, the cooling means and molten steel contact each other, and a solidifeid shell 6 is not generated at said zone. As described above, the magnetic pressure acts on molten steel at the zone where the feeding means, the cooling means and molten steel contact each other, and the molten steel also is simultaneously heated by an eddy current induced by the magnetic field. The molten steel is heated concentratedly and effectively at the zone where the feeding means, the cooling means and molten steel contact each other, and a solidified shell is prevented from being formed at said zone. Since the magnetic field convergence plate is heated by the eddy current induced upto a very high temperature and a magnetic property of the magnetic field convergence plate is lowered, the magnetic field is desired to be generated while the magnetic field convergence plate is being cooled. The high-frequency magnetic field is generated by flowing a high-frequency electric current through a coil. The frequency of the electric current is desired to be from 500 to 10000 Hz. When the frequency of the electric current is less than 500 Hz, a desired magnetic pressure cannot be obtained. When the frequency of the electric current is over 10000 Hz, an inputted power is increased and a power loss is increased. The frequency of the electric current is desired to be from 2000 to 6000 Hz. ExampleAn example of the present invention will now be described with specific reference to the appended drawings. Figures 1 and 2 are partially sectional views illustrating apparatuses for executing a method for continuous casting of steel according to the present invention. Figure 1 is a partially sectional view illustrating an apparatus for continuous casting of steel wherein a water cooled mold as cooling means for cooling molten steel is connected to a refractory nozzle as feeding means for feeding molten steel. Molten steel in a tundish ( not shown ) is led to a mold 2 through a refractory nozzle 1. The mold 2 is made of copper and cooled by water. The molten steel 5 led to the mold 2 is cooled, and a solidified shell 6 is formed. A magnetic field convergence plate 3 is placed between the nozzle 1 and the mold 2, both of which are connected to each other via the magnetic field convergence plate 3. A coil 4 is arranged around an outer circumference of the nozzle 1 near the magnetic field convergence plate 3. The magnetic field convergence plate 3 is positioned directly contacting the mold 2 and constantly cooled. In the method for contiuous casting of steel wherein the apparatus as shown in Figure 1 is used, billets are intermittently or successively withdrawn from the mold 2. When a high-frequency electric current is flowed through the coil 4 during withdrawing of billets, a great magnetic pressure is concentrated on a zone where the nozzle 1, the mold 2 and molten steel 5 contact each other. Even if a great electric current is not flowed, a space 7 is formed at the zone where the nozzle 1, the mold 2 and molten steel 5 contact each other. A round billet of 60 mm in diameter was produced using an apparatus as shown in Figure 1. A magnetic pressure generated at the zone where the nozzle 1, the mold 2 and molten steel 5 contact each other was found by means of a simulation. The result of the simulation is shown in Figure 3. The production condition is shown in Table 1. Inside diameter d₁ of the refractory nozzle40 mm Inside diameter d₂ of the mold60 mm Material for the magnetic field convergence plateelectrical steel plate Thickness of the magnetic field convergence plate1.5 mm Relative magnetic permeability100 High-frequency electric current3000 A Frequency3000 Hz The variation of the magnetic pressure of from A point on an end face of the magnetic field convergence plate 3 inside the mold 2 to O point at the corner of the nozzle 1 on the side of the mold 2 is shown in Figure 3. The magnetic pressure is represented in terms of molten steel column height. In Figure 3 a curve of 1 ○ denotes a variation of the magnetic pressure on condition shown in Table 1, and a curve of 2 ○ denotes a variation of the magnetic pressure in the case where the magnetic field convergence plate 3 is not used and the magnetic field is not converged. As clearly seen from Figure 3, the magnetic pressure at the A point was about 10 cm in the case of 2 ○ where the magnetic field was not converged. The magnetic pressure in the case of the example of 1 ○ was about 100 cm in terms of molten steel column. The magnetic pressure at the A point was increased about ten times by converging the magnetic field. The magnetic pressure in the case where the magnetic field was converged at the zone where the nozzle 1 and the mold 2 contact molten steel 5 also is presumed to be increased ten times compared with the case where the magnetic field is not converged. Casting of steel was carried out by means of a continuous withdrawing for the case where the magnetic field was converged in the example and for the case where the magnetic field was not converged in comparison respectively in accordance with the result of the simulation. As a result, it was confirmed that surface properties of an obtained billet were good and the billet was stably produced in the case where a high-frequency electric current of 2000 A and 3000 Hz was flowed in the example, and that the results of the example were better than in the case where a high-frequency electric current of 5000 A and 3000 Hz was flowed in the comparison. A cooling water passage 30 is made in the magnetic field convergence plate 3 of the apparatus for continuous casting of steel as shown in Figure 6. The magnetic field convergence plate 3 is cooled by water flowing in the cooling water passage 30. Figure 2 (A) and (B) are partially sectional views illustrating a top pouring apparatus for continuous casting of a steel sheet having two cooled rolls. Figure 2 (A) is an elevation of the apparatus. Figure 2 (B) is a side elevation of the apparatus. Reference numeral 10 denotes cooled rolls which rotate and are positioned in parallel with each other and adjacent to each other, and 11 a refractory dam which forms a basin to store molten steel 5 on the cooled rolls 10, being arranged adjacent to both the ends of the cooled rolls. The magnetic field convergence plate 3 is placed along a circularly arcking zone where the end face of the cooled roll 10, the refractory dam 11 as a connecting refractory and molten steel 5 contact each other. A cooling box 12 is placed directly under this magnetic field convergence plate 3 and connected to this plate 3 as a united body, whereby the plate 3 is cooled constantly. The coil 4 is positioned on the magnetic field convergence plate 3. The molten steel 5 fed to the basin is cooled by the cooled roll 10 during casting of a steel sheet. A solidified shell is formed around the cooled roll 10. The solidified shell moves successively downwardly with rotation of the cooled roll 10 and converts to a steel sheet 13, being pressed between the cooled rolls 10. On this occasion, a great magnetic pressure acts concentratedly on a circularly arcked zone when a high-frequency electric current is flowed through the coil 4. Consequently, even if a great electric current is not flowed through the coil 4, a space is formed in the aforementioned circularly arcked zone. Subsequently, a magnetic pressure generated in the aforementioned circularly arcked zone during casting of a steel sheet by the use of an apparatus having the same structure as that in Figure 2 was found by means of a simulation. According to the result obtained by the simulation, the magnetic pressure in terms of molten steel column was 50 cm in the case of converging the magnetic field ( in the example ) whereas the magnetic pressure in terms of molten steel column was 5 cm in the case of not converging the magnetic field ( in the comparison ). The magnetic field was increased ten times by converging the magnetic field. The condition in this case was shown in Table 2. Material for magnetic field convergenceelectric steel Thickness of magnetic field convergence plate1.5 mm Relative magnetic permeabiltiy of magnetic field convergence plate100 High-frequency electric current2000 A Frequency3000 Hz As a result, it was understood that a steel sheet with good surface properties can be manufactured stably even if no great electric current is flowed through the coil 4. Since the method of the present invention is a method wherein a magnetic pressure is caused to act concentratedly on the zone where the cooling means, the feeding means and molten steel contact each other by generating a high-frequency magnetic field near said zone and by converging the high-frequency magnetic field on the magnetic field convergence plate, any solidified shell cannot be formed at said zone by forming a space where there is no molten steel at said zone, using only a small amount of electric power. Accordingly, the electric power can be greatly reduced and a cast product with good surface properties can be stably, manufactured without causing a high-frequency electric power source to have a large capacity. Reference signs in the claims are intended for better understanding and shall not limit the scope.	A method for continuous casting of steel, comprising the steps of: feeding molten steel to cooling means for cooling molten steel by use of feeding means for feeding molten steel, said feeding means being followed by said cooling means; cooling fed molten steel by said cooling means; and generating a high-frequency magnetic field near a zone where said feeding means, said cooling means and molten steel contact each other; characterized by converging said high-frequency magnetic field on the zone where said feeding means, said cooling means and molten steel contact each other. The method of claim 1, characterized in that said high-frequency magnetic field is generated by a coil placed near a zone where said feeding means, said cooling means and molten steel contact each other. The method of claim 1, characterized in that said magnetic field is converged by a magnetic field convergence plate which is made of a soft magnetic material and which has a cooling device. The method of claim 3, characterized in that said soft magnetic material is one selected from the group consisiting of a silicon steel, pure iron and permalloy. The method of claim 1, characterized in that said feeding means is a refractory nozzle (1); said cooling means is a water-cooled mold (2), molten steel being fed from the nozzle to the mold; said high-frequency magnetic field is generated by a coil (4) arranged around a circumference of said nozzle; and said magnetic field generated is converged by a magnetic field convergence plate (3) positioned between said nozzle and said mold. The method of claim 1, characterized in that said cooling means are two rotating cylindrical rolls (10) arranged at intervals, molten steel fed into between said two cylindrical rolls being cooled by said rolls; said feeding means are refractory dams (11) positioned on both end faces of the cylindrical rolls to store molten steel on the two rolls as the cooling means; said high-frequency magnetic field is generated by the coil (4) placed near a zone where the refractory dam, the cylindrical rolls and molten steel contact each other; and said magnetic field generated is converged by the magnetic field convergence plate (3) along a zone where the refractory dam, the cylindrical roll and molten steel contact each other. The method of claim 6, characterized in that said magnetic field convergence plate has a cooling box (12) thereunder. An apparatus for continuous casting of steel, comprising: feeding means for feeding molten steel; cooling means for cooling molten steel fed by said feeding means, said feeding means being followd by said cooling means; and generating means for generating a high-frequency magnetic field near a zone where said feeding means, said cooling means and molten steel contact each other; and characterized by converging means for converging the magnetic field on the zone where said feeding means, said cooling means and molten steel contact each other. The apparatus of claim 8, characterized in that said generating means is a coil positioned near the zone where said feeding means, said cooling means and molten steel contact each other. The apparatus of claim 8, characterized in that said converging means is a magnetic field convergence plate made of a soft magnetic material. The apparatus of claim 10, characterized in that said soft magnetic material is one selected from the group consisting of a silicon steel, pure iron and permalloy. The apparatus of claim 10, characterized in that said feeding means is a refractory nozzle (1); said cooling means is a water-cooled mold (2), molten steel being fed from the nozzle to the mold; said generating means is a coil (4) arranged around a circumference of said nozzle; and said converging means is a magnetic field convergence plate (3) positioned between said nozzle and said mold. The apparatus of claim 10, characterized in that said cooling means are two rotating cylindrical rolls (10) arranged at intervals, molten steel fed into between said two rolls being cooled by said rolls; said feeding means are refractory dams (11) positioned on both end faces of the cylindrical rolls to store molten steel on the two cylindrical rolls as said cooling means; said generating means is a coil (4) placed near a zone where the refractory dam, the cylindrical rolls and molten steel contact each other; and said converging means is a magnetic field convergence plate (3) arranged along the zone where the refractory dam, the cylindrical rolls and molten steel contact each other. The apparatus of claim 10, characterized in that said magnetic field convergence plate has a cooling box (12) thereunder.	NIPPON KOKAN KK; NKK CORPORATION	ISHII TOSHIO C O PATENT AND LI; MORI KENTARO C O PATENT AND LI; NAKADA MASAYUKI C O PATENT AND; OOSAKO TAKASHI C O PATENT AND; SATO TOSHIO C O PATENT AND LIC; SUGIYAMA SHINICHI C O PATENT A; ISHII, TOSHIO, C/O PATENT AND LICENSE DEP.; MORI, KENTARO, C/O PATENT AND LICENSE DEP.; NAKADA, MASAYUKI, C/O PATENT AND LICENSE DEP.; OOSAKO, TAKASHI, C/O PATENT AND LICENSE DEP.; SATO, TOSHIO, C/O PATENT AND LICENSE DEP.; SUGIYAMA, SHINICHI, C/O PATENT AND LICENSE DEP.
EP-0489351-B1	489,351	EP	B1	EN	20,000,308	1,992	20,100,220	new	G06F9	null	G06F9, G06N5	G06F 9/44G4	Software work tool	A software work tool used in a work for a program or data on information processor and aiming at realizing a general purpose software work tool capable of automatically performing a software operation based on the information regarding the work comprises a software operator for operating a program or data, a work knowledge storer for storing as a work knowledge the information for an operation by the software operator, a communicator for externally transmitting communication information including a work request or a work report, and a controller for controlling, based on the work knowledge stored in a work knowledge storer, the software operator, the work knowledge storer, and the communicator.	Background of the Invention1. Field of the InventionThis invention relates to an information processing apparatus and, more particularly, to a method of constructing a software work tool used in software work on the information processing apparatus.2. Description of the Related ArtInformation processing apparatuses range from devices for processing numeric data (i.e., computers) to devices for processing general information, such as sentences, voices and images. Recently, by effectively utilizing results of research into artificial intelligence (AI), information processing apparatuses have been developed that can even handle knowledge of human beings such as natural languages.However, almost all the information processing apparatuses are based on the stored program system. Therefore, development and operation of software (i.e., programs and information such as document, specification, environment definition and data) are indispensable to the information processing apparatus' function. Work on software development and software operation involves creation of a program execution environment; activation of a program; input of information to the program; supervision of the program; decoding of the program's processed result; decoding of the program's output; and input, manipulation, output and creation of information.In work like software development, software operation, etc. a person must initially operate the software, observe the processing situation and determine the operation to be executed next.For this reason, software development and software operation takes a lot of time and money.Thus, to save time, a variety of software tools have been created on the information processing apparatus so that the software can be operated automatically. Various tools have been created to facilitate this software work and are now well known.However, all software work cannot be automated by the use of a computer and an operating system. In practice, conventional operating systems have a component called a job controller by which software activation can be supervised and the simple succeeding processing can be activated depending on the processed result. However, the mechanism for automating the software work according to the prior art is very primitive.This is because the conventional technology provides only software work tools such as job controllers in which a special tool for manipulating particular information is created and special tool groups ore activated in substantially the given order. Accordingly, if the software work becomes slightly complicated, additional works such as development and operation of special tools are needed. This hardly contributes to the saving of labor. Rather, it increases the number of software and makes the software work more complicated. In addition, these special tools are not designed to communicate with each other with respect to software work. Therefore, if a file output from a certain special tool is input to another special tool, then special tools for converting the format must be developed and operated only for that set of two special tools. Consequently, the number of special tools is markedly increased. For example, whereas 4 special tools need 6 sets, 5 special tools need 10 sets and 100 special tools need 4,950 sets.So long as software work tools are created by the conventional program creating method, they are created such that special knowledge is examined and fixed to the program. This results in the shortcoming that knowledge cannot be investigated and added with ease while the software work tool is being operated. Further, a process such as a design of a work plan in which a correct answer and an optimum solution are searched from a lot of possibilities, depends on a human being. This process frequently takes a lot of time and also frequently degrades the quality of the software work tool.An expert system and a cooperation type expert system are now available as well-known technologies resulting from research into AI technology. Since expert systems includes knowledge and an inference device and are flexible in their forms of expression, they have a characteristic which enables knowledge to be easily investigated and added while they are being operated. Further, expert systems can execute processing for searching the correct answer and the optimum solution from a lot of possibilities in a short period of time. Furthermore, in the case of cooperation type expert systems, an instruction for executing a communication between two expert systems is prepared so that the communication is frequently performed on the basis of an object-oriented calculation model which can transmit and receive information as an inference material.However, even though individual expert systems have been developed as special systems in which particular software is operated and observed by requesting the operating system, a software operation unit is not incorporated in their design. Thus, they are not useful for users who want to operate different software. Also, even if the software is the same, such expert systems are not sufficiently useful for users who need different experience and knowledge. In every specialized field, it is necessary to create a special expert system for requesting the operating system to operate the software. This problem has not yet been solved.Software tools (such as Automator marketed by Direct Technology for IBM compatible PCs), which is as well be called software robots, for use by personal computers are now commercially available in the U.S. market. According to these software tools, a picture screen, a central processing unit (CPU) register, a memory, a key depression or a supervisory program for checking the condition by reading a timer are activated on the memory, and the picture screen, the memory, an application program or data output to a host computer are carried out automatically instead of requiring a key depression by the user in accordance with a procedure and a rule described by the user. Thus, the fixed form work of the user is replaced.Let us consider the arrangement of the above software tool. Firstly, it has no communication device for another software tool of the same kind. That is, it is not provided with a communicator for transmitting and receiving communication information including work requests and work reports as will be described in this invention.Secondly, it is not designed to return the execution request result from the software via the operator or the observation unit. That is, it includes only means for judging fragmentary influences output to the hardware which might be the picture screen and the memory. In other words, it is not provided with a software operating unit which will be described with regard to the present invention.Thirdly, it has a device for storing an operation procedure given by the user. However, this operation procedure merely comprises the supervision of the hardware and the input acting for the key depression, as described above. That is, it is not provided with a work knowledge storer for storing operation programs and information operation as will be described in this invention.As described above, this software tool aims at small-scale and low-level applications in which a plurality of input programs acting for the key strokes are independently operated in parallel. In conclusion, the above-mentioned software tool lacks the features of this invention and is not intended to constitute a general purpose software work tool, as is this invention, in which work is supported by expert knowledge of software development and operation in a self-differentiating fashion.It has been very difficult to design a strong general purpose software work tool because a significant amount of time cannot be saved if experience and knowledge in a specific field of the software work (e.g., the way of erasing an unnecessary file from an external storage device) are not incorporated in the other software work tool.However, a software work tool with knowledge based on experience in a variety of special fields is too large and its performance is too poor, thus requiring frequent correction.Such a software work tool may be connected to another software work tool without a communication device by direct program access, or such that one tool writes in the file while the other reads from it. With this topology, if the design of a certain software work tool is changed, the design of the other software work tool may often be greatly changed. In this case, the two software work tools depend on each other very strongly, making software development and operation very expensive. Accordingly, there is a problem that the design and maintenance of the entire system for supporting the software work are very difficult. Further, in the article A Tool to Coordinate Tools by R. Bisiani et al., IEEE Software, Vol. 5, No. 6, November 1988, pages 17-25, a so-called planner is dislosed which inputs user specific goal and constraints, and then computes a possible tool invocation sequence making use of preliminary stored goal and constraint information about all tools. However, all information about tool are goals and constraints, and no planner's communication and cooperation ability with other planners nor bi-directional request/report communication between a planner and a human user is disclosed in this article.Summary of the InventionThis invention pertains to a method of constructing a software work tool for use in software work for an information processing apparatus.It aims at providing a general purpose software work tool for isolating and minimizing work by automatically executing software operation on the basis of information concerning the work in an autonomously distributed fashion.A software work tool in an information processing apparatus comprises a work knowledge storer for storing work knowledge information; a software operator for carrying out an operation on a plurality of programs based on the work knowledge information; a communicator for transmitting and receiving communication information including work requests and work reports to and from the software work tool and at least one additional software work tool, thereby enabling the software work tool and the at least one additional external software work tool to cooperate with each other during an operation on the plurality of programs; a controller for controlling the software operator, the communicator and the work knowledge storer based on the work knowledge information stored in the work knowledge storer; and an observator for observing the programs operated on by the software operator comprised within the software work tool and for observing programs operated on by at least one software operating device provided within the at least one additional external software work tool. BriefDescriptionoftheDrawingsA better understanding of the objects, features and advantages of the invention can be gained from a consideration of the following detailed description of the preferred embodiments thereof, in conjunction with the figures of the accompanying drawings, wherein: Figure 1A is a block diagram used to explain a principle of the first embodiment of the present invention;Figure 1B is a block diagram used to explain a principle of the second embodiment of the present invention;Figure 2 is a block diagram showing an overall arrangement of the embodiment of this invention;Figure 3 is a flowchart to which references will be made in explaining the embodiment of a processing of a software operator;Figure 4 is a schematic diagram showing an embodiment of software operation request information;Figure 5 is a schematic diagram showing an embodiment of an execution command supplied from the software operator to an operating system;Figures 6A through 6D are schematic diagrams showing an embodiment of information sent to a controller from the software operator;Figures 7A through 7E are schematic diagrams showing an embodiment of contents of a work knowledge base;Figure 8 is a flowchart to which reference will be made in explaining an embodiment of a processing of a communicator;Figure 9 is a flowchart to which reference will be made in explaining an embodiment of a processing of an inference engine;Figure 10 is a flowchart to which reference will be made in explaining an embodiment of a processing of an observer;Figure 11 is a schematic diagram showing an embodiment of contents of an internal memory used in the observer;Figure 12 is a block diagram showing an arrangement of an embodiment for carrying out a processing based on a frame;Figures 13A through 13D are block diagrams showing an arrangement of an embodiment for carrying out a processing based on an object;Figure 14 is a block diagram showing an arrangement of an embodiment having a back-track device;Figure 15 is a block diagram showing an arrangement of an embodiment having a meta-knowledge and a knowledge concerning an inference process;Figure 16 is a schematic diagram showing an embodiment of a cooperation processing done among a software work tool group having a blackboard and an agenda;Figures 17A and 17B are schematic diagrams showing an embodiment in which a work knowledge storer is provided with a procedure description;Figures 18A through 18C are schematic diagrams showing an embodiment in which the work knowledge storer is provided with a knowledge input in the format of a logical chart diagram;Figures 19A through 19C are schematic diagrams showing an embodiment in which the work knowledge storer is provided with a knowledge input in the format of a decision table;Figures 20A through 20C are schematic diagrams showing an embodiment in which the work knowledge storer is provided with a knowledge input in the format of a state transition diagram;Figures 21A through 21F are schematic diagrams showing data of a list structure, a tree structure or a graph structure included in the work knowledge storer;Figure 22 is a block diagram of one of a number of computer systems in an embodiment for their coordination; andFigure 23 shows an actual application of this invention.DetailedDescriptionofthePreferredEmbodimentsPrior to the description of the preferred embodiments of the invention, principles of this invention will be described below with reference to Figures 1A and 1B.Figures 1A and 1B are block diagrams showing principles of this invention, to which references will be made in explaining principles of a software work tool used in a variety of an information processing apparatuses.Figure 1A shows the principle of the first embodiment of the present invention. As shown in Figure 1A, a software operating unit 1 executes an operation on a program provided as a software or as information. A work knowledge storer 2 is a work knowledge base which, for example, stores a method and a sequential order of operation done by the software operating unit 1 or information used to determine a logical execution condition.A communicator 3 directly or indirectly transmits/receives a work request, a work report or information about a conversation between it and the user, the operator or other similar software work tools. A controller 4 executes various control operations to instruct the software operating unit 1 to perform the operation, the communicator 3 to perform the communication and the work knowledge storer 2 to update the work knowledge on the basis of the work knowledge stored in the work knowledge storer 2.Figure 1B shows the principle of the second embodiment of the present invention. Comparing Figures 1A and 1B, the arrangement of Figure 1B is the same as that of Figure 1A except that an observer 5 is added. The observer 5 is adapted to observe a software provided as an operated result of the software operating unit 1 within its software work tool or of a software operator of another software work tool which executes the operation on the above-mentioned program or information.In this invention, the work knowledge storer 2 includes various kinds of knowledge, such as production rules, frames, objects, meta-knowledge and so on. The controller 4 controls the software operating unit 1 to execute the operation on the software on the basis of the information stored in the work knowledge storer 2, information received from the communicator 3 or information input from the observer 5, adds information to the work knowledge storer 2 or changes information, and communicates with other software work tool via the communicator 3.Cooperation in work among a plurality of software work tools is achieved by the communication and, if communication protocols are integrated, the software work tools can be connected very easily and the number of the software work tools connected can be increased. Then, it becomes possible to execute the work that should be executed within its tool while affecting the external software.More specifically, the software work tools include work knowledge storers and are designed to cooperate with each other via communication. Therefore, experience and knowledge in the special field of the software work, e.g., a method of erasing an unnecessary file from an external storage device, can be utilized independently by the individual software work tools. Further, the software work tools are connected to the outside by means of communication information so that, even if the design of the knowledge in a certain software work tool is changed, the change of the knowledge in other software work tool is very small, thus greatly simplifying the design and maintenance of the entire system for supporting the software work.Furthermore, by using inference engineering, the process of searching for a correct answer and an optimum solution from many possibilities can be made simple. For example, when a work schedule is planned by combining element works or when a cause of fault in the software, is investigated, a better solution can be obtained in a short period of time.Figure 2 is a block diagram showing an overall arrangement of an embodiment of a system in which two software work tools are connected. Referring to Figure 2, it will be seen that two [2] software work tools A and B are connected via a message switcher 6 and the two software work tools A and B are activated by a work tool activator 7 to execute operation on a software 10. Similarly to software work tool 6 shown in Figure 1B, two [2] software work tools A and B respectively comprise software operators 1a and 1b, work knowledge bases 2a and 2b, communicators 3a and 3b, inference engines 4a and 4b, and observation units 5a and 5b. The work knowledge bases 2a and 2b form the work knowledge storer 2 shown in Figures 1A and 1B. The inference engines 4a and 4b form the controller 4 shown in Figures 1A and 1B.Operation of software work tools A and B will be described in accordance with circled reference numerals 1 ○, 2 ○, .... shown in Figure 2. 1 ○ The user U supplies the message switcher 6 with a message requesting desired work.2 ○ When the message, switcher 6 detects that the work should be done by software work tool A, software work tool A is not yet activated and therefore the message switcher 6 requests the work tool activator 7 to activate software work tool A.3 ○ The work tool activator 7 loads software work tool A to a main memory from an external storage device (not shown) and activates an inference engine 4a.4 ○ The message switcher 6 transmits the request message from the user U to communicator 3a of activated the software work tool A.5 ○ The communicator 3a receives the request message, checks the message and decodes accompanying information.6 ○ The inference engine 4a sequentially determines and executes rule-type knowledge satisfying logical conditions from work knowledge base 2a by a process corresponding to the message or according to the knowledge. Also, inference engine 4a reads and writes frame type knowledge from and in work knowledge base 2a. The rule type knowledge is an inference rule formed by a combination of the logical execution condition and the processing method, and the frame type knowledge is a knowledge which describes a relation between a frame provided as a unit of data corresponding to a certain concept and a program, and a plurality of frames.7 ○ An inference engine 4a instructs software operator 1a to execute the software operation described by the knowledge. Software operator 1a includes an input file N1 of a software S1. It produces an execution command of the software S1 and requests the operating system to execute the above command such that the software S1 is operated. Further, inference engine 4a supervises the operation of the software S1. If the activation fails, inference engine 4a reads a method of recovering the failure from work knowledge base 2a and instructs the software operator 1a to execute the process.8 ○ Observation unit 5a receives from the operating system information indicating that the output of the software S1 is produced, and decodes an output P1. Knowledge for decoding the output P1 might be stored in work knowledge base 2a. Consequently, if a new software operation becomes necessary, an instruction is supplied to software operator 1a.9 ○ When requesting work of another software work tool or when requesting a knowledge of another software work tool, inference engine 4a supplies the requested work to the communicator 3a. The communicator 3a supplies its work request message to the message switcher 6. When the message switcher 6 detects that the software work tool which should execute the work is software work tool B , then software work tool B is not yet activated and requests the work tool activator 7 to activate software work tool B.The work tool activator 7 loads software work tool B to the main memory from the external storage device (not shown) and activates inference engine 4b.The message switcher 6 sends the request message to communicator 3b of thus activated software work tool B.Inference engine 4b also sequentially determines and executes rule type knowledge satisfying logical conditions from work knowledge base 2b by the process corresponding to the message or according to the knowledge. Also, inference engine 4a reads and writes frame type knowledge from and in work knowledge base 2b.Observation unit, 5b observes that the output P1 of the software S1 is output.Inference engine 4b and work knowledge base 2b infer that a software 52 must be activated to receive the output P1 in order to obtain an output P2 desired by the user. Inference engine 4b instructs the software operator 1b to make a request to the operating system such that the software S2 is activated.When observing that the output P2 is outputted, then software operator 1b analyzes and infers the output P2 in detail and examines whether or not it contains the information desired by the user.Inference engine 4b makes a work report and instructs communicator 3b to send the same to the message switcher 6.The message switcher 6 sends a message to communicator 3a of software work tool a.Inference engine 4a examines the work result on the basis of knowledge on work knowledge base 2a. If the examined result is satisfactory, then inference engine 4a instructs communicator 3a to send a work completion message to the user U.Software work tool A has no work to do, so it saves the knowledge base in an external storage device (not shown) and it thus disappears from main storage. Software work tool B remains in main storage, so it can work independently whenever an event of the same kind is observed.Figure 3 is a flowchart to which reference will be made in explaining the embodiment of the processing of the software operator.Referring to Figure 3, following the Start of operation, it is determined in decision step S20 whether or not the request is the software operation request from inference engine 4a. If it is, as represented by a YES at decision step S20, then the process proceeds to step S21, whereat an input file addressed to the software is created from the request information, if necessary. In the next step S22, a software execution command is created and in the next step S23, the execution command is sent to the operating system of this software work tool to request the activation.In the next decision step S24, it is determined whether or not the operating system normally receives the execution command. If the execution command is normally received by the operating system as represented by a YES at decision step S24, then the processing proceeds to step S25, whereat information indicating that the execution command is normally received by the operating system is sent to inference engine 4a. In the next step S26, a time-out notification after an elapse of a supervisory time is requested to the operating system and then the processing is returned to step S20. If, on the other hand, the execution command is not normally received by the operating system, as represented by a NO at decision step S24, then the processing proceeds to step S27, whereat error information indicating activation failure is sent to inference engine 4a, and then the processing is returned to step S20.If the request is not the software operation request from inference engine 4a, as represented by a NO at decision step S20, the processing proceeds to the next decision step S28. In decision step S28, it is determined whether or not the information is the ending information for the activated software from the operating system. If it is, as represented by a YES at decision step S28, then the time-out notification request to the operation system is canceled at step S29, the output file of the software is checked at step S30, an error message is checked at step S31 and a completion code is checked at step S32, and the information that the software is normally ended is sent to inference engine 4a and then the process is returned to the decision step S20.If the information is not the software ending information from the operating system as represented by a NO at decision step S28, then the process proceeds to the next decision step S34. In step S34, it is determined whether or not the information regards a time-out notification from the operating system. If the information regards the time-out notification as represented by a YES at decision step S34, the process proceeds to the next decision step S35. It is determined in decision step S35 whether or not the activated software is ended. If it is, as represented by a YES at decision step S35, then the ending information and the error information of the execution failure are both sent to inference engine 4a at steps S36 and S37 and then the processing is returned to step S20. The error information notified here indicates that an unexpected event caused the software operation to fail and terminate.It the activated software is not ended, as represented by a NO at decision step S35, the processing proceeds to step S38, wherein the request for a forced ending is sent to the operating system and the error information of the execution failure is transmitted to the inference engine 4a in step S39. Then, the processing is returned to the processing in step S20. Further, if the information does not regard a time-out notification, as represented by a NO at decision step S34, then the process is immediately returned to step S20. The error information transmitted in step S39 indicates that the software operation is compulsorily terminated because the execution time exceeds the limit value.Figure 4 shows an embodiment of software operation request information supplied to the software operator.Referring to Figure 4, the operation request information comprises execution command knowledge (a) and timer supervisory time (b).Figure 5 shows an embodiment of an execution command supplied from the software operator to the operating system.Figure 6 shows an embodiment of information sent to the controller from the software operator. Diagrams in Figure 6A and 6B show examples of information upon execution reception and illustrate normal reception and abnormal reception.Diagrams in Figure 6C and 6D show examples of the sent information upon execution completion and illustrate examples of normal completion and abnormal completion.Figures 7A through 7E show an embodiment of contents of a work knowledge base. Figure 7A shows the entire content in which the content of the work knowledge base is composed of a method 41, a procedure 42, a rule 43, tree structure knowledge 44 and object control knowledge 45.Figure 7B shows an example of a method which utilizes a selector name received by the software work tool from the communicator as identification data, and a list of arguments as parameters.Figure 7C shows an example of the procedure 44 which utilizes a command group defined as functions accessed from the rule.Figure 7D shows the embodiment of the rule 43, formed as a set comprising of a condition part for inference and a command.Figure 7E shows an example of the tree structure knowledge 44. The tree structure knowledge stores data and facts in the tree structure, and the method, the procedure and the rule may also be considered as a kind of tree structure knowledge. The object control knowledge 45 includes names and high and low relations as tree structure data for carrying out management functions such as retrieval and generation and erasure of the method, the procedure, the rule and the tree structure knowledge.Figure 8 shows a flowchart of the embodiment of the process executed by the communicator.Referring to Figure 8, following the Start of operation, it is determined in decision step S47 whether or not the activation information is issued from the message switcher 6 shown in Figure 2. If a YES is output, then a character string of the message is received by the work knowledge base 2a and the format of the message is checked at step S48. Then, accompanying information is decoded at step S49, the format of the accompanying information is arranged at step S50, the message is supplied to the inference engine 4a at step S51 and then the processing is returned to decision step S46.If the information is not the activation information from the message switcher 6 as represented by a NO at decision step S46, then the process proceeds to the next decision step S52. It is determined in decision step S52 whether or not the information is the activation information from the inference engine 4a. If a YES is output, then the format of the request message is checked at step S53, the format of the request message is arranged as a transmission message at step S54, the message switcher 6 is activated at step S55, a character string of the message is supplied from the work knowledge base 2a to the message switcher 6 at step 56, information indicating that the character string of the message is normally transmitted to the message switcher 6 and sent to the inference engine 4a at step S57, and then the process is returned to decision step S46. If the information is not the activation information from the inference engine 4a as represented by a NO at decision step S52, then the process is immediately returned to decision step S46.Figure 9 is a flowchart of the embodiment of the processing done by the inference engine.Referring to Figure 9, following the Start of operation, it is determined at decision step S60 whether or not information from the communicator 3a is received. If it is, as represented by a YES at decisions step S60, then the process proceeds to step S61. In step S61, messages whose message selectors as described in connection with Figure 7 are coincident, are searched from the work knowledge base 2a. Then, arguments thereof are compared at step S62 and a procedure stored in the work knowledge base 2a is decoded at step S63 to thereby execute the command. In the next step S64, a presently effective rule group whose condition is established is searched from work knowledge base 2a and it is determined in decision step S65 whether or not a rule group exists whose condition is established. If there is such a rule group, as represented by a YES at decision step S65, then a command corresponding to that condition is executed at step S66 and the steps following step S64 are repeated. If there is no rule group whose condition is established, as represented by a No at decision step S65, the process is returned to decision step S60.The rule group whose condition is established is searched at steps following step S64 after the command has been executed at stop S63 because the inference engine 4a must search a rule group whose condition is established from the rule groups when a value of a variable X indicating the number e.g. of incoming partners, is changed from zero [0] to three [3] by the command execution in step S63.More specifically, if the rule if X>1, always then Y=2 and ring a bell exists within the work knowledge base 2a, then the value of X is changed from zero [0] to three [3] in step S63, thereby making this rule effective and necessitating the rule group to be examined and bell to be rung. Further, if rule if Y=2, then always print a picture exists, then it is discovered by checking the rule group in step S64 and the rule is printed on the screen. As described above, the rule is checked in steps S64 and S65 until no rule remains to be activated. When it is determined that no rule exists, the process is returned to decision step S60, whereat it is determined whether or not the information from the communicator 3a is received.If it is not, as represented by a NO in decision step S60, then the process proceeds to the next decision step S67. In decision step S67, it is determined whether or not the information from observation unit 5a is received. As will he described later, when a certain event takes place, an event identifier and detailed information such as on an error code, a time and so on are sent from the observation unit 5a as information associated with the event so that, if the information from the communicator 3a is received, an instruction corresponding to the event is executed by the associated information received at step S68. Thereafter, similarly as described before, an instruction corresponding to an effective rule group whose condition is established is executed in steps following step S64. If the information from observation unit 5a is not received, as represented by a NO at decision step S67, then the process proceeds to the next decision step S69. It is determined in decision step S69 whether or not the information is a report from software operator 1a. A typical example of a reported content from software operator 1a is as follows. When inference engine 4a, for example, supplies an instruction to software operator 1a such that the software operator 1a activates a program p, then the software operator 1a requests the operating system to activate the program p and reports the normal work ending at a timing point in which software operator 1a recognizes that the work is ended normally. Also, at that time, if the supervision of 60 minutes is executed by the observer 5a, then the abnormal state in which the program p, which is normally ended within a few minutes, is not ended after 60 minutes is detected by a timer and a detected result is reported to the inference engine 4a. This is a typical example of the content received by the observation unit 5a at decision step S69.If the information that the program p is ended normally is reported from the software operator 1a, as represented by a YES at decision step S69, the process proceeds to step S70. in step S70, a return information is supplied to the software operation instruction currently being executed and the next instruction is executed. For example, if two [2] instructions are written in the software operation instruction as (execute a program p) (input the result and execute q) and if the above two [2] instructions are respectively stored in addresses 200 and 230, inference engine 4a stores address 200 at the timing at which it requests the software operator 1a to execute the program p and receives the return information that the program p is ended normally at a timing at which the process is returned from the software operator 1a. Consequently, to advance the address 200 to the next address 230 such that the instruction execute q is executed, the program q is executed by the software operator 1a. In that case, if a list of employees is returned in the program p, then such data is supplied to the program q as return information and data involving a list of wages is returned. Thus, the return information may be expanded into a variety of data.The operation in which the instruction execution is continued in step S70 not only means that the instruction next to the instruction P halted by request is executed but also means that, as far as possible, instructions arranged in the procedure type are executed sequentially. If the instructions are completely executed in step S70, the processing proceeds to step S64, whereat the existence of instructions to be executed by the rule unlike the procedures which are supplied sequentially, is determined. Further, if the information is not the report from software operator 1a, as represented by a NO at decision step S69, then the process is immediately returned to the decision step S60, whereat it is determined whether or not the information from the communicator 3a is received.Figure 10 shows a flowchart to which reference will be made in explaining the processing of the observer according to the embodiment.As shown in Figure 10, following the Start of operation, it is determined in decision step S80 whether or not the information is the observation request from the inference engine 4a. This observation request is frequently carried out at the same time when the inference engine supplies an instruction to the software operator. When the observation is carried out constantly, the observation is requested soon after the software work tool is activated and thereafter events occurring regardless of the software operation timing, that is, events occurring asynchronously, are supervised sometimes.If the information is the observation request from the inference engine 4a as represented by a YES at decision step S80, then the process proceeds to step S81, whereat information of an event to be observed and an event judging process are received from the work knowledge base 2a and stored in the internal memory of the observation unit 5a. In the next decision step S82, it is determined whether the event to be observed is a timer activation event or a message activation event. If it is a timer activation event, then the process proceeds to step S83, whereat the operating system is requested which receives a timer activation instruction after a certain time. Then the process is returned to decision step S80. If on the other hand the event to be observed is the message activating event, then no process is executed and the process is returned to decision step S80.The timer activation request made in step S83 is made such that when an electronic mail arrival is examined every ten [10] minutes, for instance, the operating system is requested to timer-activate observer 5a after every elapse of ten [10] minutes.If the information is not about the observation request from inference engine 4a, as represented by a NO at decision step S80, then the process proceeds to the next decision step S84. It is determined in decision step S84 whether the information is the timer activation instruction from the operating system. If it is, as represented by a YES at decision step S84, the event decision process is accessed from the internal memory and executed at stop S85. In the next decision step S86 it is determined whether or not the resultant event is treated as an occurrence of an event. If a YES is output at decision step S86, then the above event and the information of the event decision process are deleted from the internal memory at step S87. In the next step S88, as described before, the event identifier and detailed information such as the error code, the time and the like of that event are, if necessary, transmitted to the work knowledge base 2a as the associated information of the event that occurred and the occurrence of the event is reported to the inference engine 4a in step S89. Then the process is returned to decision step S86. If a NO is output in step S86, then the processing is returned through step S83 to decision step S80.Here, as a concrete example of event judgment process executed in S85, a case is explained where a received electronic mall is from a boss, assuming that the electric mail arrival is examined every ten [10] minutes, as described earlier. A First Step: The number of mails delivered to a file called an electronic mail box is counted.A Second Step: If the number is zero [0] the process terminates, or go to the next step otherwise.A Third Step: One [1] electronic mail is read, and if there is none the process terminates.A Fourth Step: It is judged whether or not the originator of the electronic mail is a boss. The process continues to the next step if the judgment is affirmative, or reverts to the third step if the judgment is negative.A Fifth Step: Because a boss originates the electronic mail, the electronic mail is considered as an urgent mail. A message A mail has arrived from a boss. Please see the mail box as soon as possible. is displayed on a monitor. Then, the process from the third step is repeated.In such an event judgment process, it is assumed that the head end address of the process procedure is stored in a later described function address column shown in Figure 11.If the information is not the timer activation request from the operating system, as represented by a NO at decision step S84, then the process proceeds to the next decision step S90. In decision step S90, it is determined whether or not the information is a message from the operating system. If it is, as represented by a YES at decision step S90, the process proceeds to the next step S91, whereat it is determined by the internal memory whether or not the message is the message event to be requested. A checked result is determined in the next decision step S92. If the message is the message event requested, as represented by a YES at decision step S92, then in the next step S93 a decision process corresponding to the message event is accessed from the internal memory and executed. It is determined in decision step S94 whether or not the message event is treated as the occurrence of an event. If it is, as represented by a YES at decision step S94, then the process is returned to decision step S80 through steps S87 through S89. Further, if the information is not a message from the operating system, as represented by a NO at decision step S90, and if the event is not the requested event, as represented by a NO at decision step S92, then the process is immediately returned to decision step S80.Figure 11 shows an embodiment of the content of the internal memory in the observer.Referring to Figure 11, after the busy display, 0 in non-use and 1 in use, the type of event to be observed, 1 in the timer activation and 2 in the message activation, is stored, and a timer interval and an address of a function for executing the event decision process are stored for the timer activation event. Also, a message identifying information and an address of a function for executing the event decision process are stored for the message activation event.Figure 12 is a block diagram of the arrangement of an embodiment in which processing is carried out on the basis of a frame. Figure 12 corresponds to Figure 1 and shows only portions which need be described. In this case, a frame means a frame of knowledge used to solve the problem and in which data corresponding to a certain concept, a program and a relation with another concept are described as a unit according to the format of this frame. The concept of a passenger seat 101, for example, includes a date, a train number, a seat number and the existence or absence of a reservation as data concerning the concept of the seat. It also includes a vacant situation inquiry, reservation and cancel as associated programs. Further, the relation indicates an entirety versus portion relation such that the seat frame 101 comprises a reserved seat frame 102 and an unreserved seat frame 103 and also indicates a general versus special relation such that a non-smoking reserved seat frame 104 is a kind of reserved seat frame 102. An inference engine 107 based on the frame goes from a special concept back to a general concept, accesses date and program, and makes an inference by utilizing the entirety versus portion relation.Figure 13 is a block diagram showing the arrangement of the embodiment in which the processing based on an object is executed. As shown in (a) in Figure 13, the work knowledge storer includes a seat object 110, a reserved seat object 111 and a ticket issuing object 112. A controller comprises a fundamental unit 113 and a processing unit 114 based on the object. Diagram (b) in Figure 13 shows a charge inquiry process provided in the inside of the seat object 110, diagram (c) in Figure 13 shows a reservation process provided in the inside of the reserved seat object 111, and diagram (d) in Figure 13 shows the content of a ticket issuing process provided within the ticket issuing object 112.When an instruction for sending a message to the knowledge specified by the object is executed by the controller, the processing unit 114 based on the object reads the process identified by the message from the designated processing, i.e. method, and executes the same. Even when the charge inquiry message is sent to the reserved seat object 111, the reserved seat object has no such processing. However, from a succession relationship, the reserved seat object 111 is related to the seat object 110 in the form of a parent and child relationship so that the processing unit 114 based on the object activates the charge inquiry processing of the seat object 110.Figure 14 is a block diagram showing the arrangement of an embodiment provided with a back-tracking device.As shown in Figure 14, the work knowledge storer 2 stores therein data 1 ○ and data 2 ○ and rules 3 ○ through 6 ○.An inference engine 116 within the controller executes a backward inference in order to prove X = true. More specifically, since X lies on the right-hand side of rule 4 ○, the inference engine 116 infers that B is true. Also, since B lies on the right-hand side of rule 3 ○, the inference engine 116 infers that A is true. However, they are not coincident with data because of the data 1 ○, and the inference engine 116 fails in its inference. At this time, the back-tracking device 117 returns the content of an inference work memory 118 varied in the process of the above-mentioned inference and makes an inference for the next case. In that case, since a result C is true, D becomes true so that an inference result in which X becomes true is derived.Figure 15 is a block diagram showing the arrangement of an embodiment in which processing based on meta-knowledge and processing based on a knowledge concerning the inference process are executed.As can be seen in Figure 15, the work knowledge storer stores therein general knowledge 120 concerning a processing object, knowledge concerning knowledge itself, i.e., meta-knowledge 121 and knowledge 122 concerning an inference process, and a controller comprises an inference engine 124 based on the meta-knowledge and an inference engine 125 based on the knowledge concerning the inference process.Let it be assumed that the meta-knowledge 121 includes knowledge, i.e., metaknowledge, in which once a rule whose description begins, for example, when a symbol a is executed, such a rule cannot be executed again in the inference. Then, when the inference engine 124 based on the metaknowledge decodes this metaknowledge, the fundamental unit 123 carries out such control for the inference using the general knowledge 120 by using the information of the decoded metaknowledge.Further, let it be assumed that knowledge expressed by (max - rule = 10000) in which an abnormal end is effected if the rule executed in the inference 10,000 times or more is stored as the knowledge 122 concerning the inference process. When the inference engine 125 based on the knowledge concerning the inference process decodes that knowledge, then the fundamental unit 123 executes such control on the inference using the knowledge 120.Figure 16 is a black diagram showing the arrangement of an embodiment which utilizes a blackboard and an agenda.As shown in Figure 16, three software work tools 127, 128 and 129 are generated in the inference process, and cooperate with one another in inference by using a blackboard 130 provided as a memory in which information used in the inference are written and an agenda (i.e., memorandum) provided as a memory in which information concerning a solved problem and an unsolved problem are written. The respective software work tools 127, 128 and 129 include accessing means 132, 133 and 134 for accessing the blackboard 130 and the agenda 131.As shown in Figure 16, if the software work tool 127, for example, reserves a seat and writes a reservation date, a car number and a seat number in seat data on the blackboard 130, then the software work tool 129 immediately starts to calculate the charge on the assumption that the software work tool 129 has a rule for calculating a charge on the basis of the seat data, and writes charge data in the blackboard 130. Then, in response thereto, the software work tool 128 transmits seat data and charge data to a terminal of a station. Thus, the work is executed by the cooperation of the software work tools 127, 128 and 129 as described above.Also, the cooperative work is executed as follows. If the software work tool 128 writes want to obtain seat data and want to obtain charge data in the agenda 131, then the software work tool 127 reserves a seat and the software work tool 129 calculates a charge and rewrites the problem on the agenda 131 as a solved problem.Figure 17 is a block diagram showing the arrangement of an embodiment in which the work knowledge storer includes a procedure description indicative of work. As shown in Figure 17A, the work knowledge storer stores a procedure. The procedure describes work in the form of instructions arranged in a sequence and the controller 4 sequentially executes them.In particular, when the procedure is provided in the form of the tree structure shown in Figure 17B, the instructions are executed in the sequence of instruction 1, instruction 2, instruction 3, instruction 4 and instruction 5, according to the rule.Figure 18 shows an embodiment in which the work knowledge storer includes information input in the format of a logic chart diagram. As shown in Figure 18A, a logic chart diagram 140 is supplied to the work knowledge storer 2 as information whose format is converted by a converter 141, i.e., by a procedure 142. The logic chart diagram 140 graphically illustrates the processing flow as shown in Figure 18B and this logic chart diagram 140 is equivalent to procedure knowledge shown in Figure 18C.Instead of the above embodiment in which the software work tool includes the converter 141 and the converter 141 converts the input logic chart diagram into the procedure knowledge 142 and stores the same into the work knowledge storer 2, a variant of this embodiment may be considered as follows. The logic chart diagram 140 is not converted, but is directly stored in the work knowledge storer 2 and the controller of the software work tool carries out the condition decision, the repetition and the instruction execution in accordance with the logic chart diagram 140.Figure 19 shows an embodiment in which the work knowledge storer includes information input in the format of a decision table. In this embodiment, as shown in Figure 19A, information input in the format of a decision table 145 is converted into procedure knowledge 147 by a converter 146 and stored in the work knowledge storer 2. As shown in Figure 19B, the decision table 145 shows combinations of condition decision and instruction execution in the form of a table. In the decision table 145, one case is illustrated in a column, where Y represents a YES and N represents a NO. The first column shows that, when conditions 1 and 2 are YES, only instruction 1 is executed. Diagram in Figure 19C shows that the decision table shown in Figure 19B is converted into procedure knowledgeInstead of the above embodiment in which the converter 146 of the software work tool converts the decision table 145 into the procedure knowledge 147, a variant of this embodiment may be considered as follows. The decision table 145 is directly stored in the work knowledge storer 2 and the controller of the software work tool carries out the condition decision and the instruction execution in accordance with the decision table 145.Figure 20 shows an embodiment in which the work knowledge storer includes information input in the format of a state transition diagram. In Figure 20A, information input in the format of a transition diagram 150 is converted into a rule 152 by a converter 151 and then stored in the work knowledge storer 2. The state transition diagram is a diagram of the format such that, as shown in, Figure 20B, the state of a certain thing is represented by an open circle, the state transition is represented by an arrow and the condition and the processing in the transition are described on the side of the arrow. A rule statement shown in Figure 20C is equivalent to the state transition diagram shown in Figure 20B.Instead of the embodiment in which the input state transition diagram 150 is converted into the rule knowledge 152 by the software work tool converter 151, such a variant of the embodiment may also be considered, in which data of the state transition diagram is directly stored in the work knowledge storer 2 and the controller 4 of the software work tool carries out the condition decision and the instruction execution in accordance with the state transition diagram.Figure 21 shows an example of knowledge in the embodiment in which the work knowledge storer stores information of a list structure, a tree structure or a graph structure as knowledge. Diagram in Figure 21A shows an example of data of the list structure wherein data A, B and C are arrayed in that order. The diagram in Figure 21B shows an example in which data is converted in the format indicating the list structure.Diagram in Figure 21C shows an example of knowledge of the tree structure, in which data A, B, C and D are provided in the form of lists, which might be called a tree structure because the list is branched like a tree. Diagram in Figure 21D shows an example in which data in of Figure 21C is converted into the format indicating the tree structure.Diagram in Figure 21E shows an example of knowledge of the graph structure, in which branches are extended from arbitrary nodes. Diagram in Figure 21F shows an example in which the knowledge in of Figure 21E is converted into the format indicating the graph structure.When the software work tools described in detail above are used, it becomes crucial to interlink them across multiple systems.Figure 22 is a block diagram of an embodiment of a computer system for performing such interlinked operations.Figure 22 shows the configuration of one of the multiple computer systems connected through the network. This system comprises a controller 200, a storer 201, and a man-machine interface 202 including a monitor and a keyboard.The controller 200 comprises a soft robot 210 as a software tool of this invention, the message exchange mechanism 211 described earlier, a software tool booting-up mechanism 212, an editor 213 as a system editing program, a screen/operation controller 215 for an operating system (OS), and a communication controller 216 for the operating system (OS). The storer 201 internally stores both a work list file 214 for storing works performed by the soft robot 210, which are searched by editor 213, and a work knowledge base 217 as an external memory for the work knowledge base within the soft robot 210.As shown in Figure 22, the software work tool, i.e. the soft robot 210, is highly versatile having the ability to standardize the representations of its work irrespective of the computer model or the kind of operating system (OS). It is apparent from the examples of character codes that different computers express data differently. However, an appropriate intermediary can interlink different expressions, e.g. by a character code conversion process, across computers.An automatic operation of such a conversion tool by the software work tool, i.e. a soft robot 210, enables the data formats exchanged on the network to be uniform. An automatic exchange of uniform format data, e.g. by the message exchange mechanism 211, into those conforming to the home system computer format, when respective soft robots receive them or send them to the network, enables the data to be processed according to the format used by the home system.Alternatively, it is possible to standardize the data handled by soft robots, such that the software operators in the soft robots convert the standardized data into formats conforming to the operating system of the home system computer.As described above, this invention is distinguished by its ability to describe work knowledge by masking dependency on a computer model or its operating system. Thus, it has an epoch-making significance as a means of executing software in a distributed environment comprising different computer models.A further application of this invention is described in detail by referring to Figure 23.Figure 23 shows the usage of the soft robot when an operative A manipulating the computer system 220 finds a fault therein and asks a developer B to investigate the matter within the same system 220.As shown in Figure 23, upon finding an abnormality, the operative A asks the soft robot 221 as his/her personal secretary for a fault investigation in [1]. The soft robot 221, as A's secretary, calls from a software operator a software tool called an editor 224 as an editing program, adds a work item, and receives a notification from the editor 224 of a normal termination.The soft robot 221, as A's secretary, gives a fault investigation soft robot 223 the information from the operative A in [2] and asks for the fault investigation. Upon receiving the request for the fault investigation, the fault investigation soft robot 223 returns a response of a normal request reception to the soft robot 221 as A's secretary.The fault investigation soft robot 223 creates a fault report file 228 by using an editor 226. It tries to analyze the contents of the fault from its own knowledge. However, it cannot sufficiently analyze the contents, so it asks the developer B for help. Then, the fault investigation soft robot 223 sends a message to a soft robot 222 as B's secretary in [3] requesting B's assistance.The soft robot 222, as B's secretary, finds B's schedules from B's work list 229 by using an editor 225. If it is found that B has spare time, editor 225 notifies the fault investigation soft robot 223 of the acceptance of the fault investigation request.The soft robot 222, as B's secretary, calls up the computer immediately if it is already logged on to it. Otherwise, it logs on to the computer and then the soft robot 222, as B's secretary, notifies the content of a work request, i.e. fault investigation, in [4]. At the same time, the soft robot 222, as B's secretary, adds the fault investigation to B's work list 229 by using the editor 225.The developer B analyzes the fault phenomenon to find the cause and plans the correction. Upon completion, the developer B notifies the soft robot 222, as B's secretary, of the solution for the fault in [5]. The soft robot 222, as B's secretary, writes to B's work list 229 the results of the fault investigation work by using editor 225. These data are stored for future reference.The soft robot 222, as B's secretary, notifies the fault investigation soft robot 223 in [6] of the normal completion of the fault investigation and sends information regarding the cause of the fault and the necessary corrective action. The fault investigation soft robot 223 writes to a work report file 228 the cause and correction by using editor 226. The fault investigation soft robot 223 sends to the soft robot 221 as A's secretary a message that the operative A who requested the work return an acknowledgement in [7]. After sending the fault report to the soft robot 221 as A's secretary, the fault investigation work is completed.The soft robot 221, as A's secretary, shows a fault report to the operative A in [8] and confirms A's satisfaction by the result to determine the completion of A's fault investigation work. The soft robot 221, as A's secretary, writes to a column of the fault investigation work in A's work list 227 the work completion by using editor 224. These data are stored for future reference.As described above, the use of a soft robot as a software work tool of this invention enables the soft robot to retain the knowledge corresponding to the fault investigation. This makes it possible, for instance, for the fault investigation soft robot 223 to make a request to C when the developer B is absent. Also, because a fault report file is created, if similar kinds of subsequent faults are created, they can be handled automatically.In addition to the embodiments described in detail above, the following embodiments may be considered: an embodiment in which the work knowledge storer 2 includes an inference rule or fact involving an expression of ambiguity or confidence or probability or uncertainty except true or false value in order to derive the work procedure, and the above-mentioned controller 4 includes therein an inference engine for executing an inference engineering (involving fuzzy inference and inference with confidence) on the basic of the inference rule or fact;an embodiment in which the work knowledge storer 2 includes an inference rule or fact involving an expression of inevitability and accident or an expression of true or false on the time base in order to derive the work procedure, and the above controller 4 includes therein an inference engine which executes an inference engineering (inference based on modal logic or tense logic) based on the inference rule or fact;an embodiment in which the work knowledge storer 2 includes an inference rule or fact involving an expression such that a variable range is classified into a range in which the variable falls in order to derive the work procedure and the above controller 4 includes therein an inference engine which executes an inference engineering (qualitative inference) based on the inference rule or fact;an embodiment in which the observer 5 or the work knowledge storer 2 or the communicator 3 or the controller 4 includes a pattern recognition device or information processing device which imitates a nerve cell of brain nervous system (i.e., neuro simulator);an embodiment in which the software operator 1 includes means for operating the hardware via a software provided by a system (i.e., an operating system);an embodiment in which the observer 5 includes means for observing the hardware via a software provided by a system (i.e., an operating system);an embodiment in which in an information processing apparatus housed in a mechanical apparatus similar to a robot or in an information processing apparatus for controlling the robot from outside the software operator 1 or the communicator 3 includes means for outputting information for operation of the robot or the state change of the robot or for output from the robot to the external world through a control program of the robot;an embodiment in which in an information processing apparatus housed in a machine apparatus similar to a robot or in information apparatus for controlling the robot from outside the above observer 5 or the communicator 3 includes means for inputting a state observed by the robot from the external world or the state of the robot through the control program of the robot;an embodiment which includes a timer for transmitting an interrupt signal to the above controller 4 when a certain time is passed for control;an embodiment which includes a clock for holding date or day-of-week or time and to which the above controller 4 can input data;an embodiment which includes a watchdog timer for receiving a signal from the above controller 4 of the software work tool at a predetermined time interval in the normal state and for transmitting an interrupt signal to the controller 4 or forcing the controller 4 to be disabled in response to a signal indicating an elapse of time if no signal is transmitted thereto from the controller 4 after a predetermined time has passed because an abnormality occurs in the processing of the controller 4;an embodiment in which said software operator 1 includes means for performing creation, addition, deletion, alteration, correction, replacement, division, merging, copying, transfer or similar operations on a part of the software work tool itself;an embodiment in which said observer 5 includes means for performing access, comparison, listing, investigation, diagnosis or similar observations on a part of the software work tool itself;an embodiment in which the software operator 1 includes means for creation, addition, multiplication, activation, stopping, freezing, defrosting, deletion, alteration, correction, replacement, division, merging, copying, transfer of a similar software work tool except its own software work tool or similar operations;an embodiment including a memory device (i.e., a stack) for transmitting state data of the request side from the work knowledge storer 2 and storing the same prior to the request in order to continue front and rear works correctly when its own software work tool is directly or indirectly requested (i.e., recursive call) and transferring the state data to the work knowledge storer 2 one more time to recover the same after the requested work has been finished;an embodiment including information input apparatus for inputting information from a user or operator and said work knowledge storer 2 including means for describing the processing of the input information from the information input apparatus, and an embodiment in which the above communicator 3 includes at its front stage a device for integrating information format in order to process a communication similarly to the communication with the user or operator when information communicated to the above communicator 3 is a communication from its own and other similar software work tools;an embodiment including information output unit for outputting information to a user or operator and in which the work knowledge storer 2 includes means for describing a method of outputting information to the information output apparatus, and an embodiment in which the communicator 3 includes at its succeeding stage a device for converting an integrated information format into an expression format addressed to a human being only when information is output to the user or operator in order to process the communication similarly to the communication with the user or operator if information communicated via the communicator 3 is a communication with its own and other similar software work tools;an embodiment including a name, a nickname, a symbol, a frame display, a coordinate, a face, a figure, sound information or voice information for identifying its own software work tool from another software work tool so that the information can be transmitted to the communicator 3 or displayed to the user or operator;an embodiment in which the work knowledge storer 2 includes information concerning the fact that its own software work tool has a function, a using method, a using example or a using record different from those of other software work tools so that the information can be transmitted to the communicator 3 or displayed to the user or operator.an embodiment in which the work knowledge storer 2 includes information concerning a function, a using method, a using example or a using record of a software to be operated by the software operator 1 so that the information can be transmitted to the communicator 3 or displayed to the user or operator.an embodiment in which the work knowledge storer 2 includes information concerning a using method of a software to be operated by the software operator 1 and the controller 4 decides the next instruction in accordance with the information concerning the using method; an embodiment in which the work knowledge storer 2 includes therein information concerning a plurality of software groups to be operated by the software operator 1 and the controller 4 selects a software to be operated on the basis of the information and instructs the software operator 1 to operate the software properly;an embodiment having a temporary storage area for executing work, an embodiment including means (i.e., a dump) for outputting the contents of the temporary storage area to another storage device when a fault occurs or when the user instructs an investigation and a further embodiment including means for processing information by accessing the dump;an embodiment including means (i.e. a dump) for outputting the content of the work knowledge storer 2 to another storage device when a fault occurs or when the user instructs an investigation and a further embodiment including means for processing information by accessing the dump;an embodiment including means (i.e., log or trace) for recording an instruction treated by the controller 4, information treated by the above instruction, a place of instruction or a completed state of instruction in another storage device in order to understand details of a processing, or a further embodiment having means for processing information by accessing the log or trace;an embodiment including means (i.e., a snap) for pausing the above controller 4 and recording an instruction, information treated by the instruction, a place of instruction or a completed state of instruction in another storage device when an instruction is issued in order to understand details of the processing or when a logic condition is satisfied, or a further embodiment including means for processing information by accessing recorded information such as a snap or the like;an embodiment in which the software operator 1 accesses the operating system to request the operation for software on its own and other an information processing apparatuses;an embodiment in which the observation unit 5 accesses the operating system to request an input, to supervise or to send information on its own, and other an information processing apparatuses;an embodiment in which the communicator 3 includes means for communicating with a similar software work tool on other an information processing apparatuses; an embodiment in which the software operator 1 connects a device for accessing a software tool which describes or evaluates the system arrangement by combining devices or softwares; a software tool which describes or evaluates performance, scale, capacity, reliability, work planning, schedule or cost of the system; or a software tool in which terms, concept, data, a relation between data, function, processing, picture, document, telegram or knowledge necessary for realizing a business are stored, processed, analyzed, converted, displayed or printed and which executes a part of the system design or analyzing work;an embodiment in which the software work tool 1 connects a device for accessing a software tool for creating a more detailed specification description from a program specification description; a software tool for creating a program or on environment definition from a specification description; a software tool for extracting a specification description from a program; or a software tool for checking, displaying or printing the specification description, the program or the environment definition, and executes a part of software development work;an embodiment in which the software operator 1 connects a device for supervising a program activation condition, preparing program input information or program control information, activating a program, supervising a program state, sending information to a program, forcing the program to be stopped, changing a program's priority, recovering a program when an abnormality occurs, judging an executed result of a program or analyzing output information of a program, and executes a part of software operation work;an embodiment in which the software operator 1 connects a software tool which checks a program or environment definition varied in association with the change of a program or environment definition, a software tool which changes a program or environment definition varied in association with the change of a program or environment definition, a software tool which changes an associated program or environment definition when a specification description is changed or a software tool which changes a specification description when the program or environment definition is changed and executes a part of software maintenance and an expansion work;an embodiment in which the software operator 1 connects a device for accessing a software tool which extracts a specification description from a program of the present system or a software tool in which the specification description of the present system; inputs and converts program or information (i.e., a conversion) into a specification description of a newly developed system, a program or information; and then outputs and executes a part of software converting work;an embodiment in which the software operator 1 connects a device for accessing a software system introduction and management tool or a customized tool in which software are adjusted for customers and executes a part of software introducing work;an embodiment in which the software operator 1 connects an accessing and updating device for accessing and updating a data base having a specific structure, a file, an image file, a voice file or a specific file and executes a data input and output processing or treatment processing; an embodiment in which the software operator 1 or the communicator 3 communicates with a telephone, a facsimile, a word processor, a teleconference, a so-called pocket bell, a terminal, an electronic switcher or a similar network appliance;an embodiment in which the communicator 3 communicates with a software work tool having only a controller and a work knowledge storer without a software operator, regardless of whether or not it has a similar communicator, to thereby obtain a part of knowledge or a calculated value from the software tool;an embodiment including another software work tool creating device for creating or erasing later a similar software work tool (i.e., another software work tool) when work increases;an embodiment including another remote software work tool creating device for creating or erasing later a similar software work tool (i.e., another software work tool) on another an information processing apparatus when the other an information processing apparatus different from the activated information processing apparatus need be operated;an embodiment including a remote transmission device for transmitting its own information to an information processing apparatus, recovering later or erasing later the same when another an information processing apparatus different from the activated information processing apparatus need be operated; an embodiment in which the work knowledge storer 2 includes knowledge concerning a method of preparing a work environment and executes work for an environment preparation prior to the main work; an embodiment in which the work knowledge storer 2 stores a rule, a fact or other knowledge concerning a work planning method and planning details composed of a work method, a work order or a logic execution condition forming the work or evaluating the plan prior to the work; an embodiment in which the work knowledge storer 2 includes a rule, a fact or other knowledge concerning a work supervisory method, work executed by the software operator 1 or another similar software work tool via the communicator 3 is observed by the above communicator 3 or by the observer 5 and the controller 4 executes the control on the basis of an observed result; an embodiment in which the controller continues a process requiring no answer until an answer of an item requested of another similar software work tool, the user or the operator via the communicator 3 is obtained and executes a process requiring the answer when the answer is obtained;an embodiment in which a timer detects that an answer concerning an item requested of another similar software work tool, the user, or the operator via the communicator 3 is not obtained during a predetermined period of time and the controller inquires again, demands or regards the requested item as an abnormality;an embodiment in which a format permitted as information received by the communicator 3 or information concerning the meaning of the information is stored in the work knowledge storer 2, the checking or analysis of the meaning is executed upon reception on the basis of the format information or the meaning information and a corresponding process is executed on the basis of the analyzed result;an embodiment in which the software operator 1 or the work knowledge storer 2 includes a data base (i.e., an object-oriented data base) which manages en bloc a variety of data as an integrated unit (i.e., an object) of data and processing;an embodiment including a device (i.e., a device for generating software work tool B asked on an object orientation) for generating the content of at least the work knowledge storer 2 from the content of a work knowledge storer of a more general software work tool of the software work tool by carrying out the succession (i.e., the inheritance);an embodiment in which the work knowledge storer 2 includes remote command and a corresponding method of operation for operating the software by the software operator 1 in accordance with information (i.e., a remote operation command) received at the communicator 3 in order to operate the software by a command from a remote place connected by a line or other places such as space, or a further embodiment including the observation unit 5 to transmit input information to a remote place;an embodiment in which the work knowledge storer 2 includes a necessary data group and a set of operations to be executed when the data are prepared and the above controller 4 determines whether or not the necessary data are prepared and a device (data flow computer) activates the operations sequentially or in parallel;an embodiment including a power supply control device for switching on an information processing apparatus which is operated instead of a communicator to thereby activate the controller 4 when information is received by the above communicator 3;an embodiment including a power supply control device for executing a process after a predetermined period of time when information is received by the above communicator 3 and for switching off a power switch of an information processing apparatus whose software work tool is being operated; an embodiment including a power supply control device for counting time with a timer or clock and switching on a power switch of an information processing apparatus at a predetermined time;an embodiment in which a receiving unit of the above communicator 3 is activated by a designating (i.e., call) operation for the software work tool from an external program to receive information of a call parameter prepared in the external program or a transmitting unit executes a transmission by varying a value of a call parameter activating the transmitting unit of the above communicator 3 or by a return value to thereby execute a return operation to the external program;an embodiment (i.e., a nested arrangement) in which components may include a similar software work tool, or a further embodiment in which an internal software work tool is dynamically created or erased or a software work tool including its own software work tool is dynamically created or erased at its outside;an embodiment in which a common content of the work knowledge storer 2 or the controller 4 of at least a plurality of software work tools is stored in the only storer and made common to the software work tool groups and individual contents of at least the work knowledge storer 2 include storage for respective software work tools in a one-to-one relation, thereby esnabling a common unit to be operated in a reenterable fashion;an embodiment including a log file, a log acquisition device and a recovery device in an external storage unit, wherein the log acquisition device properly writes a changed content of a storage device allocated at least by the work knowledge storer 2 in the log file and the recovery device reads out the changed content from the log file when the software work tool resumes the processing after the software work tool has paused the process due to some fault to thereby recover the work knowledge storer, or a further embodiment in which a recovery process for an external software is executed by the software operator 1;an embodiment including a log file, a log acquisition device and a back out device in an external storage unit, wherein the log acquisition device properly writes a changed content of a storage device allocated at least by the work knowledge storer 2 in the log file and the back out device reads out the changed content from the log file when the software work tool cancels the integrated processing due to some fault to thereby recover (i.e., back out) the work knowledge storer, or a further embodiment in which a back out processing for an external software is executed by the software operator 1;an embodiment including a log file and a log acquisition device in an external storage unit, wherein the log acquisition device writes uptime statistical information, accounting statistical information, performance statistical information or security control information in the log file in accordance with the processing of the software work tool, or a further embodiment in which the information is input by the software operator 1, or an embodiment having the observation unit 5 wherein the information is input by the observation unit 5;an embodiment in which a plurality of software work tools include converting devices for converting information when the respective communicators 3 thereof communicate information of different formats or of different meanings;an embodiment in which the above observer 5 connects means for inputting from the outside a load (i.e., availability) of a component of an information processing apparatus, a using amount of a storage device or a buffer memory, a processing speed of software work, a wait condition of work request information for the software work tool, a component of the an information processing apparatus or a component fault condition of the software work tool;an embodiment including information (i.e., a HELP file) which answers when the user asks for an operation method and in which the content of the HELP file is answered when the user questions via some route;an embodiment which accesses or updates, in accordance with a proceeding of control, name management information, relating information, software resource management information, a directory, a catalog file, a data dictionary, a data directory, an integrated resource management dictionary, information repository, an object manager, an object server, a name server, a concept dictionary, a function dictionary, a terminology dictionary, an item dictionary, an electronic dictionary, a kana-kanji conversion dictionary, a language translation dictionary or similar dictionaries provided on the outside;an embodiment including a document processing unit for the above software operating unit 1 wherein a document is created, edited, displayed or printed out by the document processing unit; or a document is input, analyzed or understood by the software operating unit 1 or by the observation unit 5, or a further embodiment in which a printing apparatus, a word processor or a copying apparatus is connected to the document processing unit so that they can be operated in a linked configuration;an embodiment including an analysis unit linked to the above software operating unit 1, wherein a content of a display file, which is output in a two-dimensional array from an external software for the user, is analyzed without the interposition of a user or with the decreased interposition of a user, and an analyzed result is sent to the controller;an embodiment including a key information composing unit linked to the above software operating unit 1, wherein a content of an input file, which is requested in a one-dimensional array by an external software in order to read a user's key input, mouse input or touch input, is composed without the interposition of a user or with the decreased interposition of a user, and a composed result is sent to the external software;an embodiment including a field input information composing unit linked to the above software operator 1, wherein a content of an input file, which is requested in a two-dimensional array by an external software in order to read information generally input to an area (i.e., field) of a picture by the user, is composed without the interposition of a user or with the decreased interposition of a user and a composed result is sent to the external software;an embodiment in which the above software knowledge storer 2 includes version information of the work knowledge or further a plurality of work knowledge of different versions;an embodiment including an external display device, wherein input and output of at least the software work tool group are separately allocated to a plurality of windows forming a part of the display screen of the display device;an embodiment in which the work knowledge storer 2 includes a plurality of descriptions of information constraint between blocks of information and the above controller 4 includes a constraint process unit for executing a process on the basis of the constraint;an embodiment in which communication information, work request information or a work result when a work is executed is stored in the above work knowledge storer 2 and returns the information (i.e., example) to a question from a user who executes new work, or a further embodiment in which the user executes a selection and a correction from the example, or a further embodiment in which the difference between the example and the new work is judged so as to minimize conversation between it and the user;an embodiment in which communication information, work request information or a work result when a work is executed is stored in the above work knowledge storer 2 and utilized as knowledge on the work for a new work (i.e., learning function);an embodiment including natural language processing unit connected to the above communicator 3, wherein a conversation is conducted between the users or between similar software work tools by means of a natural language, and a further embodiment including voice and thought connected to the natural language processing unit, wherein a conversation is conducted between the users or between similar software work tools by means of voice; andan embodiment including a feeling storer connected to the above controller, wherein the feeling storer includes a variable imitating a feeling concept similar to joy and sorrow of human beings, a feeling variable is varied on the basis of a work processing information in accordance with the proceeding of control, the feeling variable is accessed in accordance with the proceeding of control and the feeling storer activates the controller so that the controller selects at least a display of shape of face, expression of words or expression of voice from information displayed via some route by effectively utilizing the value of the feeling variable.As set out in detail above, according to this invention, it becomes possible to provide a general purpose software work tool in which software operations can be executed automatically on the basis of information concerning the work in the development and operation of the software, and in which the work can be made independent and minimized by creating the information concerning work in a self-distributed fashion.In comparing the software work tool of this invention to a human being, it should be noted that the work knowledge storer and the controller correspond to a person's brain, the communicator corresponds to his mouth and ears, the software operator corresponds to his hands and the observer corresponds to his eyes. As described above, according to this invention in which the software work tool is arranged as a robot in the software world, a device in which the software is produced and the software work tool is operated by this software in the an information processing apparatus as if a robot produced and operated the machine in the factory becomes possible from a man's work standpoint. On this basis, research results of AI technology or the application of such as a distributed processing technology becomes very effective. It is expected that the application field of this invention will be rapidly extended in the future and therefore this invention may contribute greatly to the development of the an information processing apparatus.Although preferred embodiments of this invention have been described in detail with reference to the accompanying drawings, it is to be understood that the invention is not limited to these precise embodiments, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope of the invention as defined in the appended claims.	A software work tool in an information processing apparatus comprising: a work knowledge storer means (2) for storing work knowledge information;a software operating means (1) for carrying out operations on a plurality of programs based on said stored work knowledge information;a communicator means (3) for transmitting and receiving communication information including work requests and work reports to and from said software work tool and at least one additional external software work tool, thereby enabling said software work tool and said at least one additional external software work tool to cooperate with each other during an operation on said plurality of programs;a controller means for controlling said software operating means (4) , said communicator means (3) and said work knowledge storer means (2) based on said work knowledge information stored in said work knowledge storer means (2); andan observation means (5) for observing said programs operated on by said software operating means (1) comprised within said software work tool and for observing programs operated on by at least one software operating device provided within said at least one additional external software work tool.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores one or more inference rules defining a logical executing condition and a processing method for operating on said program, and said controller means (4) further includes an inference engine which executes said inference rules.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores a plurality of frames as units of information, each of said plurality of frames corresponding to one concept of data and knowledge describing a relation between said plurality of frames, and said controller means (4) further includes an inference engine which executes said programs on the basis of said knowledge describing said relation between said plurality of frames.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores one or more objects provided as units of information, each said object corresponding to one concept of data, an order of said objects being based on a successive relation between each attribute included in each said concept, each said concept being able to communicate with each other and, said controller means (4) includes a processing unit for executing said program on the basis of said objects.A software work tool according to claim 1 wherein said work knowledge storer means (2) stores said work knowledge corresponding to a concept, each said concept being in an order based on a continuous relation between each attribute included in each said concept, and said work knowledge is provided with at least one object comprising a group of information which can mutually communicated with each other, and said controller means (4) is provided with a processing unit for executing said program based on the object.A software work tool according to claim 1, wherein said work knowledge storer means (2) stores one or more descriptions of a function, said controller means executes said programs on the basis of said function.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores one or more fact clauses as descriptions indicating facts and one or more rule clauses as descriptions indicating rules, and said controller means (4) further includes an inference engine for executing said program on the basis of said fact clauses and said rule clauses.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores one or more rules of inference defining a logical execution condition and a processing method for operating on said program and, said controller means (4) includes an inference engine which executes said program based on said rule of inference and a back track device which searches for a next inference rule when a failure takes place in the execution of said program based on said rule of inference.The software work tool according to claim 1, wherein said work knowledge storer stores metaknowledge as rule knowledge and knowledge relating to an inference process and, said controller means (4) includes an inference engine for executing said program based on said metaknowledge or based on said knowledge.The software work tool according to claim 1, further comprising a blackboard memory which stores information produced in an inference process such that a plurality of said software work tools cooperate with each other through communication with said blackboard memory, and accessing means for enabling said plurality of said software work tool to access said blackboard memory in order to communicate with each other.The software work tool according to claim 1, further comprising an agenda memory which stores information concerning an unsolved problem and a solved problem such that a plurality of software work tools cooperate with each other through communication with said agenda memory, and accessing means for enabling said plurality of said software work tools to access said agenda memory in order to communicate with each other.The software work tool according to claim 1, further comprising a message switcher connected to said communicator means (3) and to a communicator of another software work tool, to transmit and receive a communication message such that a plurality of said software work tools work in cooperation with each other through communication. The software work tool according to claim 12, wherein said communicator means (3) determines whether or not said communication message from said message switcher is an activation request, if said communication message is said activation request, then said communicator means (3) receives a character string of a message, checks a format of said message, decodes said communication message transmits said decoded message to said controller means (4) and determines whether or not the said message is said activation request from said message switcher; if said communication message is not said activation request from said message switcher, then the communicator means (3) determines whether or not said message is an activation request from said controller means (4), if said message is the activation request from said controller means (4), said communicator means (3) checks a format of said request message, prepares a transmission message format, activates said message switcher, supplies a character string of said message to said message switcher, informs said controller means (4) that the message is normally transmitted and then determines whether or not said message is the activation request from said message switcher; andif said message is not said activation request from said controller means (4), then said communicator (3) determines whether or not said message is the activation request from said message switcher.The software work tool according to claim 1, further comprising a work tool activating device which receives a communication message from a software work tool, activates a software work tool designated by said communication message and transmits said communication message to said designated software work tool such that a plurality of said software work tools work in cooperation with each other through said work tool activating device.The software work tool according to claim 1, wherein said work knowledge storer means (2) further stores a data base.The software work tool according to claim 1, wherein said work knowledge storer means (2) further stores a procedure description indicating a work. The software work tool according to claim 1, wherein said work knowledge storer means (2) stores a logical chart diagram in which a flow of processing indicative of a work procedure is illustrated in a graphical fashion or stores information in a logical chart diagram.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores a decision table of data, each said datum indicating a plurality of conditions and commands relating to a work procedure, or stores data in a decision table.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores a state transition diagram expressing a condition of a state transition relating to a work procedure or stores information in a state transition diagram.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores information in a list structure, a tree structure or a graph structure relating to a work procedure or stores information in a list structure, a tree structure or a graph structure.The software work tool according to claim 1, wherein said observation unit (5) comprises an event observation unit for observing events occuring in said software work tool and designating whether said observation event is a timer activation event or a message activation event, and an internal memory unit for storing a timer element used for performing an event judgment process when said observed event is said timer activation event and for storing a message identifying information used for performing an event judgment process when said observed event is said message activation event.The software work tool according to claim 1, wherein said work knowledge storer means (2) stores a list of selector names acting as an identifying name of a message received from said communicator (3), an argument acting as a variable parameter, a plurality of rules formed as a set of conditions for inference, a command, a command group defined as a function accessed by said method and said rule, a tree structure knowledge in which data and fact are stored in a tree structure fashion and, an object control knowledge formed as tree structure data for controlling said method, said rule, said procedure and said tree structure knowledge.The software work tool according to claim 1, wherein said software operating means (1) determines whether or not a request is a software operation request from said controller means (4), if said request is said software operation request from said controller means (4), then said software operating means (1) makes an input file addressed to software from a request information if necessary, makes a software executing command from said request information, transmits said executing command to an operating system to request an activation, determines whether or not said operating system normally receives said activation request, if said operating system receives said activation request, then said software operating means (1) informs said controller means (4) that said operating system is normally activated, requests said operating system to make a time-out notification after an elapse of a supervisory time, and repeats the processings following determining whether or not said request is said software operation request from said controller means (4); if said operating system does not normally receive said activation request, then said software operating means (1) transmits an error information indicative of activation failure to said controller means (4) and repeats the processings following determining whether or not said request is said software operation request from said controller means (4);if said request is not said software operation request from said controller means (4), then said software operating means (1) determines whether or not said request is an ending information of the software activated by said operating system, if said request is said ending information, then said software operating means (1) cancels the time-out notification request for said operating system, checks a software output file, an error message and a completion code and repeats the processings following determining whether or not said request is said software operation request from said controller means (4) and repeats the processings following determining whether or not said request is said software operation request from said controller means (4) after having transmitted a normal ending information to said controller means (4);if the information is not the ending information of said software activated from said operating system, then said software operating means (1) determines whether or not a request from said operating system is a time-out notification, if said request is the time-out notification, it is determined by said software operating means (1) whether or not the software activated is ended, if the software activated is ended, then said software operating means (1) repeats the processings following determining whether or not said request is said software operation request front said controller means (4) after having transmitted an ending information and an error information indicative of an execution failure to said controller means (4);if the activated software is not ended, then said software operating means (1) requests said operating system to execute a forced ending of said software and repeats the processings following determining whether or not said request is said software operation request from said controller means (4) after having transmitted an execution failure error information to said controller means (4); andif the request from said operating system is not a time-out notification request, than said software operating means (1) repeats the processings following determining whether or not said request is said software operation request from said controller means (4).The software work tool according to claim 1 for use in a computer system as an information processor, wherein said controller means includes : a man-machine interface (202) including a monitor and a keyboard;message exchange mechanism means (211) for exchanging communication messages with communicators of said software work tools external to said communicator means (3) and for enabling a plurality of software tools to operate in a coordinated manner through mutual communications;work tool booting-up mechanism means (212) for receiving a communication message, for invoking a software tool designated by said communication message, and for passing a communication message to said software work tool, such that a plurality of software work tools operate in a coordinated manner through mutual communications;an editing program;a screen/manipulation controller (215) of an operating system; anda communication controller (216) of an operating system for a network connecting said message exchange mechanism with said operating system, and said work knowledge storer means includes :a work list file (214) used by said editing program; anda work knowledge base (217) as an external memory for a work knowledge base in said software work tool (210).The software work tool according to claim 24 for use in a computer system as an information processor, further comprising : software operating means for converting data standardized within software work tools to a format conforming to a home system, thereby manipulating a program in said software work tool or information within a home system.The software work tool according to claim 24 for use in a computer system as an information processor, wherein: said message exchange mechanism means (211) further performs a bi-directional conversion between a data format used by said home computer system and a data format standardized for exchanging a communication message with said network through said communication controller means (216) of said operating system, for enabling a software work tool in said home system to operate in a manner coordinated with a software work tool in a foreign system.The software work tool accoding to claim 1, wherein said controller means (4) activates a predetermined constant operation as a demonstration based on said work knowledge stored in said work knowledge storer means (2) when said observed operated on program satisfies predetermined conditions.The software work tool according to claim 1, wherein said observation means (5) includes an internal memory for storing a type of event indicating whether an observation event type is a timer activation event or a message activation event, a timer interval and an address of a function, for executing an event determining processing if said type of event is said timer activation event and a message identifier information and an address of a function for executing an event determining processing if said type of event is said message activation event.The software work tool according to claim 1, wherein said controller means (4) determines whether or not said communication information is received from said communicator means (3), if said information is received from said communicator means (3), then said controller means (4) searches messages having a coincident message selector from the content stored in said work knowledge storer means (2), compares arguments, decodes a procedure stored in said work knowledge storer means (2) to execute an instruction, detects a rule having a condition established from rule groups stored in said work knowledge storer means (2) and which are now effective after said instruction was executed, repeatedly executes an instruction on the rule having the established condition, if there is detected no rule whose condition is established, then said controller means (4) repeats the process following determining whether or not said information is received from said communicator means (3); if said information is not received from said communicator means (3), then said controller means (4) determines whether or not said information is received from said observation means (5), if said information is received from said observation means (5), then said controller means (4) executes an instruction corresponding to an event on the basis of a received associated information, detects a rule having a condition established from rule groups stored in said work knowledge storer means (2) and which are now effective and repeats the process following executing said instruction corresponding to said condition; andif said information is not received from said observation means (5), then said controller means (4) determines whether or not said information is said report from said software operating means (1), if said information is said report from said software operating means (1), then said controller means (4) supplies a return information to a software operation instruction, being executed so that said software operation instruction is continuously executed, detects a rule having a condition established from rule groups stored in said work knowledge storer means (2) and which are now effective, repeats the functions following executing said instruction corresponding to said condition, if said information is not said report from said software operating means (1), then said controller means (4) repeats the functions following determining whether said information is received from said communicator means (3).The software work tool according to claim 1, wherein said observation means (5) determines whether or not a request is said observation request from said controller means (4), if said request is said observation request from said controller means (4), then said observation means (5) receives an event to be observed and information of an event decision from said work knowledge storer means (2), stores said event and said event information in an internal memory, determines whether said event is a timer activation event or a message activation event, if said event is said timer activation event, said observation means (5) repeats the functions following determining whether or not said request is said observation request from said controller means (4) after having requested the operating system to supply a timer activation information after a certain period of time, if said event is said message activation event, then said observation means (5) immediately repeats the functions following determining whether or not said request is said observation request from said controller means (4); if said request is not said observation request from said controller means (4), said observation means (5) determines whether or not said request is said timer activation request from said operating system, if said request is said timer activation request, said observation means (5) reads out a corresponding event decision processing from said internal memory, executes said event decision processing to determine whether or not said timer activation request is treated as an occurrence of an event, if said timer activation request is treated as said occurrence of said event, then said observation means (5) deletes said event and said information of the event decision processing from said internal memory, transmits an associated information to said work knowledge storer means (2) and repeats the functions following determining whether or not said request is said observation request from said controller means (4), if said timer activation request is not treated as said occurrence of said event, said observation means (5) repeats the functions following determining whether or not said request is said observation request from said controller means (4) after having requested said operating system to supply a timer activation request after a certain period of time; andif said request is not said timer activation request from said operating system, then said observation means (5) determines whether or not said request is said message request from said operating system, if said request is said message request from said operating system, then said observation mean (5) checks by the content of said internal memory whether said message request is a target message event, determines whether or not said event is a target event, if said event is said target event, then said observation means (5) reads said event decision processing corresponding to said event and executes said event decision processing to thereby determine whether or not said event is treated as an occurrence of event, if said event is treated as said occurrence of event, then said observation means (5) repeats the functions following deleting said event and said information of said event decision processing from said internal memory and then repeats the functions following the determining whether or not said request is said observation request from said controller means (4) when said event is not treated as said event decision, when it is determined by said checking within said internal memory that said event is not a target events and when it is determined that a message is not said request message in the decision processing far determining whether or not said message is said request message from said operating system.	FUJITSU LTD; FUJITSU LIMITED	ISHIZAKI AYUMI; KONDOH TATSUO; SONOBE MASAYUKI; ISHIZAKI, AYUMI; KONDOH, TATSUO; SONOBE, MASAYUKI
EP-0489359-B1	489,359	EP	B1	EN	19,950,524	1,992	20,100,220	new	B23B31	B23B47	B23B47, B23B29, B23B37, B23Q3	B23B 47/34	Vibrating cutting tool	A vibrating cutting tool having an input shaft (1) driven by a live spindle of a machine tool and an output shaft (2) having a cutter mounting portion. The input shaft (1) and the ouptut (2) shaft are coupled together through a coupling mechanism so as to be at least circumferentially movable relative to each other. Recesses (15) are formed in one of the input shaft and the output shaft and holes (21) are formed in the other at locations opposite to the recesses. Moving elements (23) are mounted between the recesses (15) and the holes (21) with a predetermined gap defined between the moving elements (23) and the recesses (15) or the peripheral surfaces of the holes. The gaps serve to restrict a circumferential movement of the moving elements. Springs (26) are provided to urge the moving elements against the recesses. The movement of the moving elements is restricted by stoppers. An adjusting ring may be provided to adjust the biasing force of the springs.	This invention relates to a cutting tool having the features of the precharacterizing part of claim 1. Such a tool can impart vibrations effective for cutting to a rotary cutter such as a drill, an end mill or a tap. Fig. 7 shows how a work a is cut with a cutter of a conventional cutting tool. b is a cutting edge moving to the lefthand side of the figure. c designates a chip produced by cutting. The chip c consists of tiny blocks c' produced by compression and shearing with the cutting edge b, which moves back and forth intermittently while repeating compression and shearing as shown by the arrow. The vibration produced by such back-and-forth movement is a self-excited vibration. Such vibration is generally microscopic in amplitude but this type of cutting may be considered to be vibrating cutting in a broad sense. If its amplitude reaches a certain level due to changes in the cutting conditions, it is called chattering. Fig. 8-I shows a curve representing waveforms of vibration amplitude produced by the above-described conventional cutting tool, which is very irregular. At portions where the amplitude is small, the edge is likely to be heated while at portions where it is large, the work tends to be scratched remarkably. This worsens the surface roughness. Heretofore, in order to reduce the amplitude of vibration where it is detrimentally large, a tool mounting structure was used which has as high a rigidity as possible. But the higher the rigidity of the tool mounting structure, the smaller the amplitude of vibration tends to be at the portions of the curve where the amplitude is small. This may increase the temperature of the chips or the cutter edge or cause the growth of the built-up edge, thus worsening the cutting ability of the cutter. Thus, to improve the cutting ability, it is necessary to smooth out the vibration as represented by the curve of Fig. 8-II by reducing any larger amplitudes while increasing any smaller ones. In one known vibrating cutting tool, an external vibration source is used to vibrate the cutting edge forcibly and thus to obtain a uniform vibration curve as shown in Fig. 8-II. This type of cutting tools having a forcible vibration source have an excellent cutting ability. Many of these cutting tools use, as a vibration generator, electro-striction type or magneto-striction type vibrating elements which are excited by an oscillator. Others use vibrating elements of electro-magnetic vibration type, electro-hydraulic type or mechanical-hydraulic type. Some of them require complicated electric circuits or mechanisms. Others require large-sized and expensive hydraulic cylinders for vibrating a work supporting table. All of them utilize resonance to obtain a suitable amplitude of vibration at the cutter edge. Thus, they can be used only within a limited range of frequency. This makes it difficult to cope with changes in the cutting conditions. EP-A-0 292 651 disclosed the cutting tool according to the precharacterizing part of the claim. In said cutting tool two different kinds of springs are provided, one acting in an axial direction and the other acting in an radial direction. It is an object of this invention to provide a cutting tool which can obtain, as opposed to irregular vibration at the cutter edge as shown in Fig. 8-I, vibration of a uniform amplitude at the cutter edge as shown in Fig. 8-II, irrespective of changes in the cutting conditions, without using a complicated and expensive forcible vibration generator which can be used only within a predetermined range. In order to solve the above problem, according to this invention, there is provided a vibrating cutting tool as claimed in claim 1. The dependent claims are related to further advantageous embodiments. An adjusting ring may e.g. be provided to adjust the biasing force of the springs. To start cutting operation, the input shaft secured to the live spindle of a machine tool is rotated and moved forward together with the live spindle to press the cutter fixedly mounted on the cutter mounting shaft of the output shaft against the work. In the above cutting process, irregular microscopic vibration is produced at the cutter edge due to fluctuations in the cutting force. In case of a prior art cutting tool in which the input and output shafts are integral with each other, such vibration at the cutter edge is extremely irregular as represented by the amplitude fluctuation curve shown in Fig. 8-I. In contrast, with a tool embodying the present invention, in which the input shaft and the output shaft are movable relative to each other within a predetermined limited range, the amplitude is smoothed out as shown in Fig. 8-II. In Figs. 8-I and 8-II, the horizontal axis represents time and the vertical axis represents amplitude. When the cutter cuts into the work, the turning torque is transmitted from the input shaft to the output shaft through the moving elements pressed against the recesses in the input shaft by the springs. While the fluctuation of the cutting force is small, the torsional rigidity for torque transmission is small because it is determined mainly by the springs. Thus, the cutter edge can vibrate relatively freely and the amplitude of vibration is large compared with a conventional integral type cutting tool. When the fluctuation of cutting force grows and thus the springs are compressed to a greater extent, the moving elements displace until they abut the stoppers. Now the output shaft is rotated directly by the input shaft irrespective of the springs. Thus, the torsional rigidity between the input shaft and the output shaft increases to a value near to the value obtained with a conventional integral type cutting tool, thus suppressing the amplitude of vibration at the cutter edge. The amplitude of vibration at the cutter edge is kept large where it is small with a conventional integral type cutting tool and kept small where it is large with a conventional tool. As a result, the amplitude of vibration is smoothed out as a whole as shown in Fig. 8-II. In a tool embodying this invention, the input shaft and the output shaft are circumferentially movably coupled together. Moving elements are mounted between the recesses formed in one of the input and output shafts and the holes formed in the other. The turning torque is transmitted by urging the moving elements against the recesses with the springs. The movement of the moving elements is restricted only in a circumferential direction and a direction in which the springs are compressed within a predetermined range. In this arrangement, among the irregular vibrations produced at the cutter edge of a conventional integral type cutting tool, any part where the amplitude is small grows large, since at this part the torsional rigidity for torque transmission between the input shaft and the output shaft is determined mainly by the springs. Thus, the vibration at the cutter edge is not restricted so much and thus kept large. In contrast, at parts where the amplitude is large, the amplitude at the cutter edge is suppressed since the movement of the moving elements is restricted and thus the torsional rigidity between the input shaft and the output shaft increases. As a result, the amplitude at the cutter edge is smoothed out as a whole. This also makes it possible to reduce fluctuations in the cutting force. Thus, the feed speed and the number of revolution during cutting can be increased compared with a conventional integral type cutting tool. This contributes to increased productivity, better finished surface roughness of the work after cutting and long life of the tool. Further, as compared with a cutting tool which utilizes a forcible vibration source, no complicated, large-sized and expensive device is necessary. Its appearance is not different from a prior art integral type cutting tool. Thus, adjustment and handling are easy. It also has various other advantages including the advantage that it can be used within a large range of vibration frequency. Other features and objects of embodiments of the present invention will become apparent from the following description taken with reference to the accompanying drawings, in which: Fig. 1 is a vertical sectional side view of one embodiment of the cutting tool according to this invention; Fig. 2 is a vertical sectional side view of a portion of the same showing the state in which the torque is small; Fig. 3 is a cross-sectional view taken along line A-A of Fig. 1; Fig. 4 is a cross-sectional view taken along line B-B of Fig. 1; Fig. 5 is a front view of the ring; Fig. 6 is an enlarged sectional view of the same showing the function of the moving elements; Fig. 7 is an enlarged sectional view of the cutting edge showing its operating state; Figs. 8-I and 8-II show waveforms of the vibration at the respective cutter edges; Fig. 9 is a partially vertical sectional side view of another embodiment of this invention; Figs. 10A - 10C and 11A - 11C are enlarged sectional views of the vibrating units in the respective embodiments showing how they function. In the embodiment shown in Figs. 1 - 6, numeral 1 designates an input shaft and 2 does an output shaft. The input shaft 1 has a straight shank portion 3 at the rear part thereof and is integrally formed with a flange 4 at the front part thereof. The input shaft 1 has a center bore 5 in which a small-diameter shank 6 provided at the rear of the output shaft 2 is rotatably mounted. The shank 6 is provided at the rear end thereof with a stepped small-diameter portion 7. A protrusion 9 is formed on the inner peripheral surface of the center bore 5 at an intermediate portion thereof. A thrust bearing 10 is mounted outside the protrusion 9. A stop bolt 11 is provided at the rear end thereof with a large-diameter head which is supported on the thrust bearing 10. The bolt 11 rotatably extends through the protrusion 9 and is threaded into a small-diameter shank 6. A plurality of steel balls 13 are mounted between the small-diameter stepped portion 7 and the front side of the protrusion 9. As shown in Figs. 1 - 3, the flange 4 is formed in the front surface thereof with a plurality of recesses 15 arranged along a circle concentric with the center of the input shaft 1. Further, the flange 4 is formed in the front inner side thereof with an annular recess 17 extending over the entire circumference thereof. A plurality of steel balls 20 are arranged in the recess 17 on a protrusion 19 formed on a rear end face of a large-diameter portion 16 of the output shaft 2 at the inner part thereof. As shown in Figs. 1 - 4, the output shaft 2 is formed in the large diameter portion 16 with a plurality of axial through holes 21 and threaded holes 22 which are arranged on a circle concentric with the center of the output shaft 2. The through holes 21 and the threaded holes 22 correspond to the recesses 15 formed in the flange 4. The threaded holes 22 are provided at the rate of one for a plurality of through holes 21. A moving element 23 in the form of a steel ball is fitted in each of the through hoels 21 and the threaded holes 22 at the rear end thereof. The moving elements 23 are partially engaged in the recesses 15 of the flange 4. A spring 26 is mounted in each hole 21 while a setscrew 27 as a stopper means is threaded in each threaded hole 22. A tiny gap is defined between the rear end of the setscrew 27 and each moving element 23. The gap can be adjusted by adjusting the position of the setscrew 27. Further, a setscrew 30 having a roller pin 29 is threaded into the front end of each threaded hole 22. The pins 29 protrude toward the front surface of the large-diameter portion 16. A ring 31 is slidably fitted on the front side of the large-diameter portion 16 of the output shaft 2. It has holes 32 in which the roller pins 29 fit. (Fig. 5) As shown in Fig. 5, the ring 31 is formed in the front face thereof with a plurality of arcuate grooves 33 arranged concentrically with the center of the ring. As shown in Fig. 6, each groove 33 has its bottom tapered so that it will become deeper from one end to the other and also have an arcuate cross-section. An adjusting ring 34 is mounted on the front side of the ring 31. It is formed in the back surface thereof with a plurality of recesses 36 to receive steel balls 35. The ring 34 is integrally formed on the rear portion thereof along the outer edge with a skirt 37 engaging the outer periphery of the ring 31. (Fig. 1) The large-diameter portion 16 is formed in the front portion thereof along the outer edge with a stepped portion 39 to receive the rear end of the skirt 37 of the ring 34. The adjusting ring 34 is formed with a plurality of radial threaded holes 40 to threadedly receive setscrews 41 having their inner ends engaged in one of a plurality of engaging recesses 42 formed in the outer periphery of the output shaft 2. Thus, the ring 34 is coupled to the output shaft 2. The output shaft 2 is provided at the front end thereof with a cutter mounting portion 46 which is provided on the outer periphery thereof with male threads 43 and is formed concentrically with a forwardly widening tapered hole 44. A collet 51 is mounted in the tapered hole 44 and fastened in position with a tightening screw 54 threaded on the male thread 43. Fig. 9 shows another embodiment. The setscrews 27 have a threadless shank at the tip thereof and have their threaded portions threaded into threaded holes formed in a receiving ring 28 fixed to the output shaft 2. Each recess 15 on the flange 4 has a conical section. Otherwise this embodiment is the same as the first embodiment shown in Fig. 1. Thus, like parts are denoted by like numerals and their description is omitted. Now we shall describe a vibrating unit which constitutes the main feature of the present invention with reference to Figs. 1, 6, 9, 10 and 11. It comprises the recesses 15 formed in the flange 4 of the input shaft 1, the through holes 21 and the threaded holes 22 formed in the large-diameter portion 16 of the output shaft 2, moving elements 23 loosely fitted in the recess 15 at the front end of either the through holes 21 or the threaded holes 22, the springs 26 and the setscrews 27 and 30. Now we shall describe the operation of the embodiments. The input shaft 1 is secured at the straight shank portion 3 to the spindle of a machine tool. A cutter 55 such as a drill is secured to the cutter mounting portion 46 of the output shaft 2 through the collet 51 and the like. At first, as shown in Figs. 10A and 11A, the moving elements 23 are biased by the springs 26 against the wall of the recesses 15 in the flange 4, coupling the input shaft 1 and the output shaft 2 together. Thus, the rotation of the input shaft 1 is transmitted to the output shaft 2 and the cutting operation begins. When the cutting operation begins in this state, supposing that the flange 4 integral with the input shaft 1 is rotating in the direction of arrow in the vibration unit shown in Figs. 10 and 11, because the moving elements 23 biased by the springs 26 are in contact with both the input shaft 1 and the output shaft 2 as shown in Figs. 10B and 10C and 11B and 11C, the torque is transmitted from the input shaft 1 to the output shaft 2. As the edge of the cutter 55 cuts into the work, irregular microscopic vibration occurs at the edge of the cutter 55. This vibration at the cutter edge is transmitted to the vibrating unit through the output shaft 2, causing the moving elements 23 shown in Figs. 10 and 11 to repeatedly move back and forth microscopically. Such repeated movement, i.e. vibration, is composed chiefly of a microscopic rolling vibration and the moving elements 23 are always kept in contact with the curved or straight surfaces of the recesses 15. The amplitude of vibration of the moving elements 23 is no more than several ten microns. They never vibrate in such a way that the moving elements 23 rebound or jump several millimeters off the recesses 15. Of course, the setscrews 27 as stoppers never allow such a movement. As described above, while the moving elements 23 are pressed against the inner peripheral surfaces of the through holes 21 at their ends, the springs 26 are compressed. While the cutting force is small, as shown in Figs. 10B and 11B, the torsional rigidity of the vibrating unit in transmitting torque is mainly determined by the springs 26 and thus is relatively small. Since the vibration at the cutter edge is not limited so much in this state, the amplitude of vibration at the cutter edge is kept large within the range in which the effect of cutting is large, when compared with a conventional integral type cutting tool. As the cutting force at the cutter edge grows and thus the springs 26 are compressed to a greater degree, as shown in Figs. 10C and 11C, the relative position of the moving elements 23 changes. This also changes the relation of torque transmission between the input shaft 1 and the outut shaft 2. Namely, the moving elements 23 abut the inner peripheral surfaces of the through holes 21 and the end faces of the setscrews 27. Thus, the output shaft 2 is directly coupled to and driven by the input shaft 1 through the moving elements 23, irrespective of the springs 26. Thus, the total torsional rigidity of the vibrating unit increases to a level near the value obtained with a conventional integral type cutting tool. As a result, the amplitude of vibration at the cutter edge reduces or is limited within a range in which the effect of cutting is kept large. Thus, any excessive amplitude at the cutter edge is suppressed while vibrations having smaller amplitudes grow larger than with a conventional integral type cutting tool. Thus, the amplitude of vibration is smoothed out as shown in Fig. 8-II. We have described the operation of the embodiment of Fig. 9 with reference to Figs. 10 and 11. The operation of the first embodiment shown in Figs. 1- 6 is similar to the operation of the embodiment of Fig. 9. Namely, while the cutting force is small, the gap between the moving element 23 and the setscrew 27 (Fig. 6) is maintained and they do not abut each other. Thus, the torsional rigidity of the vibrating unit in transmitting torque is mainly determined by the springs 26, so that the amplitude of vibration at the cutter edge is relatively large. When the cutting force at the cutter edge increases and the springs 26 are compressed to a greater degree, the moving elements 23 will abut the ends of the setscrews 27 in the threaded hole 22. Now the output shaft 2 is directly coupled to the input shaft 1 through the moving elements 23, so that the total torsional rigidity of the vibrating unit increases and thus the amplitude of vibration at the cutter edge is limited. In order to change the biasing force exerted by the springs 26 on the moving elements 23, after loosening the setscrews 41 in the adjusting ring 34, the ring 34 is turned with respect to the output shaft 2. The balls 35 rollable together with the ring 34 will move in the grooves 33 so that the rings 31 move axially as shown in Fig. 2, changing the biasing forces of the springs 26. The gap between the moving elements 23 and the setscrews 27 can be adjusted by moving the setscrews 27 in the threaded holes 22 or the through holes 21. After adjusting the positions of the setscrews 27 and the force of the springs 26, the setscrews 41 are tightened into engagement with the respective recesses 42. Thus, the amplitude and frequency of the vibration at the cutter edge can be adjusted to values effective in cutting. In the above embodiments, the vibrating unit is shown to be arranged axially. Namely, the recesses 15 are formed in the end face of the input shaft 1 and the moving elements 23 are biased by the springs 26 inserted in the axial through holes 21 formed in the output shaft 2, with the setscrews 27 being inserted in the through holes 21 or the threaded holes 22. But a radially-arranged vibrating unit is equally effective. For example, the recesses 15 may be formed in the outer periphery of the output shaft 2. In this case, the through holes 21 or the threaded holes 22 are formed in the input shaft 1 in a radial direction. The springs 26 are mounted in the through holes 21 to urge the moving elements 23 against the wall of the recesses 15. The setscrews 27 are of course inserted in the radial through holes 21 or the threaded holes 22. Further, the recesses 15 and the springs 26 may be arranged opposite to the arrangement of the embodiment of Fig. 1. That is, the former may be provided in the output shaft 2 and the latter in the input shaft 1.	A vibrating cutting tool comprising an input shaft (1) driven by a live spindle of a machine tool, an output shaft (2) having a cutter mounting portion, means for coupling said input shaft and said output shaft together so as to have a limited movability circumferentially relative to each other, one of said input shaft (1) and said output shaft (2) being formed with recesses (15), the other being formed with holes (21, 22) at locations opposite to said recesses (15), moving elements (23) mounted partially in said recesses (15) and partially in said holes (21), and springs (26) mounted at least in some of said holes (21) for pressing at least some of said moving elements (23) against said recesses (15),characterized in that a predetermined amount of first gap in circumferential direction is defined between each moving element (23) and the respective recess (15) or the peripheral surface of the respective hole, said first gap restricting circumferential movement of each moving element (23), and in that stopper means (27, 30, 29) are mounted in at least some of said holes (22) with a predetermined amount of second gap defined between said stopper means (27, 30, 29) and some of said moving elements (23) for restricting the movement of the respective moving element (23) in the direction away from said recess (26). A vibrating cutting tool as claimed in claim 1, further comprising a retractable ring (31) supporting said springs (26) and an adjusting ring (34) provided at the front side of said retractable ring (31) to adjust the axial position of said retractable ring (31). A vibrating cutting tool as claimed in claim 1, wherein the position of said stopper means (27, 30, 29) with respect to the respective moving element (23) is adjustable to adjust the amount of first gap between said moving element (23) and said stopper means (27, 30, 29).	NIPPON PNEUMATIC MFG; NIPPON PNEUMATIC MANUFACTURING CO. LTD.	AOKI TSUTOMU C O NIPPON PNEUMA; IDA MASAHIRO C O NIPPON PNEUMA; NAJIMA KOZO C O NIPPON PNEUMAT; TSUYUGUCHI HIROHUMI C O NIPPON; WAKANO FUKUO C O NIPPON PNEUMA; AOKI, TSUTOMU, C/O NIPPON PNEUMATIC MANUFACT.; IDA, MASAHIRO, C/O NIPPON PNEUMATIC MANUFACT.; NAJIMA, KOZO, C/O NIPPON PNEUMATIC MANUFACT.; TSUYUGUCHI, HIROHUMI, C/O NIPPON PNEUMATIC MANUFAC; WAKANO, FUKUO, C/O NIPPON PNEUMATIC MANUFACT.
EP-0489361-B1	489,361	EP	B1	EN	19,960,529	1,992	20,100,220	new	B29B9	null	C08L69, B29B9, C08J3, B29B13	B29B 9/12, L29C269:00, B29B 9/06	Uniform distribution polycarbonate pellets	Polycarbonate pellets characterized in that (a) the median particle size of said pellets is between 250 and 1,000 microns; (b) the particle size dispersion of said pellets is less than 100 microns; and (c) the skew of the particle distribution is less than 0.25; each as determined according to ASTM Designation D 1921-63. These pellets are further characterized in that, (a) when said polycarbonate pellets are agitated on a screen having a mesh opening size of 850 microns, and when those pellets not retained on said 850 micron screen are then agitated on a screen having a mesh opening size of 710 microns, the portion of said pellets which together is retained on one or the other of said screens is more than 85 percent by weight; and (b) none of said pellets are retained when agitated on a mesh screen having a mesh opening size of 1,500 microns or more. These pellets are prepared by cutting molten polycarbonate as it is emitted from a die, preferably cutting the polycarbonate at the face of the die. Polycarbonate pellets thus characterized are easier to handle and process than those which have a larger median size, size dispersion and/or skew distribution.	This invention relates to polycarbonate in the form of pellets having a specified size range and distribution and to the use of those pellets for the production of films, extruded sheets, multi-layer laminates and shaped or molded articles. Polycarbonate can be prepared for shipment by manufacturers in forms which differ to a significant degree in terms of size. For example, polycarbonate pellets which are too large to pass through a sieve having a mesh opening size in the range of 2.5 to 4 mm are known. However, polycarbonate in powder form is also known where the powder granules may range in size from less than 100 to as much as 2,000 microns. Polycarbonate in powdered form is typically prepared by chopping or crushing polycarbonate which is not melted or dissolved. For example, in Narita. U.S. Pat. No. 4,074,864, methods and apparatus are disclosed for continuous production of polycarbonate powder from a polycarbonate solution. This involves mixing and kneading a polycarbonate solution while heating same and while simultaneously repeating the feeding of the solution forward and backward with the aid of meshing spiral blades in a twin screw extruder. As the solvent in the polycarbonate solution is evaporated by the applied heat, the product undergoes drying, grinding and powdering and is then discharged through an outlet in powder form. Although the polycarbonate powder is reported in Narita to have an average grain size of 1,700 microns, a minor portion of it is as small as 200 mesh or less. Koda, U.S. patent n° 4,184,911, also discloses a process for producing powdery polycarbonate from a polycarbonate solution by (a) charging the solution into a desolvating apparatus which is constituted of at least two intermeshing screws in a casing, the casing having an evaporating zone and a powdering zone ; (b) evaporating the solvent in the evaporating zone by crushing between the screws ; (c) powdering the dried polycarbonate in the powdering zone ; and (d) discharging the powdery polycarbonate from the product exit in the powdering zone. JP-A-1 234 212 discloses a process for producing fine particles of thermoplastic resin consisting in melting and kneading by an extruding machine the thermoplastic resin, extruding it through a nozzle having a hole diameter of 0,2 to 1,5 mm, and cutting the same into pieces by a revolving cutter blade. Handling any susbstance in powder form presents a problem with dust (extremely fine particles which become airbone) and the consequent loss of material and increased difficulty of housekeeping. Material in powder form is also more difficult to clean from an extruder when there is a change of feedstock and is frequently more difficult to melt uniformly in an extruder. Although polycarbonate in pellet form is generally not subject to such difficulties as are inherent in powder, even the usefulness of polycarbonate pellets often depends on the appropriateness of the pellet size for the intended operation. For example, pellets which have too broad a size distribution are more difficult to convey in a pneumatic system than pellets which are 85 percent or more within a specified size range. Accordingly, it would be desirable to have an easily practiced method of producing polycarbonate in the form of pellets characterized by a specified size range and distribution so that the convenience of being able to handle polycarbonate in pellet form would be available regadless of the size of pellet needed. In one aspect, this invention involves a composition of matter comprising polycarbonate pellets characterized in that (a) the median particle size of said pellets is between 250 and 1,000 microns; (b) the particle size dispersion of said pellets is less than 100 microns; and (c) the skew of the particle distribution is less than 0.25; each as determined according to ASTM Designation D 1921-63. This invention also involves a composition of matter comprising polycarbonate pellets characterized in that, (a) when said polycarbonate pellets are agitated on a screen having a mesh opening size of 850 microns, and when those pellets not retained on said 850 micron screen are then agitated on a screen having a mesh opening size of 710 microns, the portion of said pellets which together is retained on one or the other of said screens is more than 85 percent by weight; and (b) none of said pellets are retained when agitated on a mesh screen having a mesh opening size of 1,500 microns or more. Further, this invention involves a polycarbonate pellet characterized in that (a) it is retained when agitated on a mesh screen having a mesh opening size within the range of 200-1,000 microns; (b) it is not retained when agitated on a mesh screen having a mesh opening size of 1,500 microns or greater; and (c) it is formed by cutting polycarbonate which has been forced through a die. In another aspect, this invention involves a process for preparing polycarbonate pellets comprising (a) melting polycarbonate; (b) forcing such melted polycarbonate through a die having die holes with a diameter of 0.25 to 0.8 mm; and (c) cutting such polycarbonate upon its exit from said die to form pellets. The methods of this invention are useful for producing polycarbonate pellets, such pellets being useful, for example, in the production of films, extruded sheets, multi-layer laminates and molded or shaped articles of virtually all varieties, especially appliance and instrument housings, automobile body panels and other components for use in the automotive and electronics industries. This invention involves the production of polycarbonate in pellet form. A polycarbonate pellet of this invention, being that which is produced by the methods of this invention, is characterized by a size which is less than 1,500 microns, is advantageously less than 1,000 microns, is preferably less than 900 microns, and is more preferably less than 800 microns, but is as well greater than 200 microns, is advantageously greater than 500 microns, is preferably greater than 600 microns, and is more preferably greater than 700 microns. Size in this respect is determined by whether a pellet passes through, or is retained, as a result of agitation on a sieve or screen having a mesh opening size as stated. If the pellet passes through the sieve or screen, it is described as having a size which is equal to or less than that of the mesh opening, and if the pellet is retained, it is described as having a size that is greater than the mesh opening. However, a polycarbonate pellet of this invention is not retained after agitation on a sieve or screen having a mesh opening size of 1,500 microns or greater. The size characteristics of a sample, assay or specimen of polycarbonate pellets of this invention may be described by measurements made according to ASTM Method D 1921-63. This method involves use of a mechanical sieve-shaking device which imparts a uniform rotary motion to a group of sieves. The sieves are nested together in order of diminishing mesh opening size with a collection pan on the bottom. Those pellets which pass through one sieve are agitated on the sieve below, and so on until all pellets are either retained on a screen or drop to the collection pan. The number and mesh opening sizes of the sieves are selected based on the expected range of particle sizes of the pellets to be analyzed. The results obtained from this test are the median particle size of the sample studied, the dispersion of particle sizes across the whole sample, and the skew of the particle distribution. Median size and particle size dispersion are both expressed in microns ( µ , 10⁻⁶ meters). Skew is unitless. These characteristices are frequently determined with reference to a parcel, batch or lot of polycarbonate pellets weighing at least 150 pounds, advantageously at least 300 pounds, preferably at least 750 pounds, and more preferably at least 1,500 pounds, although it is not required that the batch or sample be any particular weight. A sample or batch of the polycarbonate pellets of this invention has, according to ASTM Method D 1921-63, (i) a median particle size of 250 to 1,000 microns, advantageously a median particle size of 500 to 900 microns, preferably a median particle size of 600-800 microns, and more preferably a median particle size of 650-750 microns; (ii) a particle size dispersion of less than 100 microns, advantageously less than 60 microns, and preferably less than 40 microns; (iii) a particle distribution skew of less than 0.25, advantageously less than 0.1, preferably less than 0.05, and more preferably zero. A parcel or assay of the polycarbonate pellets of this invention is further characterized in that, when said polycarbonate pellets are agitated on a screen having a mesh opening size of 850 microns, and when those pellets not retained on said 850 micron screen are then agitated on a screen having a mesh opening size of 710 microns, the portion of said parcel or assay of pellets which together is retained on one or the other of said screens is more than 85 percent by weight, is advantageously more than 90 percent by weight, is preferably more than 95 percent by weight, and is more preferably more than 98 percent by weight. The polycarbonate pellets of this invention are formed by cutting polycarbonate to the desired size after it has been forced through a die. This is typically accomplished by melting polycarbonate in heating means such as a screw-type extruder whereby the polymeric material is melted in a heated barrel and is, in molten form, forced through a die with openings of a size appropriate to obtain a pellet of the size desired. Pressure on the molten extrudate to force it through the die can be supplied, for example, by a screw (a rotating internal member with raised spiral flights) and/or by an optional gear pump. The polycarbonate when fed into an extruder for melting will typically already have been dried of solvent, and (although it is not required for purposes of this invention) the polycarbonate will typically have a solvent content of not more than 1.0 percent by weight, and preferably not more than 0.1 percent by weight. The methods of this invention for producing polycarbonate pellets within the size ranges set forth above involve steps to adjust the temperature of the polycarbonate melt for the purpose of attaining temperature uniformity within the extruder or other melting device, and controlling the viscosity of the melt. The methods of this invention also involve control of the flow rate at which the melted polymer exits the die, and the frequency with which the melted polymer is cut to form pellets. Back pressure in an extruder is typically increased when die hole size is decreased. Pressure can be mesured by a Bourdon-type or other pressure gauge mounted in the extruder barrel. (If desired, a needle or gate valve can be used to adjust pressure inside the extruder, or a gear pump can be used to boost pressure.) The smaller die hole used to obtain the pellets of this invention is typically 0.25 to 0.8 mm in diameter, is advantageously 0.5 to 0.75 mm in diameter, and is preferably 0.6 to 0.7 mm in diameter. In and of itself, use of a smaller die hole typically not only increases back pressure but also reduces flow rate out of the die. Reduced flow rate has the benefit of allowing more time for mixing of the melt within the extruder, which promotes temperature uniformity. However, it may be desirable to utilize an increase in screw speed to maintain flow rate and compensate for the increased back pressure caused by use of a smaller die hole. This results in more power being used to run the screw with the consequence of more shear heating. Conductive heating from the barrel may therefore be reduced as shear heating increases from increased back pressure, particularly after the solid bed has broken up and melting is complete. However, the barrel heat should be no lower than a level which, together with the shear heat, maintains a visosity low enough that the melted polymer can be readily forced through the die at an appropriate flow rate in relation to the frequency of cutting and the pellet size desired. The temperature of the polymer in an extruder can be measured by a pyrometer in the barrel, such as a thermocouple, or by a manual probe. Barrel heater bands as a source of heat in an extruder should be adjusted so that conductive heat supplied from the barrel in the melting section is sufficient to aid in formation of a molten film near the barrel surface. This avoids excessive shearing within the solid bed which would increase mechanical work input and the heat generated by shearing action of the polymer to an undesirable level. To the extent that heat supplied by the barrel can be held to a minimum so that it does not compete with, but rather supplements, the heat generated by the shearing action, proportionally more of the heat will come from the one source of shearing, making it easier for temperature uniformity to be achieved by thorough mixing of the melt. Supplying just enough conductive heat through the barrel to maintain the temperature of the polycarbonate just above its softening temperature is a good measure of the heat input required from the barrel heaters. The heat derived from the barrel heaters and from shearing action should together be sufficient, in relation to the melt flow value of the polymer, to keep the viscosity of the polymer low enough that a rate of flow out of the die is established which is appropriate, in relation to the frequency of cutting the extrudate, for the size of pellet desired. Attempting to overcome temperature non-uniformity in the melt by adding heat at the die is generally not a desirable practice. The die should be held at a temperature which will maintain the target temperature of the melt in the forward section of the barrel as it approaches the die. Since the melt cannot be mixed in the die, and because the heat conduction path length varies in the die from one die opening to another, the application of extra heat at that point typically only aggravates the problem of temperature non-uniformity. After the molten polycarbonate is forced through a die, by extrusion or other means, it can be pelletized. Pelletization can be performed in a variety of different ways. The molten extrudate can either be cut as it emerges from a die, or it can be cooled and hardened in a water bath in the form of a strand which is cut. When the molten extrudate is cut at the face of the die, a stream or spray of air and/or water is directed at the cutting site to help cool the pellets and move them toward a discharge chute. The pellets may then go into a slurry where further quenching will occur. Quenching will help solidify the exterior shell of the pellet so that agglomeration is prevented, although there is usually enough residual heat content in the interior portion of the pellet so that moisture remaining on the surface of pellet after removal from the slurry will evaporate. Systems are also known where cutting actually occurs under water, and the pellets are quenched and go into a slurry immediately upon being cut. Molten extrudate cut at the die face is, in most instances, cut by a rotating circular multiple blade knife. However, pelletizers are also known which employ a rotary, screw-shaped knife at the die face, or a helically-grooved cutter may be disposed about a cylindrical die. In the case of a centrifugal pelletizer, however, the polymer melt is fed into a rotating die and is forced through peripheral holes in the die as it spins. The emerging extrudate is cut by a stationary knife as each die hole spins past. When the die is spinning fast enough to force the extrudate out of the die holes, sufficient angular momentum is imparted to pellets formed by a spinning die to cause them to be thrown into the quenching bath or slurry without need for as much direct assistance from an air and/or water stream. When using a pelletizer which has a spinning blade, sufficient angular momentum must be imparted by the blade to the pellets so that they are cast into the quenching system quickly enough that any tendency to agglomerate is substantially avoided. A blade speed of at least 2,500 rpm, and preferably at least 3,000 rpm, is typically needed to obtain a cutting frequency which not only produces the desired pellet size but imparts angular momentum to the cut pellets sufficient to substantially avoid a problem of agglomeration. An upward adjustment in blade speed may be needed if the extrudate is higher in the range of acceptable viscosities because more of the energy causing the blade to spin will be absorbed in cutting than in the case of an extrudate which is lower in the appropriate viscosity range. If too much energy is absorbed in cutting, insufficient angular momentum may be imparted to the pellet to allow it to be hurled into the slurry without agglomeration. A tendency toward agglomeration of the pellets may also exist if the die holes are too close together. Die holes should be spaced a minimum of at least 4.0 mm, and preferably at least 5.0 mm, measured center line to center line. Blade speed should also be adjusted in relation to the flow rate at which the polymer exits the die so that the frequency with which the extrudate is cut produces a pellet of the desired size. The pellets of this invention are typically cylindrical in shape, i.e. shaped like a circular column, but may also be shaped like an eliptical column or an oblate spheroid. The length/diameter (L/D) ratio of a cylindrical pellet is preferably 1/1 but may vary from as much as 2/1 to 1/2. A geometrically correct right cylinder may, in one aspect, be considered to be a circular column having a top and bottom surface each formed by a flat circle and a shaft or body, extending between said flat circular ends, defined by parallel sides. The shape of the cylindrical pellets of this invention may vary from that of such a right cylinder in numerous ways while nevertheless remaining substantially cylindrical. Representative examples of such variances in shape may take the form of a top and/or bottom which is not flat but rather has a convex, domed shape where the point of greatest deviation of the top above a flat surface, or the bottom below a flat surface, is typically no more than 3L/8, and is more typically no more than L/4. Such deviation of the top and/or bottom of a cylindrical pellet of this invention from a flat surface may be the same or different. The sides of the shaft or column of a cylindrical pellet of this invention may not be truly parallel but may rather, by way of further example, be slightly concave. The point of greatest deviation of such a concave side from the line of a parallel side is typically disposed inward toward the center line of the cylinder no more than D/8, and more typically no more than D/16. The amount of such deviation from the parallel of the sides of the shaft or column of a cylindrical pellet of this invention may or may not be constant about the circumference of the cylindrical shaft or column. However, the top, bottom and side surfaces of the cylindrical pellets of this invention, when compared for example to powdered polycarbonate, are smooth with no strings, jags or pointed protrusions. The polycarbonate involved in this invention is typically prepared from an aromatic dihydroxy compound which is reacted with a carbonate precursor, such as a carbonic acid derivative. A carbonic acid derivative such as the carbonyl halide phosgene is useful for such purpose. However, even with the application of heat, the direct contact of an aromatic dihydroxy compound and a carbonic acid derivative does not produce a reaction with a rate sufficient to form polycarbonate. The reaction should therefore be facilitated by the presence in the reaction mixture of pyridine or another tertiary amine. The salt-like adduct of the carbonic acid derivative which is formed with the amine reacts more favorably with the dihydroxy compound than the carbonic acid derivative itself. The reaction should be carried out in the absence of water to avoid hydrolysis of the carbonic acid derivative, and a non-reactive organic solvent is used which will keep the polycarbonate product in a viscous solution as it forms. The non-reactive solvent is frequently methylene chloride or another halogenated hydrocarbon, or benzene or toluene. When the formation of polycarbonate is complete, the reaction mixture is washed with an aqueous solution of a mineral acid to convert any remaining amine to its corresponding salt, and the organic phase is washed further with water to remove acidic electrolytes. The solvent can be removed from the organic phase by distillation. Alternatively, the polycarbonate may be precipitated from the organic phase by a non-solvent such as petroleum ether, methanol, isopropanol or an aliphatic hydrocarbon. However, even at temperatures as low as from 0°C to 40°C, a carbonic acid derivative reacts at a better rate with deprotonated aromatic dihydroxy compounds than it does in a non-aqueous system. A solution is formed of (i) an aromatic dihydroxy compound and a strong base in aqueous phase, and (ii) an inert, immiscible organic solvent which will dissolve both the carbonic acid derivative and the polycarbonate product. Solvents such as xylene or methylene chloride or other chlorinated hydrocarbons are suitable for such purpose. Caustic such as the the alkali or alkaline earth carbonates, oxides or hydroxides function best as the base, the total amount of which may be added at the beginning of, or incrementally during, the reaction. A pH of 10 to 13 is typically maintained throughout the reaction. The base forms the dianion of the aromatic dihydroxy compound in the aqueous phase, and the aqueous phase forms a continuous phase with the organic solvent dispersed, upon agitation, as droplets therein. Carbonic acid derivative is bubbled into this mixture, is dissolved in the organic solvent, and reacts with the aromatic dihydroxy compound at the interface of the droplets with the aqueous phase. Catalysts accelerate the rate of the reaction sufficiently to allow the formation of high polycarbonates at the same low temperature at which the reaction began. Suitable catalysts for such purpose are tertiary amines such as triethylamine or N,N-dimethyl-cyclohexylamine, or quaternary ammonium bases such as tetramethyl ammonium hydroxide or triethyl benzyl ammonium hydroxide, or quaternary phosphonium, quaternary arsenium or tertiary sulfonium compounds. A bisaryl ester can be used in place of a carbonic acid derivative. Polycarbonate can additionally be made by transesterification, which is accomplished by reacting a dihydroxy compound with a bis carbonic acid ester. A strongly alkaline catalyst such as the alkali metals and the alkaline earth metals and their oxides, hydrides or amides, or the basic metal oxides such as zinc oxide, lead oxide and antimony oxide is used as an accelerator, and the reaction is run at temperatures of between 150°C and 300°C, using vacuum to remove the residue of the bis carbonic acid ester. At temperatures between 150°C and 200°C, low molecular weight polycarbonate terminated with bis carbonic acid ester groups is formed, which can then interreact at temperatures above 250°C to form higher weight polycarbonate by splitting off the original bis carbonic acid ester. This process is carried out at reduced pressure. Suitable dihydroxy compounds for the preparation of polycarbonate are those wherein the sole reactive groups are two hydroxyl groups, such as variously bridged, substituted or unsubstituted aromatic diols (or mixtures thereof) represented by the general formula where (a) X is a substituted or unsubstituted divalent hydrocarbon radical containing 1-15 carbon atoms, or is a mixture of more than one of such radicals, or is -S-, -S-S-, -SO-,-SO₂-, -O-, -CO-, or a single bond; (b) Y is independently a halogen such as fluorine, chlorine, bromine or iodine; or is a monovalent organic radical such as an alkyl group of 1-4 carbons, an aryl group of 6-8 carbons (e.g. phenyl, tolyl, xylyl or the like), an alkoxy group of 1-4 carbons, or an aryloxy group of 6-8 carbons; and (c) m is 0 or 1, and n is 1-24 inclusive. When n is less than 4, the other position(s) is/are occupied by hydrogen. The carbonate polymers employed in the present invention can also be based on dihydroxy benzenes such as pyrocatechol, resorcinol and hydroquinone (and their halo- and alkyl-substituted derivatives), and on dihydroxy naphthalenes and anthracenes. The carbonate polymers employed in the present invention can also be linear or branched. Although the polycarbonates mentioned above, such as those derived from 2,2-bis(4-hydroxyphenyl)propane ( Bisphenol-A ) or from 1,1-bis(4-hydroxyphenyl)-1-phenyl ethane ( Bisphenol-AP ), can each be employed in this invention as a homopolymer (i.e. the product obtained when only one dihydroxy compound is used to prepare the polycarbonate), the carbonate polymers used herein can also be derived from two or more different dihydroxy compounds, or mixtures thereof, in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired. For example, a typical copolymer is that which is made from Bisphenol-A and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane ( Tetrabromo Bisphenol-A ) wherein either co-monomer can be present in a 1-99 to 99-1 molar ratio. Copolymers can also be formed when a bisphenol is reacted with a carbonic acid derivative and a polydiorganosiloxane containing α,ω-bishydroxyaryloxy terminal groups to yield a siloxane/carbonate block copolymer (as are discussed in greater detail in Paul, USP 4,569,970), or when a bisphenol is reacted with a bis(ar-haloformylaryl) carbonate to yield an alternating copolyestercarbonate, the bis(ar-haloformylaryl) carbonate being formed by reacting a hydroxycarboxylic acid with a carbonic acid derivative under carbonate forming conditions. Copolyestercarbonates are discussed in greater detail in Swart, USP 4,105,533. Also useful in this invention are physical blends of two or more of the carbonate homo- and/or copolymers described above. The term polycarbonate as used herein, and in the claims appended hereto, should therefore be understood to include carbonate homopolymers, carbonate copolymers (as described above), and/or blends of various carbonate homopolymers and/or various carbonate copolymers. The methods generally described above for preparing carbonate polymers suitable for use in the practice of this invention are well known; for example, several methods are discussed in detail in Schnell, USP 3,028,365; Campbell, USP 4,384,108; Glass, USP 4,529,791; and Grigo, USP 4,677,162. Blends of polycarbonate and other polymers are also suitable for formation of the pellets of this invention. Other polymers suitable for preparing such blends with polycarbonate include, but are not limited to, the following: polyacetal, including that which is formed by the bond opening and polymerization of the carbonyl group of an aldehyde to give a -(-CH₂-O-)-repeating unit, as well as the reaction products of polyols and aldehydes; polyacrylate; polyamide, including that which is prepared by the reaction of a diamine and diacid or the self polymerization of a cyclic lactam; polyester, including that which is prepared by the condensation reaction of a diacid and a diol or the self esterification of a hydrocarboxylic acid, and copolymers thereof; poly(ethylene oxide); polymethacrylate; polyolefin, including copolymers thereof; poly(phenylene ether), including that which is prepared by the oxidative coupling polymerization of a phenol to give a -(-pAr-O-)-repeating unit; polystyrene, including copolymers thereof; polyurethane, including that which is prepared by the reaction of a diisocyanate and a polyol; and vinyl polymers, including poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl amide), poly(vinyl chloride), and poly(vinyl ether), including copolymers of each; where Ar in the foregoing list of polymers is an aromatic organic (e.g., C₆-C₁₀) radical. Numerous additives are available for use in the compositions of this invention for a variety of purposes including protection against thermal, oxidative and ultra-violet degradation. Representative of thermal and oxidative stabilizers which can advantageously be utilized herein are hindered phenols, hydroquinones, phosphites, including substituted members of those groups and/or mixtures of more than one thereof. A preferred phenolic anti-oxidant is Irganox™ 1076 anti-oxidant, which is available from Ciba-Geigy Corp. and is discussed in greater detail in U.S. Patents 3,285,855 and 3,330,859. Ultra-violet light stabilizers such as various substituted resorcinols, salicylates, benzotriazoles, benzophines and hindered phenols can also be usefully included herein, as can be lubricants; colorants; fillers such as talc; pigments; ignition resistance additives; mold release agents; and reinforcing agents such as fiberglass. Additives and stabilizers such as the foregoing, and others which have not been specifically mentioned, are known in the art, and the decision as to which, if any, to use is not critical to the invention. However, such additives, if used, will typically not exceed 50 percent by weight of the total composition, and preferably will not exceed 30 percent by weight thereof. Illustrative Embodiments. To illustrate the practice of this invention, examples of several embodiments are set forth below. It is not intended, however, that these examples (Examples 1-16) should in any manner restrict the scope of this invention. Some of the particularly desirable features of this invention may be seen by contrasting the characteristics of Examples 1-16 with those of various controlled formulations (Controls A-G) which do not possess the features of, and are not therefore embodiments of, this invention. Numerous samples of polycarbonate, and a sample of a blend of polycarbonate and an acrylonitrile/butadiene/styrene ( ABS ) copolymer, were tested for particle size by ASTM Method D 1921-63. This method involves use of a mechanical sieve-shaking device which imparts a uniform rotary motion to a group of sieves. The sieves are nested together in order of diminishing mesh opening size with a collection pan on the bottom. The number and mesh opening sizes of the sieves are selected based on the expected range of particle sizes. The results obtained from this test are the median particle size of the sample studied, the dispersion of particle sizes across the whole sample, and the skew of the particle distribution. Median size and particle size dispersion are both expressed in microns ( µ , 10⁻⁶ meters). Skew is unitless. The melt flow rate ( MFR ) for polycarbonate is determined according to ASTM Designation D 1238-89, Condition 300/1.2. Controls A-F. Samples of several commercially available brands of polycarbonate resin were tested for particle size according to the method described above. These samples were in powdered form when obtained and could be subjected to sieve testing without further processing. The median particle size, particle size dispersion and skew are shown for Controls A-F in Table I. The respective weight percentages of the sample retained on the various sieves of decreasingly smaller mesh size, and the density, are shown for Controls A-F in Table II. Median Particle Size, Dispersion, Skew and Density for Controls A-F Median particle size in microns Particle size dispersion in microns Skew Density, lbs/ft³ Control A3452050.3426.2 (419.7 kg/m³) Control B1751260.3142.5 (680.9 kg/m³) Control C4904300.2343.7 (700.1 kg/m³) Control D9404300.0732.5 (520.7 kg/m³) Control E6304380.1939.3 (629.6 kg/m³) Control F2201250.2835.0 (560.7 kg/m³) Percent Retained on Screen for Controls A-F Percent of sample retained on each sieve (mesh size in microns) 2,000 1,400 1,000 850 710 500 250 106 <106 Control A002.123.893.3911.6552.0226.280.65 Control B000.500.550.581.3233.9342.1820.94 Control C04.837.1512.797.6115.1122.6220.859.04 Control D0.4416.2118.5524.427.9518.5911.561.950.33 Control E09.6012.03--23.6914.7424.3013.572.07 Control F01.613.27--15.4414.9435.9524.784.01 Controls A-F show the relatively large particle size dispersion and skew which is characteristic of powdered polycarbonate. Example 1. Polycarbonate with a melt flow rate of 3.0 was fed to a 3½ inch (8.9 cm) diameter single screw extruder at the average rate of 364 lbs/hour (165.1 kg/hr). The molten polycarbonate was extruded through a die housing containing 392 die holes having a diameter of 0.028 inch (0.07 cm). The extruded polycarbonate was cut into pellets at the die face. The median particle size, the particle size dispersion and the skew of the particle distribution for Example 1 are shown below in Table III. Example 2. Polycarbonate with a melt flow rate of 13.5 was fed to a 2½ inch (6.35 cm) diameter single screw extruder at the average rate of 150 lbs/hour (68.04 kg/hr). The molten polycarbonate was extruded through a die housing containing 99 die holes having a diameter of 0.031 inch (0.079 cm). The extruded polycarbonate was cut into pellets at the die face. The median particle size, the particle size dispersion and the skew of the particle distribution for Example 2 are shown below in Table III. Example 3. Polycarbonate with a melt flow rate of 13.5 was fed to a 2½ inch (6.35 cm) diameter single screw extruder at the average rate of 60 lbs/hour (27.22 kg/hr). The molten polycarbonate was extruded through a die housing containing 99 die holes having a diameter of 0.031 inch (0.079 cm). A hot face cutter was used to cut the extruded polycarbonate into pellets at the die face. The median particle size, the particle size dispersion, the skew of the particle distribution, and the density for Example 3 are shown below in Table III. The respective weight percentages retained on the various sieves of decreasingly smaller mesh size are shown for Example 3 in Table IV. Example 4. Polycarbonate with a melt flow rate of 14.5 was fed to a 90 mm diameter twin screw extruder at the average rate of 495 lbs/hour (224.5 kg/hr). The molten polycarbonate was extruded through a die housing containing 280 die holes having a diameter of 0.027 inch (0.0686 cm). A hot face cutter having eight cutting blades, and rotated at 4,200 rpm, was used to cut the extruded polycarbonate into pellets at the die face. The median particle size, the particle size dispersion, the skew of the particle distribution, and the density for Example 4 are shown below in Table III. The respective weight percentages retained on the various sieves of decreasingly smaller mesh size are shown for Example 4 in Table IV. Median Particle Size, Dispersion, Skew and Density for Examples 1-4 Median particle size in microns Particle size dispersion in microns Skew Density, lbs/ft³ Example 1920450.11-- Example 2880600-- Example 386045042 lbs/ft³(672.8 kg/m³) Example 486055-0.0943.7 lbs/ft³(700.1 kg/m³) Percent Retained on Screen for Examples 3 and 4 Percent of sample retained on each sieve (mesh size in microns) 2,000 1,000 850 710 500 250 Example 30066.230.92.80 Example 400.1151.6246.032.210.03 Control G and Examples 5-9. Polycarbonate with a melt flow rate of 3.0 was fed to a 3½ inch (8.9 cm) diameter single screw extruder at the average rate of 364 lbs/hour (165.1 kg/hr). The molten polycarbonate was extruded through a die housing containing 392 die holes having a diameter of 0.028 inch (0.07 cm). A hot face cutter having four or eight cutting blades, and rotated at different speeds, was used to cut the extruded polycarbonate into pellets at the die face. The median particle size, the particle size dispersion, the skew of the particle distribution, the cutter speed, the number of blades, the melt flow value, the extruder feed rate and the density are shown below for Control G and Examples 5-9 in Table V. The respective weight percentages retained on the various sieves of decreasingly smaller mesh size is shown below for Control G and Examples 5-9 in Table VI. Control G and Examples 5-9 Median particle size in microns Particle size dispersion in microns Skew Density, lbs/ft³ Cutter speed, rpm Number of cutter blades Control G1,0005000.6826.8 (417.8 kg/m³)2,0008 Example 5 850400.2544.3 (709.7 kg/m³)3,600 4 Example 6 78040043.7 (700.1 kg/m³)3,6008 Example 778040043.7 (700.1 kg/m³)3,3008 Example 880040043.7 (700.1 kg/m³)3,0008 Example 9890950.1640.6 (650.4 kg/m³)2,5008 Control G and Examples 5-9 Percent of sample retained on each sieve (mesh size in microns) 2,000 1,000 850 710 500 250 Control G47.931.4420.0529.800.760.02 Example 50.050.1867.7532.000.020 Example 60.28.0505.4089.624.180.02 Example 71.331.392.7793.041.440.03 Example 83.980.917.6486.860.580.03 Example 913.511.2150.6934.420.160.01 Examples 10-14. Polycarbonate was fed to a 2½ inch (6.35 cm) diameter single screw extruder. The molten polycarbonate was extruded through a die housing containing 210 die holes having a diameter of 0.028 inch (0.07 cm). A hot face cutter having three cutting blades, and rotated at 4,200 rpm, was used to cut the extruded polycarbonate into pellets at the die face. The median particle size, the particle size dispersion, the skew of the particle distribution, the melt flow value, the extruder feed rate and the density are shown below for Examples 10-14 in Table VII. The respective weight percentages retained on the various sieves of decreasingly smaller mesh size are shown below for Examples 10-14 in Table VIII. Examples 10-14 Median particle size in microns Particle size dispersion in microns Skew Density, lbs/ft³ Melt Flow Value Feed Rate, lbs/hr Example 10705300.1740.6 (650.4 kg/m³)14.5100 (45.4 kg/hr) Example 1171060038.7 (620 kg/m³)14.5150 (68 kg/hr) Example 1279545042.5 (680.85 kg/m³)3.5200 (90.8 kg/hr) Example 1380040043.1 (690.5 kg/m³)3.5150 (68 kg/hr) Example 1477040043.7 (700.1 kg/m³)3.5100 (45.4 kg/hr) Examples 10-14 Percent of sample retained on each sieve (mesh size in microns) 2,000 1,000 850 710 500 250 Example 1000.070.6348.0250.900.38 Example 1100.321.6444.1453.870.03 Example 1200.077.7190.971.250 Example 1300.027.7390.831.420 Example 1400.172.0194.353.480 Examples 1-14 show the desirably low particle size dispersion and skew which are characteristic of the polycarbonate pellets of this invention, regardless of the pellet size selected for production. Control G shows the result of using too low a cutter speed, for example less than 2,500 rpm. Sufficient agglomeration of pellets occurred in Control G to raise not only the median particle size, but the particle size dispersion and skew as well, to undesirable levels. Examples 15 and 16. Polycarbonate ( PC ) with a melt flow rate of 13.5 and acrylonitrile/butadiene/styrene copolymer ( ABS ) containing, by weight, 17.0 percent acrylonitrile, 6.5 percent butadiene and 76.5 percent styrene were fed to a 2½ inch (6.35 cm) diameter single screw extruder at different feed rates. The molten PC/ABS blend was extruded through a die housing containing 210 die holes having a diameter of 0.7 mm. A hot face cutter having three cutting blades, and rotated at 4,250 rpm, was used to cut the extruded PC/ABS blend into pellets at the die face. The median particle size, the particle size dispersion, the skew of the particle distribution, the component feed rate, the speed, melt temperature and pressure (before the die plate) of the extruder, and the density are shown below for Examples 15 and 16 in Table IX. The respective weight percentages retained on the various sieves of decreasingly smaller mesh size are shown below for Examples 15 and 16 in Table X. Examples 15 and 16 Example 15 Example 16 Median Particle Size800925 Particle Size Dispersion4033 Skew00.08 Density, lbs/ft³41 (656.8 kg/m³)41 (656.8 kg/m³) Polycarbonate Feed Rate, lbs/hr132 (59.9 kg/hr)198 (89.8 kg/hr) ABS Feed Rate, lbs/hr68 (30.8 kg/hr)102 (46.3 kg/hr) Extruder Speed, rpm80150 Extruder Melt Temperature, °C300303 Extruder Melt Pressure, psi550 (3.79 MPa)940 (6.48 MPa) Examples 15 and 16 Percent of sample retained on each sieve (mesh size in microns) 2,000 1,000 850 710 500 250 Example 1500.328.1690.760.730 Example 1601.0298.110.8700 Examples 15 and 16 show the desirably low particle size dispersion and skew which are characteristic of the pellets of this invention when they are prepared from polycarbonate blended with another polymer, for example ABS.	Polycarbonate pellets which are formed by cutting polycarbonate which has been forced through a die characterized in that (a) the median particle size of said pellets is between 250 and 1,000 microns ; (b) the particle size dispersion of said pellets is less than 100 microns ; and (c) the skew of the particle distribution is less than 0.25 ; each as determined according to ASTM Designation D 1921-63. The polycarbonate pellets of Claim 1 characterized in that the particle size dispersion of said pellets is less than 60 microns. The polycarbonate pellets of claim 1 characterized in that the particle size dispersion of said pellets is less than 40 microns. The polycarbonate pellets of claims 1, 2 or 3 characterized in that the skew of the particle distribution is less than 0.1. The polycarbonate pellets of claims 1, 2 or 3 characterized in that the skew of the particle distribution is less than 0.05. The polycarbonate pellets which are formed by cutting polycarbonate which has been forced through a die characterized in that, (a) when said polycarbonate pellets are agitated on a screen having a mesh opening size of 850 microns, and when those pellets not retained on said 850 microns screen are then agitated on a screen having a mesh opening size of 710 microns, the portion of said pellets which together is retained on one or the other of said screens is more than 85 percent by weight ; and (b) none of said pellets are retained when agitated on a mesh screen having a mesh opening size of 1,500 microns or more. The polycarbonate pellets of claim 6 wherein more than 90 percent by weight of said pellets are together retained on one or the other of said screens. The polycarbonate pellets of claim 6 wherein more than 95 percent by weight of said pellets are together retained on one or the other of said screens. The polycarbonate pellets of claims 1, 2, 3, 4, 5, 6, 7 or 8 being further characterized in that they are formed by cutting molten polycarbonate at the face of a die. The polycarbonate pellets of claims 1, 2, 3, 4, 5, 6, 7 or 8 being further characterized in that they comprise polycarbonate blended with one or more polymers selected from the group consisting or polyacetal ; polyacrylate ; polyamide ; polyester ; poly(ethylene oxide) ; polymethacrylate ; polyolefin ; poly(phenylene ether) ; polystyrene ; polyurethane ; vinyl polymers ; and acrylonitrile/butadiene/styrene copolymers. Use of the polycarbonate pellets of claims 1 to 10 for the production of films, extruded sheets, multi-layer laminates and shaped or molded articles.	DOW CHEMICAL CO; THE DOW CHEMICAL COMPANY	KIRK RICHARD ODETT; KIRK, RICHARD ODETT
EP-0489366-B1	489,366	EP	B1	EN	19,951,018	1,992	20,100,220	new	B41F23	F26B23	F26B23, B41F23	F26B 23/02B, B41F 23/04B6B	Drying apparatus and its control device for rotary printing press	In the drying apparatus for rotary printing press for drying the ink on the printed paper (2) which has a direct fired deodorizing apparatus (8) and a heat recovery apparatus (9) for heating the hot air circulating in a drying apparatus by using the exhaust gas from the deodorizing apparatus (8), the drying apparatus and its control device are so adapted that a bypass line (20) is installed on the hot air circulation line to bypass the heat recovery apparatus (9) to control the temperature of printed paper (2) and/or the temperature of hot air blowing from nozzles (3) by adjusting the degree of opening of bypass damper (21) disposed in the bypass line (20), and the burning amount of the burner for deodorization (10) is controlled so that the deodorizing apparatus furnace temperature corresponding to the blowing hot air temperature or paper temperature is obtained. Further, the control device carries out the control in response to the change in printing speed. Thus, the control responsiveness can be enhanced.	The invention relates to a drying control device for printed paper drying apparatus which evaporates the solvent in ink by blowing hot air onto the printed paper. More particularly it relates to a hot air heating type drying apparatus for a rotary printing press which evaporates the solvent in ink by feeding printed paper into a drying apparatus body having a negative pressure and by blowing hot air onto the paper. The apparatus, according to this invention can be applied to exhaust gas disposal apparatus for solvent-containing substances in the production process of plastic film and the like. Still more particularly, this invention relates to a paper temperature control device of drying apparatus for a rotary printing press. A conventional drying apparatus for a printing press will be described with reference to FIG. 9. Reference numeral 1 denotes a drying apparatus body, 2 denotes printed paper, 3 denotes a hot air blowing nozzle provided in the drying apparatus 1, 4 denotes a burner for heating the hot air, 5 denotes a blower for the first zone, 6 denotes a blower for the second zone, and 7 denotes an exhaust gas blower, and 8 denotes a deodorizing apparatus. The paper 2 printed by the printing press is fed into the drying apparatus body 1, and the hot air from the burner 4 is blown onto the paper through the hot air blowing nozzles 3 so that the solvent in ink is evaporated. The hot air, which has been blown onto the paper 2 in the drying apparatus body 1 from the hot air blowing nozzles 3, is returned to the suction side of the blower for the first zone 5 and the blower for the second zone 6, and is then reheated by the burner 4 and sent to the hot air blowing nozzles 3. Part of the hot air is sucked by the exhaust gas blower 7 and sent to the deodorizing apparatus 8, where the gas is deodorized. Part of the deodorized gas is returned to the drying apparatus body 1, and the remnant is discharged into the atmosphere. For pollution prevention, a negative pressure is produced in the drying apparatus body 1 to prevent the hot gas (exhaust gas) in the drying apparatus body 1 from discharging to the outside. The conventional drying apparatus for a rotary printing press shown in FIG. 9 has the following disadvantages: (1) The apparatus has a high consumption of fuel because the fuel supplied to the burner 4 is burned to reheat the hot air circulating in the drying apparatus body. (2) The operation cannot be performed while the amount of exhaust gas is restricted because if the concentration of solvent in the exhaust gas is raised by the restriction of exhaust gas discharged from the deodorizing apparatus 8, the temperature in a catalytic reactor provided in the deodorizing apparatus 8 becomes too high (rises to about 500 °C, the upper limit of temperature). (3) A large-size exhaust gas blower 7 is required. This is because large amounts of outside air (air for combustion) is introduced into the drying apparatus body 1 since the temperature of circulating hot air or the temperature of paper is kept at about 190-250 °C by controlling the burning conditions of burner 4 disposed in the circulation line, so that large amounts of exhaust gas must be discharged by the exhaust gas blower 7 to maintain the negative pressure in the drying apparatus body 1. (4) The capacity of burner 4 disposed in the circulation line must be 3-5 times higher than the capacity needed for normal operation in order to speed up the startup operation since the rotary printing press is frequently stopped for change of plates. To solve these problems, the inventors made an invention shown in FIG. 10 (refer to Japanese Patent Application No. 083912/1989 (1-083912)). In FIG. 10, reference numeral 1 denotes a drying apparatus body, 2 denotes printed paper, 3 denotes a hot air blowing nozzle, 4 denotes a preheating burner, 5 denotes a blower for the first zone, 6 denotes a blower for the second zone, 7 denotes an exhaust gas blower, 8 denotes a direct fired deodorizing apparatus, 9 denotes a heat recovery apparatus, 10 denotes a burner for deodorization, 11 denotes a preheater, 12 denotes a direct fired reactor, 13 denotes a hot air temperature control device for regulating burning at the burner 10 for deodorization for the direct fired deodorizing apparatus 8 based on a value detected by a temperature sensor 16 for the hot air blown from the nozzles, 14 denotes a paper temperature control device for regulating burning at the burner for deodorization 10 in the direct fired deodorizing apparatus 8 based on the value detected by a paper temperature sensor 17, and 15 denotes a selector switch. At the startup before the normal operation, the exhaust gas blower 7 is activated to draw the outside air (air for combustion) into the drying apparatus body 1. The outside air drawn into the drying apparatus body 1 is directed from the exhaust gas blower 7 to the inside of heat transfer tube of the preheater 11, the direct fired reactor 12, the outside of heat transfer tube of the preheater 11, and the inside of heat transfer tube of the heat recovery apparatus 9 in that sequence. Also, the outside air drawn into the drying apparatus body 1 is circulated in the drying apparatus body 1 by activating the blower for the first zone 5 and the blower for the second zone 6. Then, the air circulating in the drying apparatus body 1 is heated by igniting and burning the preheating burner 4. The air in the drying apparatus body 1 is directed as the air for combustion from the exhaust gas blower 7 to the inside of heat transfer tube in the preheater 11 and to the direct fired reactor 12. Then, the fuel for the burner for deodorization 10 is ignited and burned. The produced exhaust gas is directed from the outside of heat transfer tube of the preheater 11 to the inside of heat transfer tube of the heat recovery apparatus 9. This exhaust gas, after preheating the air, is discharged out of the drying apparatus body 1. Thus, the circulating air in the drying apparatus body 1 can be heated rapidly to a specified temperature at the startup before the normal operation. When this condition is established, the preheating burner 4 is turned off to start the normal operation. In the normal operation, the paper 2 printed by the rotary printing press is fed into the drying apparatus body 1, while hot air is blown into the paper passage through the hot air blowing nozzles 3 so that the printed paper 2 is exposed to the hot air and the solvent contained in the ink on the paper is evaporated. The hot air containing the evaporated solvent (exhaust gas of about 140-170 °C) is returned to the outside of heat transfer tube of heat recovery apparatus 9 at the suction side of the blower for the first zone 5 and the blower for the second zone 6, where the hot air is reheated to about 190-250 °C by the exhaust gas passing through the inside of heat transfer tube of the heat recovery apparatus 9, namely the exhaust gas fed from the direct fired reactor 12 of the direct fired deodorizing apparatus 8 (exhaust gas of about 400-500 °C), and directed to the hot air blowing nozzles 3. Part of the hot air in the drying apparatus body 1 is sucked by the exhaust gas blower 7 and fed into the preheater 11 of the direct fired deodorizing apparatus 8, where part of the hot air is preheated by the exhaust gas from the direct fired reactor 12. Next, the hot air is directed to the direct fired reactor 12 which is heated to about 700-1000 °C by the burner for deodorization 10, where the evaporated solvent in the hot air is burned for the deodorization of hot air. The exhaust gas produced at this time is directed to the inside of heat transfer tube of the heat recovery apparatus 9 for the above-described heat exchanging and is then discharged out of the drying apparatus body 1. The heat recovery apparatus 9 can use a shell and tube heat exchanger or a plate type heat exchanger. When drying is controlled based on the hot air temperature, the set value of deodorizing apparatus furnace temperature on the hot air temperature control device 13 is calculated for correction from the value detected by the blowing hot air temperature sensor 16. Based on the result, the burning amount of the burner for deodorization 10 is controlled, and the temperature of hot air blowing from the nozzles is kept at the set value. When drying is performed by paper temperature control, the set value of deodorizing apparatus furnace temperature on the paper temperature control device 14 is calculated for correction from the value detected by the paper temperature sensor 17. Based on the result, the burning at the burner for deodorization 10 is controlled, and the temperature of hot air blowing from the nozzles is kept at the set value. The conventional drying control device for the rotary printing press shown in FIG. 10 has the following disadvantage: since the deodorizing capability of the direct fired deodorizing apparatus 8 relates directly to the furnace temperature of direct fired reactor 12 as shown in FIG. 10, the furnace temperature must be not less than the lower limit TDL in order to comply with the regulations regarding the odor concentration. For the conventional drying control device for the rotary printing press shown in FIG. 10, nevertheless, the furnace temperature of the direct fired deodorizing apparatus 8 is not controlled. For example, in the paper temperature control, when the thermal load is decreased (for example, when the printing speed decreases), the burning amount of the burner for deodorization 10 is decreased, sometimes resulting in a decrease in deodorizing apparatus furnace temperature down to a value less than the lower limit. In the apparatus disclosed in Japanese Patent Application No. 083912/1989 (1-083912), the controllability is not high because the blowing hot air temperature does not respond to the temperature change in the reaction furnace 12 since the heat capacity of the heat exchanger 9 is high, when a speed change (i.e., thermal load fluctuation) occurs in the printing press or when an attempt is made to change a control target value (instrumental set value) of blowing hot air temperature. Furthermore, according to this conventional art, the hot air can be heated in about one minute by using the preheating burner 4 at the startup, but the apparatus has no effective mechanism for cooling the hot air when the printing speed is decreased due to troubles or adjustments in the printing press during the normal operation. That is, the responsiveness of paper temperature is very low because the deodorizing apparatus furnace temperature has a lower limit for providing proper deodorizing capability and because the heat capacity of the heat exchanger is high. Therefore, the paper temperature exceeds the specified value for a long period of time, resulting in a heavy paper loss. It is known from Japanese Patent Application No. 6963/1982 (58-124113) to suppress a useless combustion and enable a successive drying and baking of paint of belt-shaped painted matter by a method wherein a logical solvent vapor amount is calculated from painting conditions, an exhaust rate of an oven and baking conditions suitable for the exhaust rate are set, and requirements are retained quickly by a comparison of the calculation results with measured values. European Patent Application print 0 273 230 A2 describes the drying of continuously transported textile web in a treating device comprising two successively arranged treating zones with hot gas. The gas discharged from the first treating zone is fed after reheating to the second treating zone as fresh gas. At the exit from this second treating zone a first portion of the discharged gas is after-burned. The so reheated discharged first gas portion first reheats the remaining, second portion of the discharged gas and, before it is discharged to the atmosphere, reheats the gas discharged from the first treating zone and preheats the fresh gas. The object of this invention as claimed in the appended claims is to improve the first-mentioned drying apparatus in which the deodorizing apparatus furnace temperature is kept at a specified value, and the deodorizing apparatus furnace temperature does not decrease to a value less than the lower limit when the thermal load, such as the printing speed, changes. To attain the above object, according to a first aspect of this invention, a drying apparatus for rotary printing press is provided in which hot air is blown onto printed paper to dry the printed paper by evaporating the solvent in ink, and this hot air is reheated by using the exhaust gas from the direct fired deodorizing apparatus and in which the following three features may be utilized. As shown in FIG. 1, (1) A bypass line is installed on the first zone hot air circulation line for bypassing the heat recovery apparatus 9, and a damper is disposed in the bypass line to control the bypass amount. (2) The paper temperature control device 14 controls two elements: the degree of opening of bypass damper and the burning amount of preheating burner. (3) The control output setting device is disposed to detect printing speeds at regular intervals and to reset the output value of paper temperature control device 14 to a specified value in accordance with the change rate of printing speed with time. When the printing speed decreases during the operation of printing press, the paper temperature rises. Then, the paper temperature control device 14 operates the bypass damper 21 in the opening direction. Since the heat recovery apparatus 9, which is a heat source of hot air, is bypassed, the temperature of blowing hot air in the first zone is decreased, and at the same time the paper temperature returns to the original value. This operation is performed by feedback control, and additionally the concept of feedforward control is adopted to further enhance the responsiveness. The control output setting device resets the output value of the paper temperature control device to a specified value at the same time when the printing speed is changed so that the control element is suddenly changed. If the reset value is constant (for example, the degree of opening of bypass = 100% when the speed decreases), a low change rate of printing speed act rather as an external disturbance; therefore, the device is designed so that the reset value is changed in accordance with the printing speed. When the printing speed is restored, that is, it is increased, the burning amount of preheating burner is increased suddenly. This means the same operation as that at the time of startup. Further, according to a second aspect of this invention, the following three features may be utilized. (1) A bypass line is installed on the first zone hot air circulation line in the first zone to bypass the heat recovery apparatus, and the degree of opening of damper in this bypass line is controlled by the paper temperature control device when the printing speed is decreased. (2) When the printing speed is increased afterward, the existing preheating burner is ignited by the paper temperature control device and the burning amount is controlled, as with the case of startup. That is, operation is changed over from the bypass damper operation to the preheating burner operation. (3) To compensate the stationary characteristics, the printing speed is detected, an arithmetic unit is provided to calculate the set value of deodorizing apparatus furnace temperature in accordance with the thermal load change of printed paper, and a deodorizing apparatus furnace temperature control device is provided to control the deodorizing apparatus furnace temperature by regulating the burning amount of the burner for deodorization. The above features serve as follows: When the printing speed is decreased during the operation of printing press, the paper temperature rises. Then, in FIG. 7, the paper temperature control device 14 operates the bypass damper 21 in the bypass line 20 in the opening direction. The temperature of blowing hot air in the first zone is decreased suddenly, and at the same time the paper temperature returns to the original value. To protect the heat transfer tube of the heat recovery apparatus 9, part of the hot air from the blower 5 is directed to the heat recovery apparatus and joins to the hot air passing through the bypass line 20 at the exit side of the heat recovery apparatus 9. At this time, if the temperature of exhaust gas from the deodorizing apparatus 8 is high, the hot air temperature decreasing effect is inhibited. There is also a problem of heat resistance of the heat transfer tube of the heat recovery apparatus 9. Therefore, the arithmetic unit 26 calculates the set value of deodorizing apparatus furnace temperature in accordance with the printing speed, that is the thermal load of printed paper, to reduce the set value. The deodorizing apparatus furnace temperature control device 25 controls the burning amount of the burner for deodorization in response to the change in the set value. When the temperature of printed paper is increased again, the same operation as that at the time of startup is performed. Thus, together with the control of deodorizing apparatus furnace temperature, the temperature of blowing hot air is rapidly changed, enabling the control to be carried out so that the paper temperature is constant. FIG. 1 is a schematic view of a first embodiment of the drying control device for the printed paper drying apparatus according to this invention, FIG. 2 is a graph showing the relationship between the paper temperature control device output and the command value for the degree of opening of bypass damper, FIG. 3 is a graph showing the relationship between the paper temperature control device output and the command value for the degree of opening of preheating burner valve, FIG. 4 is a graph showing an example of the calculation result for a preset manual setting device, FIG. 5 is a diagram showing the details of the temperature and speed control mechanism for the drying apparatus shown in FIG. 1, FIG. 6 is a flowchart of control in a first embodiment of this invention, FIG. 7 is a schematic view of a second embodiment of the drying control device for the printed paper drying apparatus according to this invention, FIG. 8 is a graph showing the relationship between the thermal load of printed paper and the set value of deodorizing apparatus furnace temperature, FIG. 9 is a schematic view of a typical conventional drying apparatus, FIG. 10 is a schematic view of another typical conventional drying apparatus, and FIG. 11 is a graph showing the relationship between the deodorizing apparatus furnace temperature and the odor concentration in exhaust gas. The first embodiment of the drying apparatus for rotary printing press according to the first aspect of this invention is shown in FIG. 1 and will be described with reference to FIGS. 1 through 6. In FIG. 1, 1 denotes a drying apparatus body, 2 denotes printed paper, 3 denotes a hot air blowing nozzle, 4 denotes a preheating burner, 5 denotes a blower for the first zone, 6 denotes a blower for the second zone, 7 denotes an exhaust gas blower, 8 denotes a direct fired deodorizing apparatus, 9 denotes a heat recovery apparatus, 10 denotes a burner for deodorization, 11 denotes a preheater, 12 denotes a direct fired reactor, 14 denotes a paper temperature control device, 17 denotes a paper temperature sensor, 20 denotes a bypass line, 21 denotes a damper, 22 denotes a motor (or cylinder), 24 denotes a deodorizing apparatus furnace temperature sensor, 25 denotes a deodorizing apparatus furnace temperature control device, 26 denotes a control output setting device, 27 denotes a printing speed sensor, and 28, 29 denote transducers. The bypass line 20 is installed on the first zone hot air circulation line, and the damper 21 is disposed midway in the bypass line 20. The paper temperature control device 14 is connected to the motor (or cylinder) 22 via the transducer 28, and to the preheating burner 4 via the transducer 29. The operations of transducers 28 and 29 are shown in FIG. 2 and 3, respectively. When the output Cv of paper temperature control device 14 is Cv > Cv* , the pre-heating burner valve opens/closes with the degree of opening of bypass damper being 0%; and when Cv < Cv* the bypass damper opens/closes with the degree of opening of preheating burner valve being 0% (i.e., not ignited). Thus, two operational elements can be operated by one control device. Since the deodorizing capability depends on the furnace temperature of the deodorizing apparatus 8, a lower limit temperature for the deodorizing apparatus furnace temperature control device 25 is set to provide a desired deodorizing capability. The deodorizing apparatus furnace temperature control device 25 controls the burning amount of the burner for deodorization 10 so that the deodorizing apparatus furnace temperature detected by the sensor 24 is equal to the set value. The control output setting device 26 provides a reset value of output of the paper temperature control device 14. While the printing speed sensor 27 detects printing speeds at a regular intervals tp, the control output setting device 26 outputs the reset value in accordance with the change rate of printing speed with time (ΔVs/tp). The paper temperature control device 14 resumes the PID (proportionalintegral-derivative) operation with the reset value being used as the initial value. FIG. 4 shows a typical operation of the preset manual setting device. This figure indicates that when \|ΔVs/tp\| < ε , (ε is constant), there is no output. That is, the paper temperature control device 14 performs the normal PID operation. When ΔVs/tp > ε , a reset value over CV* is provided. Therefore, the degree of opening of preheating burner valve is reset to a value higher than 0% by the transducer 29. When ΔVs/tp < -ε, a reset value under CV* is provided. Therefore, the degree of opening of preheating burner valve is reset to a value higher than 0% by the transducer 28. For example, when the printing speed is decreased suddenly, the degree of opening of bypass damper immediately becomes 100%, which enables highly responsive operation without the operation delay due to feedback control. FIG. 5 shows further details of the configuration. In FIG. 5, reference numeral 30 denotes an arithmetic unit for the change rate of printing speed with time, which performs the following calculations at regular intervals (usually on the order of several seconds) tp. where, kprinting speed detection time, ΔVs(k)detected value of printing speed at the kth time point, tpcalculation interval, ΔVs/Δtchange rate of printing speed with time. The control output setting device 26 performs the following operations in accordance with the change rate of printing speed with time obtained from the arithmetic unit for the change rate of printing speed with time 30 at calculation intervals of tp (the details of operation is shown in FIG. 4), and outputs the operation result CVR (reset value of paper temperature control device output) and f (flag) for the paper temperature control device 14. where, CVR :reset value of paper temperature control device output f :flag x₁, x₂, y₁, y₂, ε :parameter given in advance. The paper temperature control device 14 outputs the control output CV by the procedure shown in FIG. 6 from the input data of paper temperature detected by the paper temperature sensor 17, target value of paper temperature obtained from the setting device 31, and CVR and f obtained from the control output setting device 26. Referring to FIG. 6, when f = 0 (i.e., the change rate of printing speed with time is within ±ε), the paper temperature control device 14 performs the normal PID operation (the details are omitted). When f = 1, the normal PID operation is not performed, but the paper temperature control device output is forcedly reset to the obtained control output value CVR in accordance with the change rate of printing speed with time. When f returns from 1 to 0 (the speed becomes constant), the PID operation is resumed with the reset value being used as the initial value. The transducers 28 and 29 perform the operation shown in FIGS. 2 and 3 in accordance with CV. They determine the command value for the degree of opening for bypass damper and the command value for the degree of opening of preheating burner valve, respectively, to control the degree of opening of bypass damper and preheating burner valve. The control output setting device 26 and the paper temperature control device 14 have a selector switch for deciding whether the operation is performed. When the switch is OFF , flag = 0 for the control output setting device 26 and { CV = CV* , CVO = CV* } for the paper temperature control device 14 (refer to FIGS. 2 and 3). When the power supply is ON , this switch is normally OFF . In the drying apparatus for rotary printing press according of this invention for drying the ink on the printed paper by the hot air heating method which has a direct fired deodorizing apparatus and a heat recovery apparatus for reheating the hot air circulating in the drying apparatus by using the exhaust gas from the deodorizing apparatus, the drying apparatus comprises a bypass line installed on the hot air circulation line to bypass the heat recovery apparatus, a control device for controlling the paper surface temperature to be the set value by regulating the degree of opening of damper installed in the bypass line or the burning amount of preheating burner, and a control output setting device for resetting the output value of the control device to a predetermined value in according with the change rate of printing speed with time when the change rate of printing speed with time exceeds a specified value. Therefore, this drying apparatus of this invention achieves the following effect. When the printing speed decreases, the heat recovery apparatus, which is a heat source, is bypassed and the bypass amount is quickly changed in accordance with the change rate of printing speed, so that control can be performed without delay. As a result, the temperature of hot air is rapidly decreased, enabling the control of paper temperature to be carried out with high responsiveness. This increases the yield of product and decreases the loss of paper. Next, the second embodiment of the drying apparatus for rotary printing press, according to the second aspect of this invention, will be described with reference to FIGS. 7 and 8. In FIG. 7, 1 denotes a drying apparatus body, 2 denotes printed paper, 3 denotes a hot air blowing nozzle, 4 denotes a preheating burner, 5 denotes a blower for the first zone, 6 denotes a blower for the second zone, 7 denotes an exhaust gas blower, 8 denotes a direct fired deodorizing apparatus, 9 denotes a heat recovery apparatus, 10 denotes a burner for deodorization, 11 denotes a preheater, 12 denotes a direct fired reactor, 14 denotes a paper temperature control device, 17 denotes a paper temperature sensor, 20 denotes a bypass line, 21 denotes a damper, 22 denotes a motor for damper, 24 denotes a deodorizing apparatus furnace temperature sensor, 25 denotes a deodorizing apparatus furnace temperature control device, 26 denotes an arithmetic unit, 27 denotes a printing speed sensor, 33 denotes a selector switch, and a denotes printing conditions (basis weight and width of paper, target paper temperature). The bypass line 20 is installed on the first zone hot air circulation line, and the damper is disposed midway in the line 20. The paper temperature control device 14 is connected to the motor (or cylinder) mounted to the damper 21 and the preheating burner 4. The operator can change over the connection with the selector switch 33. The connection may be changed over in accordance with the increase/decrease in printing speed. At the moment when the connection is changed over, the output of the paper temperature control device 14 is reset to 0. (That is, the degree of opening of damper or preheating burner valve is 0.) The deodorizing apparatus furnace temperature control device 25 controls the burning amount of the burner for deodorization 10 so that the value detected by the deodorizing apparatus furnace temperature sensor 24 is equal to the set value which is the output of the arithmetic unit 26. The arithmetic unit 26 calculates the thermal load QS in accordance with the printing speed obtained from the paper speed sensor 27 and the printing conditions a which is inputted by the operator(G, W, TS shown below) by using, for example, the following equation. QS = V · G · W · (TS - T₀) · C where QS:quantity of heat received by paper (Kcal/h), V :printing speed (m/h), G :basis weight of printed paper (kg/m²), W :width of printed paper (m), TS :target value of paper temperature (°C), T₀ :paper temperature at the entrance of drying apparatus (°C), C :specific heat of printed paper (Kcal/kg°C). Furthermore, the set value of deodorizing apparatus furnace temperature is determined in accordance with QS by using the relationship shown, for example, in FIG. 8, and sent to the deodorizing apparatus furnace temperature control device 25. The symbol TDL in FIG. 8 denotes the lower limit temperature satisfying proper deodorizing requirements. In the drying apparatus for rotary printing press according to this invention for drying the ink on the printed paper by the hot air heating method which has a direct fired deodorizing apparatus and a heat recovery apparatus for reheating the hot air circulating in the drying apparatus by the exhaust gas from the deodorizing apparatus, the drying apparatus comprises a bypass line installed on the hot air circulation line to bypass the heat recovery apparatus, a control device for controlling the paper surface temperature to be the set value by operating the degree of opening of damper installed in the bypass line or the burning amount of preheating burner, and an arithmetic unit for calculating the set value of deodorizing apparatus furnace temperature in accordance with the thermal load of printed paper obtained by the detection of printing speed, and a control device for controlling the deodorizing apparatus furnace temperature to be the calculated set value by adjusting a burning amount of a deodorization burner. Therefore, this drying apparatus of this invention achieves the following effect. When the printing speed decreases, the temperature of hot air is quickly decreased by bypassing the heat recovery apparatus, enabling the control of paper temperature to be carried out with high responsiveness. This increases the yield of product and decreases the loss of paper.	A drying apparatus for a rotary printing press for drying ink on printed paper (2) which has a direct fired deodorizing apparatus (8) and a heat recovery apparatus (9) for reheating hot air circulating in said drying apparatus by using the exhaust gas of said deodorizing apparatus (8), characterized by a bypass line (20) installed on a hot air circulation line to bypass said heat recovery apparatus (9), a control device (14) for controlling the temperature of the printed paper to a specified value by adjusting the degree of opening of a damper (21) disposed in the bypass line (20) or a burning amount of a preheating burner (4), and a control output setting device (26) for resetting an output of the control device (14) to a specified value in accordance with the change rate of the printing speed with time when, as the printing speed is being detected by a printing speed sensor (27), the change rate of the printing speed with time exceeds a specified range. The drying apparatus according to claim 1, characterized in that a burning amount of a deodorization burner (10) is controlled by an other control device (25) based on the temperature (24) of the direct fired deodorizing apparatus (8). A drying apparatus for rotary printing press for drying ink on printed paper (2) which has a direct fired deodorizing apparatus (8) and a heat recovery apparatus (9) for reheating hot air circulating in said drying apparatus by using the exhaust gas of said deodorizing apparatus (8), characterized by a bypass line (20) installed on a hot air circulation line to bypass said heat recovery apparatus (9), a control device (14) for controlling the temperature of printed paper to a specified value by adjusting the degree of opening of a damper (21) disposed in the bypass line (20) or a burning amount of a preheating burner (4), an arithmetic unit (26) for calculating a set value of deodorizing apparatus furnace temperature in accordance with the thermal load of the printed paper obtained by detection of the printing speed with a printing speed sensor (27), and an other control device (25) for controlling the deodorizing apparatus furnace temperature (24) to the calculated set value by adjusting a burning amount of a deodorization burner (10).	MITSUBISHI HEAVY IND LTD; MITSUBISHI JUKOGYO KABUSHIKI KAISHA	KUNO HIROAKI C O HIROSHIMA TEC; KUWADA CHIE C O MITSUBISHI JUK; TANOUCHI KUNIAKI C O MITSUBISH; YOKOO KAZUTOSHI C O HIROSHIMA; YOSHIDA MINORU C O MIHARA MACH; KUNO, HIROAKI, C/O HIROSHIMA TECHNICAL INSTITUTE; KUWADA, CHIE, C/O MITSUBISHI JUKOGYO K.K.; TANOUCHI, KUNIAKI, C/O MITSUBISHI JUKOGYO K.K.; YOKOO, KAZUTOSHI, C/O HIROSHIMA TECHNIC. INSTITUTE; YOSHIDA, MINORU, C/O MIHARA MACHINERY WORKS
EP-0489370-B1	489,370	EP	B1	EN	19,970,205	1,992	20,100,220	new	C08F20	null	C08F2, C08F20, C08F293, C08F297	C08F 293/00B, C08F 20/12, C08F 2/00	Process for preparing polymer	A polymer comprising at least one polymer chain is produced by polymerizing, in the presence of a radical generating source and an iodide compound, at least one monomer M₁ having a radically polymerizable unsaturated bond between a carbon atom and an iodine atom constituting a carbon-iodine bond of the iodide compound to form at least one polymer chain between the carbon atom and the iodine atom, wherein the polymerization reaction is carried out in the presence of a monomer M₂ which is different from the monomer M₁ and has a larger addition reactivity with a carbon radical which is generated by cleavage of the carbon-iodine bond of the iodine compound than that of the monomer M₁.	The present invention relates to a novel process for preparing a polymer comprising at least one polymer chain. In particular, the present invention relates to a polymerization process which is apparently a living polymerization though a reaction mechanism is inherently a radical polymerization, and further an improved process for preparing a block polymer. More concretely, the present invention relates to a process for preparing a polymer which can be used as an improver of adhesion of a hydrocarbon polymer to a fluorine-containing polymer surface; a compatibilizer of a polymer alloy which comprises a hydrocarbon polymer and a fluorine-containing polymer; a dispersant for a fluorine-containing paint; a carrier of an electrophotography; an electrostatic charge adjusting or fusion bonding preventing agent for toner particles; in case where the hydrocarbon polymer chain is hydrophilic, a fluorine-containing surfactant, an emulsifier or a dispersant of a fluorocarbon base artificial blood. Japanese Patent Publication No. 4728/1983 and U.S. Patent No. 4,158,678 disclose a process for synthesizing a block polymer by cleaving a carbon-iodine bond of an iodide compound to form a carbon radical and successively radically polymerizing radically polymerizable monomers. In the above process, since a single hydrocarbon monomer is polymerized when a hydrocarbon monomer is intended to be polymerized with a fluorine-containing iodide polymer, it is not possible to polymerize the hydrocarbon monomer effectively. Further, since a terminal carbon-iodine bond in the formed polymer is unstable, in some applications, it is necessary to replace the terminal iodine with other element which forms a stable bond. Hitherto, in a reaction for stabilizing the terminal iodine, a large amount of a peroxide is required. United States patent application US-3983187 discloses iodine molecular weight regulators in suspension polymerisation systems. An aqueous suspension graft copolymerization system is described wherein at least one polymerizable monomer is graft polymerized with at least one elastomeric polymer in the presence of elemental iodine as a molecular weight modifier. SUMMARY OF THE INVENTIONAn object of the present invention is to provide a process for preparing a polymer, which can solve the above problems of the conventional process. Another object of the present invention is to provide a process for preparing a polymer, wherein the above monomers are polymerized at a high efficiency, namely a high iodine bonding rate. One aspect of the present invention is directed to the improvement of the polymerization process disclosed in Japanese Patent Publication No. 4728/1983. According to the present invention, there is provided a process for preparing a polymer which comprises polymerizing at least one monomer M1 having a radically polymerizable unsaturated bond, in the presence of a monomer M2, which is different from said monomer M1, a radical generating source and an iodide compound having a cleavable carbon-iodine bond and capable of producing a carbon radical and an iodine atom upon cleavage to form at least one polymer chain between said carbon atom and said iodine atom, wherein said monomer M2 has a larger addition reactivity with a carbon radical than said monomer M1 and a copolymerization reaction rate r2 of substantially zero, and wherein said monomer M1 has a copolymerization reaction rate r1 greater than 1 and less than 100. According to a further aspect of the present invention, there is provided a process for preparing a polymer which comprises polymerizing at least one monomer M1, having a radically polymerizable unsaturated bond, in the presence of a monomer M2, which is different from said monomer M1, a radical generating source and an iodine compound having a cleavable carbon-iodine bond and capable of producing a carbon radical and an iodine atom upon cleavage, to form at least one polymer chain between said carbon radical and said iodine atom, wherein said monomer M2 has a larger addition reactivity with said carbon radical than said monomer M1, and a copolymerization reaction rate r2 of smaller than 2, and wherein said iodine atom of said iodine compound may be withdrawn by a radical of said M2 monomer to form a terminal iodide bond between said M2 monomer radical and said iodine atom, said iodine atom of said terminal iodide bond having substantially the same chain transfer reactivity as said iodine atom when bonded to said iodine compound. Preferred features of these processes are contained in the claims 2 and 4 to 10. Fig. 1 is an IR spectrum of a polymer prepared in Comparative Example 1. Fig. 2 is an IR spectrum of a polymer prepared in Example 1. Fig. 3 is an IR spectrum of a polymer prepared in Example 3. Fig. 4 is an IR spectrum of a polymer prepared in Example 5. Figs. 5 and 6 are IR spectra of two polymers prepared in Example 7. Fig. 7 is an IR spectrum of a polymer prepared in Example 8. Fig. 8 is a graph showing a contact angle measured in Example 10. Fig. 9 is a graph showing a surface tension of water measured in Example 11. In case where a monomer such as a hydrocarbon vinyl monomer is polymerized with a radical which is generated through cleavage of the terminal carbon-iodine bond of the iodide compound, if the vinyl monomer has a low reactivity with the carbon radical, it is difficult to proceed the addition reaction of the vinyl monomer, that is, a polymer which is bonded to an iodide residue (a residue formed by removing the iodine atom from the iodide compound) is hardly formed, even though the radical is generated from the iodide compound in the presence of the vinyl monomer. In contrast, when an unsaturated compound having a high reactivity with the carbon radical from the iodide compound is used, that is, when an unsaturated compound M2 such as ethylene or other α-olefin which can be alternating copolymerized with a fluorine-containing vinyl monomer M1 such as tetrafluoroethylene or chlorotrifluoroethylene (namely, r1 ≃ r2 ≃ 0) is used, the monomer M2 is easily added to the carbon radical from the iodide compound. Because most of well used radically polymerizable monomers such as methyl acrylate, methyl methacrylate and acrylonitrile have very low reactivities with the carbon radical from the iodide compound, a homopolymer of each monomer is produced but it is difficult to polymerize one of them with the carbon radical from the iodide compound. When, in the presence of the carbon radical from the iodide compound, an unsaturated compound having a high reactivity with such carbon radical (a monomer M2) is used in combination with the radical polymerizable hydrocarbon vinyl monomer having a low reactivity with such carbon radical, the monomer M2 bonds to the carbon radical and thereafter a hydrocarbon polymer chain comprising the hydrocarbon vinyl monomer and the unsaturated compound monomer M2 grows by the radical polymerization to give a polymer comprising the hydrocarbon polymer chain. In this case, it is essential that the hydrocarbon monomer M1 is copolymerized with the terminal radical of the unsaturated compound M1, namely 1/r2 is not zero (0). In addition, in order that a larger amount of the intended hydrocarbon vinyl monomer is contained in the hydrocarbon polymer chain segment, preferably r1 >> r2 ≃ 0. If, when the growing polymer terminal carbon radical withdraws the iodine atom from other iodide compound molecule, the withdrawal finishes at the chain end (1/r1 is not zero and 1/r2 is not zero), namely, the polymer terminal which is stopped through the withdrawal of the iodine atom to form a terminal of ---M2-I, that is, if the terminal iodine atom of the ---M2-I type terminal is easily radically chain transferred, the hydrocarbon polymer chain grows in the same manner as a living polymerization. In this case, the iodine atom of said terminal iodide bond has substantially the same transfer reactivity as said iodine atom when bonded to said iodide compound. The iodide compound used in the present invention is a compound to which at least one iodine atom is bonded, which is stable to such degree that it cannot lose effectiveness through a side reaction under the polymerization conditions and any bond of which other than the bond comprising the iodine atom is not cleaved by the attack of the radical. The iodide compound may contain a fluorine atom. Further, the iodide compound'may comprise an element other than carbon, iodine and hydrogen, such as chlorine. In addition, the iodide compound may contain a functional group such as -O-, -S-, RfN- in which Rf is a polyfluoroalkyl group, -COOH, SO3H, PO3OH, etc. Preferably, the iodide compound is a low molecular weight perfluorinated alkyl iodide. In general, the iodide compound includes not only a low molecular weight compound but also a polymeric iodide compound having a molecular weight of 2,000,000 or less which is prepared by polymerization or copolymerization of an unsaturated compound having an iodine atom; coupling of a polyiodinated fluorohydrocarbon; iodination of a polymer having a reactive atom or atom group; polymerization in a polymerization system in which a chain transfer reaction to a polymer easily takes place in the presence of iodine I2; or polymerization of a monomer which constitutes a polymer chain in the presence of iodine or a compound which can liberate an iodine atom such as KI or ROI wherein R is an alkyl group. Specific examples of the polymer chain iodide are fluorine-containing iodides, for example, iodine-containing homopolymer or copolymer prepared by the polymerization as describe above of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluorocyclobutene, perfluoro(methylenecyclopropane), perfluoroallene, perfluorostyrene, perfluorovinyl ethers (such as perfluoromethyl vinyl ether), perfluoroacrylic acid, perfluorovinylacetate, perfluoro(3-vinyloxypropionic acid), perfluoro[2-(2-fluorosulfonylethoxy)propyl vinyl ether] and polyfluorodienes. Other examples are fluorine-containing copolymers of at least one of these radically polymerizable fluorolefins with at least one hydrocarbon monomer which can form a suitable polymer chain by the copolymerization with these fluorolefins. Examples of such hydrocarbon monomer are ethylene, α-olefin (e.g. propylene and butene), vinyl carboxylate ester (e.g. vinyl acetate), vinyl ether (e.g. methyl vinyl ether) and aryl carboxylate ester (e.g. aryl acetate). In addition, further examples of the polymer chain iodide are iodine-containing compounds having a chain of the formula: -(OCF2)p-(OCF2CF2)q-[OCF2CF(CF3)]r- wherein p, q and r are independently 0 or a positive number, and at least one of them is not 0, or the formula: -(CF2CF2CXYO)n- wherein n is a positive number, and X and Y are independently a fluorine atom or a hydrogen atom. Of course, a polymer prepared according to the present invention may be used as the iodide compound. All polymer chain iodides prepared in the presence of an iodide compound by using the method of present invention are used as the hydrocarbon iodide compound. Specific examples are an ethylene/propylene rubber and polybutadiene in which iodine bonds to a molecular end. In addition, the following iodide compounds can be also used: Polymeric iodides based on polyolefin, polyether, polyester, polyamide, polyurethane or silicone, for example, I-(CH2CHPh)n-I (wherein Ph is a phenyl group), ICH2-(CH2CHOAc)n-(CH2CH2)m-I (wherein Ac is an acetate group) R-(O-R -CO)n-CH2CH2-I, R-(Ph'-O)n-CH2CH2-I (wherein Ph' is a phenylene group), R-(CO-R -NH)n-CH2CH2-I, and Specific examples of a low molecular weight iodide compound are flurorine-containing compounds such as monoiodoperfluoromethane, monoiodoperfluoroethane, monoiodoperfluoropropane, monoiodoperfluorobutane (e,g. 2-iodoperfluorobutane, 1-iodoperfluoro(1,1-dimethylethane) and the like), monoiodoperfluoropentane (e.g. 1-iodoperfluoro(4-methylbutane) and the like), 1-iodoperfluoro-n-nonane, monoiodoperfluorocyclobutane, 2-iodoperfluoro(1-cyclobutyl)ethane, monoiodoperfluorocyclohexane, monoiodotrifluorocyclobutane, monoiododifluoromethane, monoiodomonofluoromethane, 2-iodo-1-hydroperfluoroethane, 3-iodo-1-hydroperfluoropropane, monoiodomonochlorodifluoromethane, monoiododichloromonofluoromethane, 2-iodo-1,2-dichloro-1,1,2-trifluoroethane, 4-iodo-1,2-dichloroperfluorobutane, 6-iodo-1,2-dichloroperfluorohexane, 4-iodo-1,2,4-trichloroperfluorobutane, 1-iodo-2,2-dihydroperfluoropropane, 1-iodo-2-hydroperfluoropropane, monoiodotrifluoroethane, 3-iodoperfluoroprop-1-ene, 4-iodoperfluoropentene-1,4-iodo-5-chloroperfluoropent-1-ene, 2-iodoperfluoro(1-cyclobutenyl)ethane, 1,3-diiodoperfluoro-n-propane, 1,4-diiodoperfluoro-n-butane, 1,3-diiodo-2-chloroperfluoro-n-propane, 1,5-diiodo-2,4-dichloroperfluoro-n-pentane, 1,7-diiodoperfluoro-n-octane, 1-iodoperfluorodecane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, 1,2-di(iododifluoromethyl)perfluorocyclobutane, 2-iodo-1,1,1-trifluoroethane, 1-iodo-1-hydroperfluoro(2-methylethane), 2-iodo-2,2-dichloro-1,1,1-trifluoroethane, 2-iodo-2-chloro-1,1,1-trifluoroethane, 2-iodoperfluoroethyl perfluorovinyl ether, 2-iodoperfluoroethyl perfluoroisopropyl ether, 3-iodo-2-chloroperfluorobutyl perfluoromethyl ether, 3-iodo-4-chloroperfluorobutyric acid, iodopentafluorocyclohexane, 1,4-diiodotetrafluorocyclohexane and 1,4-di(iododifluoromethyl)tetrafluorocyclohexane. Further specific examples are hydrocarbon iodide compounds such as CH3I, CH2I2, CHI3, ICH2CH2I, CH2=CHCH2CH2I, CH2=CH2, iodobenzene, 1,4-diiodobenzene, 1,4-di(iodomethyl)benzene. The iodide compound is not limited to the above compounds. Specific examples of the monomer M1 are acrylic unsaturated compounds, for example, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, potassium methacrylate, cyclohexyl methacrylate, 2-(dimethylamino)ethyl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyl methacrylate, benzyl methacrylate, lauryl methacrylate, acrylamide, acrolein, methacrylamide, methacrolein, acrylonitrile, methacrylonitrile, styrene, methylstyrene, chlorostyrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl chloride, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltrimethylsilane, butadiene, isoprene, chloroprene, maleic acid, maleinimide, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, calcium maleate, allyl maleate, 2-ethylhexyl maleate, octyl maleate, maleic hydrazide, meleic anhydride, fumaric acid, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, sodium fumarate, fumaronitrile and fumaryl chloride. Specific examples of a fluorine-containing monomer M1 are tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluorocyclobutene, perfluoro(methylenecyclopropane), perfluoroallene, trifluorostyrene, perfluorostyrene, perfluorovinyl ethers [e.g. perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether) and the like], perfluoroacrylic acid, perfluorovinylacetic acid, perfluoro(3-vinyloxypropionic acid), perfluoro(2-(2-fluorosulfonylethoxy)propyl vinyl ether], α-fluoroacrylic acid, methyl α-fluoroacrylate, ethyl α-fluoroacrylate, phenyl α-fluoroacrylate, 3,3,4,4,4-pentafluorobut-1-ene, 3,3,3-trifluoropropene, 3,3,4,4,5,5,5-heptafluoropent-1-ene and polyfluorodienes. Specific examples of the monomer M2 are ethylene, other α-olefins (e.g. propylene, butene, isobutene, pentene, hexene, heptene and octene), vinyl ethers (e.g. methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and), allyl esters (e.g. allyl acetate, allyl propionate and allyl butyrate), and vinylsilanes (e.g. vinyltrimethylsilane, vinyltriethylsilane, vinyltriphenylsilane, and vinyltrichlorosilane). Among them the α-olefins are preferred. These examples do not limit the scope of the present invention. Insofar as the monomers satisfy the conditions set by the present invention, the vinyl monomer which is exemplified as the monomer M1 may be used as the monomer M2, or the vinyl monomer which is exemplified as the monomer M2 may be used as the monomer M1. According to the process of the present invention, it is possible to produce not only a polymer consisting of one polymer chain but also a block polymer consisting of at least two different polymer chains. Herein, the term different polymer chains is intended to mean that all the constituent monomers are different between two polymer chains and also that a ratio of two or more monomers and/or a bonding sequence thereof are different between the two polymer chains though the kinds of the monomers are the same. In the present invention, the Iodide Bonding Ratio (IBR) is calculated as a ratio of the polymer which is formed by the addition of the vinyl monomer to the cleaved carbon-iodine bond of the iodide compound according to the following equation: IBR (%) = The number of the carbon-iodine bonds which are cleaved and contribute to the polymerizationThe number of the carbon-iodine bonds of the iodide compound molecules x 100 Since a peak in an IR spectrum based on the terminal iodine bond of a polymer which is produced by using F(CF2CF2CF2O)n-CF2CF2I appears around 920 cm-1, IBR after the polymerization reaction can be calculated according to the following equation: (An absorbance peak height at 925 cm-1 before reaction) - (an absorbance peak height at 925 cm-1 after reaction)(An absorbance peak height at 925 cm-1 before reaction) x 100 Further, in the 19F-NMR, since a chemical shift based on -OCF2CF2I appears around -12.5 ppm, IBR can be calculated from this chemical shift. It it understood from the results in Examples that the calculated IBR values are substantially the same at the real ones. When the M2 monomer is not used, IBR is greatly influenced by a kind of the M1 monomer and, in general, considerably low. A degree of the decrease of IBR cannot be sufficiently recovered even if the polymerization temperature and/or the monomer concentration are selected in favor of the chain transfer reaction of the iodide compound, that is, a high reaction temperature and a low monomer concentration are selected since such conditions are favorable to the chain transfer reaction of the iodide compound. When the monomer M2 is used in combination with the monomer M1, the addition of only several moles of the monomer M2 increases IBR by 50 % or more depending on the kind of the monomer M2, and IBR increases up to about 100 % as the concentration of the monomer M2 increases. This is one of the most significant effects of the present invention. The polymer prepared by the present invention has a molecular weight of 4,000,000 or less, in general from 1000 to 4,000,000. If the carbon-iodine bond which is easily cleaved by heat or light remains at the terminal of the prepared polymer, the iodine atoms are easily liberated, so that some disadvantages tend to appear, for example, the polymer is deteriorated or colored, or a material which is contacted to the polymer is corroded. To prevent such disadvantages, it is preferably to replace the terminal iodine with other element which forms a stable bond with the carbon atom. In such replacing reaction, the terminal carbon-iodine bond of the polymer is cleaved with heat, light or a radical initiator in the presence of a compound containing an element which is easily radical chain transferred (e.g. isopentane, toluene, carbon tetrachloride, etc.) to form the terminal carbon radical. Then, the terminal carbon radical withdraws a hydrogen atom or a chlorine atom from the compound containing an element which is easily radical chain transferred to form a terminal carbon-hydrogen or carbon-chlorine bond. In such treatment, a compound which can capture the liberated iodine (e.g. sodium sulfite, etc.) is preferably used. The present invention will be illustrated by the following Examples and Comparative Examples. Comparative Example 1In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average of n: 27.4, average molecular weight: about 4,800) (5.0 g) and methyl acrylate (MA) (5.0 g) were dissolved in 1,1,2-trichloro-1,2,2-trifluoroethane (R-113) (30 cc). Then, azobisisobutyronitrile (AIBN) (6.4 x 10-3 g) was added. After cooling, the atmosphere was fully replaced with a nitrogen gas. Then, the atmosphere was pressurized to 1.0 kg/cm2G with the nitrogen gas. The mixture was heated to 70°C with stirring and polymerized for 5 hours. After completion of the polymerization, the autoclave was opened. The content was vacuum distilled at 40°C to remove the solvent and the residual monomer. A yield was measured to be 9.7 g. A resultant polymer had two separated parts which were a transparent oil part and a white resin part. An IR spectrum of the oil part was measured. As shown in Fig. 1, only peaks based on perfluoropolyether were observed and no peak based on poly-MA (polymethyl acrylate) was observed. A peak at 920 cm-1 based on a terminal -CF2-I group remained at the same intensity as before the reaction. In addition, an IR spectrum of the white resin part was measured. Only peaks based on poly-MA were observed. From this, it is clear that when only MA is used, only a homopolymer of MA is produced and a block polymer with a perfluoropolyether chain is not produced. Example 1In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average of n: 27.4, average molecular weight: about 4,800) (20.0 g) and MA (20.0 g) were dissolved in R-113 (120 cc). Then, AIBN (1.69 x 10-2 g) was added. The atmosphere was fully replaced with firstly a nitrogen gas, and then an ethylene gas. Then, the atmosphere was pressurized with the ethylene gas to 14.8 kg/cm2G at 70°C. The mixture was polymerized at 70°C for 5 hours. Then, AIBN (1.6 x 10-2 g) and MA (20.0 g) were added and the polymerization was continued for 9 hours. After the completion of the polymerization, the autoclave was opened. Although a small part of resultant poly-MA adhered to a wall of the autoclave, a large part of poly-MA was dispersed in R-113. After the content was vacuum dried at 40°C, a yield of the product was measured to be 56.2 g. No separation between an oil part and a resin part was observed. The resultant polymer was dispersed and dissolved again in R-113 and filtered through a glass filter. A filtrate was vacuum dried at 40°C to obtain a greasy polymer. An IR spectrum of this polymer was measured. As shown in Fig. 2, in addition to peaks based on the perfluoropolyether, peaks based on a copolymer of MA and ethylene were observed at 2,800 cm-1, 1,730 cm-1, 1,440 cm-1 and the like. A peak at 920 cm-1 completely disappeared. Accordingly, IBR was 100 %. From the result, it is seemed that a MA-ethylene random copolymer chain forms a covalent bond with a perfluoropolyether chain and accordingly the polymer was dissolved in R-113 and contained in the filtrate. Example 2In a pressure autoclave, n-C8F17I (1.3 g) and MA (15.0 g) were dissolved in R-113 (100 cc). Then, AIBN (9.3 x 10-3 g) was added. The atmosphere was fully replaced with firstly a nitrogen gas, and then an ethylene gas. Then, the atmosphere was pressurized with the ethylene gas to 30.0 kg/cm2G at 70°C. The mixture was polymerized at 70°C for 8 hours. Then, the autoclave was opened. After the content was vacuum dried at 40°C, a yield of the product was measured to be 4.9 g. R-113 was added to the resultant polymer, and then a R-113-soluble part and a R-113-insoluble part were formed. 1H-NMR and 19F-NMR spectra of each of two parts were measured. In 19F-NMR spectrum, both of the soluble and insoluble parts had a peak at about 36 ppm (an external standard of trichloroacetic acid) based on -CF 2-CH2- which indicates a covalent bond of a fluorocarbon chain with a hydrocarbon chain. In addition, a composition of the hydrocarbon chain segment and a molecular weight as a whole were determined. The result is shown in Table 1. It is apparent from Table 1 that almost all the hydrocarbon chain consists of MA units. A peak based on was not observed, although a peak based on -CH2CH2I was observed at about 3.0 ppm in 1H-NMR spectra of the both parts. From this, it is seemed that all ends of the hydrocarbon chain segments are terminated with ethylene units (-CH2CH2I). The R-113-soluble part have a higher ethylene content than in the insoluble part, since ethylene is introduced in a larger content in the fluorocarbon chain units and the terminal iodine. Ethylene unit (% by mole) MA unit (% by mole) Molecular weight R-113-soluble part 22781,160 R-113-insoluble part13872,030 Comparative Example 2In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average molecular weight: about 4,800) (7.1 g) and methyl methacrylate (MMA) (7.1 g) were dissolved in perfluorobenzene (20 cc). Then, AIBN (2.02 x 10-2 g) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized to about 1 kg/cm2G with the nitrogen gas. The mixture was heated to 80°C with stirring and then polymerized for 5 hours. After the completion of the polymerization, the autoclave was opened and the content was vacuum dried at 40°C. A yield was measured to be 12.1 g. A resultant polymer had two separated parts which were a transparent oil part and a white resin part. An IR spectrum of each of the oil and resin parts was measured. Only peaks based on the perfluoropolyether were observed in the oil part and only peaks based on poly-MMA were observed in the resin part. The transparent oil part had a peak at 920 cm-1 which had the same intensity as before the polymerization. It was found that when MMA alone is used, only a homopolymer of MMA is produced and a block polymer with a perfluoropolyether chain is not produced. Example 3In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average molecular weight: about 4,800) (15.0 g) and MMA (15.0 g) were dissolved in R-113 (90 cc). Then, AIBN (9.6 x 10-3 g) was added. The atmosphere was fully replaced with firstly a nitrogen gas, and then an ethylene gas. Then, the atmosphere was pressurized with the ethylene gas to 32.0 kg/cm2G at 70°C. The mixture was polymerized at 70°C. MMA (totally 45.2 g) and AIBN (totally 2.91 x 10-2 g) were added depending on the consumption of these in the course of the polymerization. After the polymerization for 45 hours, the autoclave was opened. Although a small part of a product adhered to a wall of the autoclave, resultant poly-MMA was dispersed in R-113. After the content was vacuum dried at 40°C, a yield of the product was measured to be 80.3 g. No separation of an oil part from a resin part was observed. The resultant polymer was dispersed and dissolved again in R-113 and filtered through a glass filter. A filtrate was vacuum dried at 40°C to obtain a greasy polymer. An IR spectrum of this polymer was measured. As shown in Fig. 3, in addition to peaks based on the perfluoropolyether, peaks based on a copolymer of MMA and ethylene were observed at 2,800 cm-1, 1,730 cm-1, 1,480 cm-1, 1,440 cm-1 and the like. A peak at 920 cm-1 completely disappeared. Accordingly, a block ratio (IBR) was 100 %. Prom the result, it is seemed that a MMA-ethylene random copolymer chain forms a covalent bond with a perfluoropolyether chain and, accordingly, the polymer is dissolved in R-113 and contained in the filtrate. Example 4In a pressure autoclave, an iodine-double-terminated rubber dispersion based on vinylidene fluoride (VdF)/hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) (molar ratio: 55/19/26) (average molecular weight: 18,000) (300 g) (solid content: 6 % by weight) was charged. Then, MMA (0.7 g), ammonium perfluorooctanoate salt (1.5 g) and (CH3)3CCOOH (5.96 g x 10-2) were added. The atmosphere was fully replaced with firstly nitrogen and then ethylene. The atmosphere was pressurized with ethylene to 27.0 kg/cm2G at 140 °C. Then, the polymerization was continued for 30 hours at 140 °C, while MMA (totally 44.8 g) which was fully bubbled with a nitrogen gas was continuously added. After the completion of the polymerization, the product was coagulated with potash alum and subjected to GPC. It was found that the rubbery polymer before the polymerization had a number average molecular weight of 18,000 and a molecular weight distribution of 1.29, and the resinous polymer after the polymerization had a number average molecular weight of 28,000 and a molecular weight distribution of 1.28. This shows that the molecular weight distribution is constant and only the molecular weight increases. It is seemed that the MMA and ethylene monomers additinally polymerize with a terminal carbon radical which is formed by a carbon-iodine bond cleavage at an end of the fluorine-containing polymer chain, and the cleavage and the monomer addition occur again, even when the polymer end is terminated with the iodine atom by drawing the iodine atom and that, accordingly the polymerization proceeds livingly. Example 5In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average molecular weight: about 4,800) (5.0 g), MA (2.0 g) and 1-hexene (4.6 g) were dissolved in R-113 (30 cc). Then, AIBN (9.7 x 10-3 g) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized with the nitrogen gas to about 1 kg/cm2G. After heating to 70°C, the mixture was polymerized for 7.9 hours. After the completion of the polymerization, the content was vacuum dried at 40°C. A yield of the product was measured to be 5.9 g. Although the resultant polymer was brownish because of the liberation of the terminal iodine atom, it was a greasy polymer having high transparency. An IR spectrum of the polymer was measured. As shown in Fig. 4, both of peaks based on the perfluoropolyether chain and peaks based on the hydrocarbon polymer chain (a random polymer chain of MA and 1-hexene) were observed. A peak at 920 cm-1 based on -CF2-I completely disappeared. Namely, IBR was 100 %. In addition, an NMR spectrum of this polymer was measured. In the 19F-NMR spectrum, the polymer had a peak at about 40 ppm (an external standard of trichloroacetic acid) based on -CF2-CH2-, which confirmed a covalent bond of a fluorocarbon chain with a hydrocarbon chain. The 1H-NMR spectrum showed that a ratio of the MA units to the 1-hexene units in the hydrocarbon chain is 62:38 (molar ratio) and the MA units are contained in larger amount than the 1-hexene units. A peak based on -CH2CH(COOCH3)-I at about 4.4 ppm and a peak based on -CH2CH(C4H9)-I at about 3.2 ppm were observed. The above result shows that the polymerization gives a block polymer which has a perfluoropolyether chain and a copolymer chain consisting of MA and 1-hexene with a large amount of MA. An experiment confirmed that a ratio of MA to 1-hexene in the polymer can be controlled by addition amount of 1-hexene. Example 6In a pressure autoclave, an iodine-double-terminated liquid rubber based on VdF/HFP/TFE (molar ratio: 52/21/27) (25.0 g), MA (24.4 g) and 1-hexene (25.0 g) were dissolved in R-113 (150 cc). Then, AIBN (6.42 x 10-2 g) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized with the nitrogen gas to about 1 kg/cm2G. The mixture was heated to 70°C. The polymerization was conducted while the monomers and the initiator [MA (totally 42.2 g), 1-hexene (totally 26.8 g) and AIBN (totally 0.14 g)] were added in the course of the polymerization. After the completion of the polymerization, the autoclave was opened. The polymer was dissolved in the solvent to form a homogeneous transparent solution before the polymerization, but an opaque liquid was formed after the polymerization. The content was vacuum dried at 40°C to give a resinous polymer having a high transparency. GPC analysis was conducted with this resultant polymer and also a polymer which was sampled after 8 hours from the initiation of the polymerization. The result is shown in Table 2. This shows that, although the molecular weight after the polymerization was at least twice before the polymerization, the molecular weight distribution was almost the same. It is confirmed that a carbon-iodine bond is cleaved at an end of the fluorine-containing polymer chain, and the polymerization proceeds livingly from a carbon free radical and that a block polymer consisting of a fluorine-containing polymer chain and a hydrocarbon polymer chain is produced. MnMwMw/MnBefore reaction4,2005,2001.23 After 8 hour reaction6,5008,2001.25 After 16 hour reaction8,50011,3001.32 Example 7In a pressure autoclave, F(CF2CF2CF2O)nCF2CF2I (average of n: 20, average molecular weight: about 3,700) (40.0 g), acrylic acid (AA) (22.5 g) and 1-hexene (26.3 g) were dissolved in R-113 (240 cc). Then, AIBN (7.59 x 10-2 g) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized with the nitrogen gas to about 1 kg/cm2G. After heating to 70°C with stirring, the mixture was polymerized for 8.0 hours. After the completion of the polymerization, the autoclave was opened. The content was vacuum dried at 40°C. A yield of the product was measured to be 54.56 g. An IR spectrum of the polymer was measured. As shown in Fig. 5, peaks based on a copolymer of AA and 1-hexene were also observed at 3,100 cm-1, 1,710 cm-1, 1,450 cm-1 and the like in addition to peaks based on the perfluoropolyether chain. A peak at 920 cm-1 completely disappeared. When the resultant polymer was extracted with R-113, an insoluble part was a powdery polymer. This powdery polymer (2.0 g) was dispersed in water (100 cc) and then NaOH was added to adjust a pH value to 7. The whole system had an increased viscosity and an opaque state turned to a transparent state. This polymer was dried and its IR spectrum was measured. As shown in Fig. 6, peaks based on a copolymer of sodium acrylate (AANa) and 1-hexene were observed at 3,350 cm-1, 2,900 cm-1, 1,560 cm-1 and the like in addition to peaks based on the perfluoropolyether chain. No peak at 920 cm-1 was observed. In addition, an NMR spectrum of this polymer was measured. In the 19F-NMR spectrum, a peak based on -CF2-CH2- was observed at 39 ppm. The 1H-NMR spectrum showed that a ratio of AANa units to 1-hexene units in the hydrocarbon chain segment is 75:24 (molar ratio) and the AANa is contained in larger amount than 1-hexene. The above result shows that the polymerization gives a water-soluble fluorine-containing block polymer which has a perfluoropolyether chain and a hydrocarbon polymer chain consisting of AANa units and 1-hexene units. An experiment confirmed that a ratio of AA to 1-hexene in the polymer can be controlled by an addition amount of 1-hexene. IBR in this Example was determined as follows: Since, in the IR spectrum, a peak at 1,100 cm-1 (probably based on an ether linkage of the perfluoropolyether) is constant before and after the polymerization, this peak is considered as a standard. Before the reaction, the iodine-terminated perfluoropolyether has the absorbance at 1,100 cm-1 of 1.434 [= ln(75.5/18)] and the absorbance at 920 cm-1 of 0.158 [= ln(82/70)]. After the reaction, the absorbance at 1,100 cm-1 in the IR spectrum is 1.609 [= ln(77.5/15.5)] and the absorbance at 920 cm-1 is 0.065 [= ln(79.5/74.5)]. Accordingly, a ratio of unreacted terminal carboniodine bonds after the reaction is calculated as follows: Number of carbon-iodine bonds after the reactionNumber of carbon-iodine bonds before the reaction =Intensity of peak at 920 cm-1 after the reactionIntensity of peak at 920 cm-1 before the reaction =Absorbance of peak at 920 cm-1 after the reactionAbsorbance of peak at 1,100 cm-1 after the reaction +Absorbance of peak at 920 cm-1 before the reactionAbsorbance of peak at 1,100 cm-1 before the reaction =ln79.5/74.5ln77.5/15.5 + ln82/70ln75.5/18 = 0.0651.609 + 0.1581.434= 0.37 A ratio of the peak at 920 cm-1 decreased by the reaction, namely a ratio of the carbon-iodine bonds which connect with the hydrocarbon chain segment by the reaction, namely IBR is calculated to be (1-0.37) x 100 = 63 %. Comparative Example 3In a pressure Pyrex autoclave, F(CF2CF2CF2O)n-CF2CF2I (average molecular weight: about 4,800) (5.0 g) and acrylonitrile (AN) (4.2 g) were dissolved in R-113 (30 cc). Then, a solution of sodium sulfite (0.10 g) in water (5 cc) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized to about 1 kg/cm2G with the nitrogen gas. The mixture was polymerized at 70°C for 8 hours while irradiating UV light. After completion of the polymerization, the autoclave was opened. The content was removed and vacuum dried at 40°C. A yield was measured to be 9.1 g. But an oil part was separated from a resultant resinous polymer. An IR spectrum of the separated oil part was measured. Only peaks based on a perfluoropolyether chain were observed, but peaks based on poly-AN chain were hardly observed. A peak at 920 cm-1 after the polymerization had almost the same intensity as before the polymerization. An IR spectrum of the resinous part was measured. Only peaks based on the poly-AN were observed, but peaks based on the perfluoropolyether chain were not observed. The result shows that when AN alone is used, only a homopolymer of AN is produced and a block polymer with the perfluoropolyether chain is not produced. Example 8In a pressure quartz autoclave, F(CF2CF2CF2O)n-CF2CF2I (average molecular weight: ____) (3.0 g), AN (1.3 g) and 1-hexene (4.6 g) were dissolved in R-113 (30 cc). Then, a solution of sodium sulfite) (0.1 g) in water (5 cc) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized with the nitrogen gas to about 1 kg/cm2G. The mixture was polymerized at 70 °C for 8.0 hours while irradiating UV light in which light having a wave length of not longer than 240 nm was cut by a fitter. After the completion of the polymerization, the content was vacuum dried at 40°C to obtain a slightly opaque and oily polymer. A yield of the product was measured to be 5.4 g. Art IR spectrum of the resultant polymer was measured. Peaks based on a hydrocarbon random polymer consisting of the AN and 1-hexene units were observed at 2,900 cm-1, 2,250 cm-1, 1,440 cm-1 and the like in addition to peaks based on the perfluoropolyether chain. A peak at 920 cm-1 completely disappeared. In addition, an NMR spectrum of the polymer was measured. In the 19F-NMR spectrum, a peak based on -CF2-CH2- was observed at about 38 ppm (an external standard of trichloroacetic acid). The 1H-NMR spectrum showed that a ratio of AN units to 1-hexene units in the hydrocarbon chain is 39:61 (molar ratio). It was confirmed that the polymerization gives a block polymer which has a perfluoropolyether chain and a hydrocarbon polymer chain consisting of AN units and 1-hexene units. An experiment confirmed that a ratio of AN to 1-hexene in the polymer can be controlled by an addition amount of 1-hexene. Example 9In a pressure Pyrex autoclave, a block copolymer having a terminal iodine bond prepared in Example 5 (2.5 g) and isopentane (3.0 g) were dissolved in R-113 (15 cc). Then, a solution of sodium sulfite (0.1 g) in water (5 cc) was added. The atmosphere was fully replaced with a nitrogen gas and then pressurized with the nitrogen gas to about 1 kg/cm2G. A polymer terminal was stabilized at 70°C for 8.0 hours while irradiating UV light. After the completion of the stabilization, the content was washed with water. Then, the solution in R-113 was vacuum dried at 40°C. The resultant polymer was greasy and highly transparent one. An elemental analysis was conducted. The, polymer had an iodine content of not more than 0.01 % by weight and iodine could be removed from the polymer by this reaction. Even when the polymer was subjected to sunlight in the air, a color of the polymer did not change to brown. The reaction gave a block polymer a terminal of which is stabilized by hydrogen. Example 10Each of R-113-soluble parts prepared in Examples 1 and 3 (namely, a block polymer having a perfluoropolyether chain and a hydrocarbon polymer chain which contains a large amount of MA units, and a block polymer having a perfluoropolyether chain and a hydrocarbon polymer chain which contains a large amount of MMA units) in different ratios was added to an about 4 % solution of poly-MMA (molecular weight: about 600,000) in acetone. After poly-MMA and block poly-MMA were homogeneously dispersed and dissolved in acetone, a solution was cast on a glass plate and acetone was evaporated to obtain a homogeneous, highly transparent and smooth film. An oil or water droplet was dropped on this film to measure a contact angle. The result is shown in Fig. 8. This result shows that when ratios of both MA-based and MMA-based block polymers to poly-MMA are increased, the contact angle increases, but when the ratios reach certain values, the contact angle does not further increase. This may be because the block polymer gives good water- and oil-repellency to the film since the hydrocarbon polymer chain of the block polymer enters in poly-MMA phase due to its compatibility with poly-MMA and the perfluoropolyether chain, which is the other component of the block polymer, appears on a surface part of the film (anchor effect). In the same manner as described above for the block polymer, the perfluoropolyether (molecular weight: about 4500) was mixed with poly-MMA in an acetone solvent and cast on a glass plate. The perfluoropolyether floated on poly-MMA and a homogeneous film containing a fluoropolymer chain could not be obtained. Example 11A block polymer prepared in Example 7 and having a pefluoropolyether chain and a hydrocarbon polymer chain which contains a large amount of acrylic acid units was added in various ratios to water to measure a surface tension of an aqueous solution. The result is shown in Fig. 9. The result shows that when the content of the block polymer in the aqueous solution is increased, the surface tension decreases to 35 dyn/cm. Fig. 9 shows that a critical micelle concentration is about 1 x 10-3 mol/l. From this, it is confirmed that the block polymer consisting of the flexible fluoropolymer chain and the water-soluble hydrocarbon polymer chain effectively decreases the surface tension of water.	A process for preparing a polymer which comprises polymerizing at least one monomer M1, having a radically polymerizable unsaturated bond, in the presence of a monomer M2, which is different from said monomer M1, a radical generating source and an iodide compound having a cleavable carbon-iodine bond and capable of producing a carbon radical and an iodine atom upon cleavage, to form at least one polymer chain between said carbon radical and said iodine atom, wherein said monomer M2 has a larger addition reactivity with said carbon radical than said monomer M1, and a copolymerization reaction rate r2 of substantially zero, and wherein said monomer M1 has a copolymerization reaction rate r1 greater than 1 and less than 100. The process according to claim 1, wherein said iodine atom of said iodine compound is withdrawn by a radical of said M2 monomer to form a terminal iodide bond between said M2 monomer radical and said iodine atom, said iodine atom of said terminal iodide bond having substantially the same chain transfer reactivity as said iodine atom when bonded to said iodide compound. A process for preparing a polymer which comprises polymerizing at least one monomer M1, having a radically polymerizable unsaturated bond, in the presence of a monomer M2, which is different from said monomer M1, a radical generating source and an iodine compound having a cleavable carbon-iodine bond and capable of producing a carbon radical and an iodine atom upon cleavage, to form at least one polymer chain between said carbon radical and said iodine atom, wherein said monomer M2 has a larger addition reactivity with said carbon radical than said monomer M1, and a copolymerization reaction rate r2 of smaller than 2, and wherein said iodine atom of said iodine compound may be withdrawn by a radical of said M2 monomer to form a terminal iodide bond between said M2 monomer radical and said iodine atom, said iodine atom of said terminal iodide bond having substantially the same chain transfer reactivity as said iodine atom when bonded to said iodine compound. The process according to any one of the claims 1 to 3, wherein said monomer M2 is an α-olefin. The process according to any one of the claims 1 to 4, wherein said monomer M1 is a radically polymerizable unsaturated hydrocarbon. The process according to any one of the claims 1 to 4, wherein said monomer M1 is an acrylic unsaturated compound. The process according to any one of the claims 1 to 6, wherein said iodide compound is a fluorine-containing iodide compound. The process according to any one of the claims 1 to 6, wherein said iodide compound is a low molecular weight perfluorinated alkyl iodide. The process according to any one of the claims 1 to 6, wherein said iodide compound is an iodine-containing fluoropolymer. The process according to any one of the claims 1 to 9, which further comprises a step for converting a terminal carbon-iodine bond of the produced polymer to a carbon-hydrogen bond.	DAIKIN IND LTD; DAIKIN INDUSTRIES, LIMITED	TATEMOTO MASAYOSHI; YUTANI YUJI; TATEMOTO, MASAYOSHI; YUTANI, YUJI; Tatemoto, Masayoshi, c/o Yodogawa Works of; Yutani, Yuji, c/o Yodogawa Works of
EP-0489375-B1	489,375	EP	B1	EN	19,960,911	1,992	20,100,220	new	G11B15	G05D13	G11B15	G11B 15/473R	A drum servo system	A drum servo system provided with a rotation control device for controlling a rotation of a drum on the basis of a phase comparison signal obtained as a result of comparing the phase of an angle-of-rotation information signal obtained according to an angle of rotation of the drum with the phase of a control signal and a comparison control device for outputting the control signal to the rotation control device by performing a phase comparison or a frequency comparison by use of a frequency de-multiplication signal obtained by effecting a frequency de-multiplication of a reference signal having a frequency higher than a frequency of the control signal. Thus a radical change in the control signal, which occurs when the phase or frequency of the control signal is changed similarly as an abrupt disturbance from the outside, can preferably be absorbed in the comparison control device. Thereby, the rotation control means can always and stably follow the abrupt change occurring in the control signal.	BACKGROUND OF THE INVENTION1. Field of The InventionThis invention generally relates to a video tape recorder (hereunder abbreviated as VTR) and more particularly to a drum servo system suitable for use in a VTR. 2. Description of The Related ArtFIGS. 1 to 3 are schematic block diagrams each for illustrating a conventional drum servo system 100. As shown in FIG. 1, for example, a control signal whose frequency is an integral submultiple of a frequency of a vertical synchronization signal separated from a composite video signal in a synchronized manner is supplied to a noninverting input terminal of a phase comparator 1 which is a composing element of a drum servo circuit (to be described later), namely, a phase control means A. Further, an angle-of-rotation information signal to be described later, which has a shaped waveform, is fed to an inverting terminal of the phase comparator 1. Moreover, the phase comparator 1 compares the phase of the angle-of-rotation signal with that of the control signal and then outputs a phase comparison signal representing the result of the comparison to a loop filter 2. Thereafter, the loop filter 2 outputs an output signal obtained from the phase comparison signal supplied thereto by removing high-frequency components thereof to an amplifier 3. Subsequently, the signal amplified by the amplifier 3 is fed to a motor 4. Thereby, a rotary head drum 5 having a well-known structure rotates in response to the signal, of which the frequency is equal to a predetermined value and the phase is controlled. An angle-of-rotation detector 6 generates an angle-of-rotation information signal according to an angle of rotation of the drum 5 and then outputs the angle-of-rotation signal to a waveform shaping device 7. Subsequently, the device 7 shapes the waveform of the angle-of-rotation signal and outputs the angle-of-rotation signal, of which the waveform is thus shaped, to the inverting input terminal of the phase comparator 1. Incidentally, the drum servo circuit is a portion composed of the phase comparator 1, the loop filter 2, the amplifier 3 and the waveform shaping device 7. Thus the rotation of the drum 5 is always controlled by the phase control means A, to which the control signal is supplied. Further, the configuration of FIG. 2 is obtained by connecting an output of a frequency demultiplier or divider 8 to the noninverting input terminal of the phase comparator 1. Incidentally, the same reference numerals designate the same parts of FIG. 1 which will not be described again hereinbelow. As shown in FIG.2, a reference clock signal having a frequency higher than the frequency of the control signal is applied to the frequency demultiplier 8. Thereafter, a frequency de-multiplication signal having a frequency equal to the frequency of the control signal is outputted from the frequency demultiplier 8 to the noninverting input terminal of the phase comparator 1 of the drum servo circuit (namely, the phase control means) A, an operation of which is described above. Incidentally, in the instant application, a frequency de-multiplication is defined as an operation of obtaining a signal whose frequency is an integral submultiple of a frequency of another signal. Therefore, the operation of the phase control means A is not explained herein again. Thus the rotation of the drum 5 is controlled by the phase control means A, to which a frequency de-multiplication signal having the frequency equal to that of the control signal is supplied. Further, in case of the configuration of FIG. 3, one of signals respectively having different frequencies is selected. Namely, a speed control signal is supplied from a reference loop 14 to a motor control loop 10 in case of employing a normal reproducing speed. In contrast, the speed control signal is fed from a speed synthesizer 16 to the motor control loop 10 in case of employing a reproducing speed other than the normal reproducing speed. This selection is performed by operating a switch 18. The reference loop 14 is composed of a frequency comparator 36 to which a vertical synchronization signal 22 is supplied, a filter 38, a voltage-controlled oscillator (VCO) 40 and a frequency demultiplier 42. On the other hand, the speed synthesizer 16 is comprised of a programmed frequency demultiplier 43, a frequency comparator 44, a filter 46, a VCO 48 and another programmed frequency demultiplier 50. The switch 18 is used to select one of an oscillation signal outputted from the VCO 40 of the reference loop 14 and another oscillation signal outputted from the VCO 48 of the speed synthesizer 16 as a speed control signal. Further, the motor control loop 10 consists of a frequency comparator 24, a loop compensating circuit 28, a polarity inverting circuit 30, a switch 32, a motor driving amplifier (MDA) 34, a motor 12 and a tachometer 26. The above described conventional drum servo systems, however, have the following drawbacks. First, when changing the control signal supplied to the drum servo circuit (namely, the phase control means) A, the drum servo circuit of each of the conventional drum servo systems responds to the change as if it received an abrupt disturbance from the outside. Namely, the drum servo circuit of each of the conventional servo systems gets into what is called a floating state . Especially, when the control signal is generated by changing a frequency de-multiplying rate used to perform a frequency de-multiplication of a reference clock having a frequency larger than the frequency of the control signal in order to change the frequency of the control signal and is fed to the drum servo circuit of each of the conventional drum servo systems, a phase error occurring in the drum servo circuit of each of the conventional drum servo systems immediately reflects this. Consequently, the drum servo circuit of each of the conventional drum servo systems responds to the change in frequency de-multiplication ratio in a manner similar to the manner of a response in case where it suffers an abrupt disturbance originated from the outside. Moreover, in case where a low-frequency (e.g., 30 hertzes (Hz) or 25 Hz) employed in a VTR is used as the frequency of the control signal, a phase error occurring in the drum servo circuit of each conventional drum servo system as the result of the change in reference phase of the reference clock signal becomes large and thus the stability of the drum servo circuit of each drum servo system is decreased. Second, in case of the conventional drum servo system of FIG. 3, when a speed control signal supplied from the speed synthesizer 16 is selected and normal reproduction is performed by releasing the switch 18 from the left position of FIG. 3 and placing the switch 18 in the right position of FIG. 3, a control signal fed to the motor control loop 10 is liable to include noises if the response characteristic of the control loop 10 is set such that the control loop 10 makes a quick response. As a consequence, the precision of frequency control becomes low. Conversely, if the precision of the frequency control is set to be high, the response of the control loop 10 becomes slow. The present invention is accomplished to eliminate the above described drawbacks of the conventional drum servo systems. It is, therefore, an object of the present invention to provide a drum servo system having a rotation control device which can always and stably follow an abrupt change occurring in a control signal. Next, another drawback of the conventional drum servo system will be described hereinafter by referring to FIGS. 4 and 5. Reference numeral 100 denotes the conventional drum servo system; 200 a reference clock generator; 8 a frequency demultiplier of which the de-multiplication ratio is 1/M; 9 a drum servo circuit; 1 a phase comparator; 2 a loop filter; 3 an amplifier; 7 a waveform shaping device; 4 a motor; 5 a drum ; and 6 an angle-of-rotation detector. As shown in FIG. 4, the conventional drum servo system 100 for controlling the rotation speed and the rotation phase of a video head (not shown) generates a control signal having no frequency deviation on the basis of a reference clock signal sent from the reference clock generator 200. Thus a drum servo operation is performed by this control signal. More particularly, as shown in FIG. 5, a reference clock signal, which has a frequency higher than the frequency of the control signal and is outputted from the reference clock generator 200, is supplied to the frequency demultiplier 8 which decreases the frequency of the reference clock signal to (1/M) times and then outputs to the noninverting input terminal of the phase comparator 1 of the drum servo circuit 9 a de-multiplication signal having the same frequency as the control signal has. A drum rotation information signal, of which the waveform is shaped, is supplied to the inverting input terminal of the phase comparator 1 which compares the phase of the drum rotation information signal with that of the control signal and then outputs a phase comparison signal representing the result of the comparison to the loop filter 2. Thereafter, the loop filter 2 outputs a signal obtained by removing high-frequency components of the supplied phase comparison signal therefrom to the amplifier 3. Subsequently, the signal amplified by the amplifier 3 is fed to the motor 5. Thereby, the rotary head drum 5 having a well-known structure rotates being controlled by the control signal having a predetermined frequency. The angle-of-rotation detector 6 outputs a drum rotation information signal (hereunder sometimes referred to as an angle-of-rotation detection signal) to the waveform shaping device 7. Thus the rotation of the drum 6 is controlled by the drum servo circuit 9 to which the frequency de-multiplication signal having the same frequency as the control signal has. This conventional drum servo system has the following drawback. Namely, in case where a video signal having a frequency deviation of, for instance, + 0.1 % and a sound signal having no frequency deviation are simultaneously recorded by means of a VTR having a well-known servo system, the drum servo system follows a reference signal separated from the video signal and thus the number of rotation of the drum is larger than a normal or regular number of rotation thereof by + 0.1 %. At the time of reproducing a record, the drum servo system follows a control signal, which has no frequency deviation and is generated from a reference clock signal, and thus the normal or regular number of rotation of the drum is maintained. Therefore, a number-of-rotations deviation of the drum is ± 0 %. Hence, if a frequency deviation occurs in a video signal to be recorded, a lapse of time when magnetic tape touches and travels around the drum in case of reproducing the video signal (hereunder sometimes referred to simply as a reproducing time) is different from another lapse of time when the magnetic tape touches and runs around the drum in case of recording the video signal (hereunder sometimes referred to simply as a recording time) because of the fact that the number of rotations of the drum at the time of recording the video signal is different from that of rotations of the drum at the time of reproducing the recorded video signal. (In this case, the reproducing time is longer than the recording time by 0.1 %.) Thus this conventional drum servo system has a drawback in that when a video signal having a frequency deviation and a sound signal having no frequency deviation are simultaneously recorded and thereafter the video and sound signals are simultaneously reproduced, a pitch of a sound indicated by the sound signal at the reproduction differs from a pitch of the sound indicated by the sound signal at the time of the recording. (In this case, the former pitch becomes lower than the latter pitch.) The present invention is created to eliminate this drawback of the conventional drum servo system. It is, accordingly, another object of the present invention to provide a drum servo system which can make a reproducing time substantially equal to a recording time. SUMMARY OF THE INVENTION To achieve the foregoing objects, in accordance with an aspect of the present invention, there is provided a drum servo system comprising the features of claim 1. The precharacterizing features of Claim 1 are disclosed in JP-A-61 067 114. Thus a radical change in the control signal, which occurs when the phase or frequency of the control signal is changed similarly as an abrupt disturbance from the outside, can preferably be absorbed in the comparison control means. Thereby, the rotation control means can always and stably follow the abrupt change occurring in the control signal. Further, in order to achieve the foregoing objects, in accordance with another aspect of the present invention, there is provided a drum servo system according to dependent claims 5-7 including a time information reading means. Thus the reproducing time can be made to be equal to the recording time with high precision. Further, even if a video signal having a frequency deviation is recorded and reproduced together with a digital sound data signal having no frequency deviation, the rotation phase (namely, the angle of rotation) of the drum can be controlled on the basis of the digital sound data signal by applying the present invention to a well-known VTR. Thereby, a video signal can be reproduced completely in synchronization with a sound signal. Consequently, extremely high-quality reproduced image and sound can be obtained. BRIEF DESCRIPTION OF THE DRAWINGSOther features, objects and advantages of the present invention will become apparent from the following description of preferred embodiments with reference to the drawings in which like reference characters designate like or corresponding parts throughout several views, and in which: FIGS. 1 to 3 are schematic block diagrams for illustrating conventional drum servo systems; FIGS. 4 and 5 are schematic block diagrams for illustrating another conventional drum servo system; FIGS. 6 to 8 are schematic block diagrams respectively illustrating a first, second and third embodiments of the present invention; FIG. 9 is a schematic block diagram for illustrating a fourth embodiment of the present invention; FIG. 10 is a schematic block diagram for illustrating a fifth embodiment of the present invention; and FIG. 11 is a diagram for illustrating time information recorded on a storage medium. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSHereinafter, preferred embodiments of the present invention will be described in detail by referring to the accompanying drawings. FIGS. 6 to 8 are schematic block diagrams respectively illustrating a first, second and third embodiments of the present invention. Incidentally, in these figures, like reference characters designate like or corresponding portions of the conventional drum servo systems of FIGS. 1 to 5. Further, the description of such portions are omitted herein for simplicity of description. The first embodiment (namely, a first drum servo system B of FIG. 6) is adapted to change one of reference clocks respectively having different frequencies to another thereof if necessary for controlling a rotating frequency of a drum. As shown in FIG. 6, this drum servo system B is comprised of a phase control means (namely, a rotation control means) A for controlling a rotating phase (thus controlling a rotation) of a drum 5 on the basis of a phase comparison signal obtained by comparing a phase of an angle-of-rotation information signal determined according to an angle of rotation of the drum 5 with a phase of a control signal and a phase locked loop (PLL), namely a comparison control means for outputting the control signal to be supplied to the phase control means A by performing phase comparison control by use of a frequency de-multiplication signal obtained by effecting a frequency de-multiplication of any one of reference clocks (namely, reference signals) a and b having frequencies higher than the frequency of the control signal. Further, the PLL is composed of a phase comparator 52, a loop filter 53, a VCO 54 and a frequency demultiplier 56. Incidentally. reference numeral 55 designates a frequency demultiplier. In case of this drum servo system B, to change the frequency of the control signal for controlling the rotation of the drum 5, a stationary contact to be engaged with a movable contact 50c of a selection switch (hereunder referred to simply as a switch) 50 is changed between a stationary one 50a to which a reference clock a is supplied and another stationary one 50b to which another reference clock 50b is supplied. In case where the switch 50 is in a switching sate as shown in FIG. 6, a frequency de-multiplication signal obtained by changing the frequency of the reference clock a into (1/A) thereof by the frequency demultiplier 51 is fed to the noninverting input terminal of the phase comparator 52. Then the phase comparator 52 outputs to the loop filter 53 a phase comparison signal obtained by comparing the phase of this frequency de-multiplication signal with that of another frequency de-multiplication signal supplied to the inverting input terminal thereof from a frequency demultiplier 56 which will be described later. Thereafter, the loop filter 53 outputs to the VCO 54 a signal obtained by removing a high-frequency component of the phase comparison signal supplied thereto. An oscillation output signal outputted from the VCO 54 is bifurcated, namely, branched into the frequency demultipliers 55 and 56. The frequency of the oscillation output signal supplied to the frequency demultiplier 55 is changed to (1/M) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator 1 of the phase control means A. On the other hand, the frequency of the oscillation output signal applied to the frequency demultiplier 56 of the PLL is changed to (1/a) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the inverting input terminal of the phase comparator 52. By setting the frequency de-multiplication ratio (1/a) of the frequency demultiplier 56 as larger than that (1/M) of the frequency demultiplier 55, the frequency of the phase comparison signal outputted from the phase comparator 52 can be set as higher than that of the phase comparison signal outputted from the phase comparator 1. Thus, in case of this drum servo system B, effects of an abrupt change of a state of a drum servo circuit (namely, a phase control means) A owing to a change of a reference clock between the clock a and the clock b, which are equivalent to effects of a radical disturbance from the outside, can be absorbed in the PLL controlled by the VCO 54. Therefore, it can be averted that a change in reference clock directly causes a phase error of the drum servo circuit. The drum servo circuit can stably follow change. in rotating phase of the drum 5 occurring due to change in reference clock. Further, the second embodiment (namely, a second drum servo system C of FIG. 7) is adapted to change a frequency de-multiplication signal obtained by performing a frequency de-multiplication of a single clock if necessary for changing a rotating frequency of a drum. As illustrated in FIG. 7, the second drum servo system C is composed of a phase control means (namely, a rotation control means) A for controlling a rotating phase (thus controlling a rotation) of a drum 5 on the basis of a phase comparison signal obtained by comparing a phase of an angle-of-rotation information signal determined according to an angle of rotation of the drum 5 with a phase of a control signal and a phase locked loop (PLL), namely a comparison control means for outputting the control signal to be supplied to the phase control means A by performing phase comparison control by selecting and using one of three frequency de-multiplication signals obtained by effecting a frequency de-multiplication of a reference clock (namely, a reference signal) having a frequency higher than the frequency of the control signal. Further, the PLL is composed of a phase comparator 64, a loop filter 65, a VCO 66, frequency demultipliers 68, 69 and 70 and a switch 71. Incidentally, the phase comparator 64, the loop filter 65, the VCO 66 and the frequency demultiplier 67 are the same as the phase comparator 52, the loop filter 53, the VCO 54 and the frequency demultiplier 55 of the first embodiment of FIG. 6, respectively. In case of this drum servo system C, to change the frequency of the control signal for controlling the rotation of the drum 5, a stationary contact to be engaged with a movable contact 63d of a selection switch (hereunder referred to simply as a switch) 63 is changed among a stationary one 63a, to which a frequency de-multiplication signal obtained by changing the frequency of a reference clock into (1/A1) thereof in a frequency demultiplier 60 is supplied, and another stationary one 63b, to which a frequency de-multiplication signal obtained by changing the frequency of the reference clock into (1/A2) thereof in a frequency demultiplier 61 is supplied, and further another stationary one 83c, to which a frequency de-multiplication signal obtained by changing the frequency of the reference clock into (1/A3) thereof in a frequency demultiplier 62 is supplied. In case where the switch 63 is in a switching sate as shown in FIG. 7, a frequency de-multiplication signal obtained by changing the frequency of the reference clock into (1/A1) thereof by the frequency demultiplier 80 is fed to the noninverting input terminal of the phase comparator 64 of the PLL. Then the phase comparator 64 outputs to the loop filter 65 a phase comparison signal obtained by comparing the phase of this frequency de-multiplication signal with that of another frequency de-multiplication signal supplied to the inverting input terminal thereof and selected by a selection switch (hereunder referred to as a switch) 71 which will be described later. Thereafter, the loop filter 65 outputs to the VCO 66 a signal obtained by removing a high-frequency component of the phase comparison signal supplied thereto. An oscillation output signal outputted from the VCO 66 is first bifurcated. The frequency of the oscillation output signal supplied to the frequency demultiplier 67 is changed to (1/M) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator 1 of the phase control means A. On the other hand, the other oscillation output signal is further branched into three oscillation output signals (hereunder referred to as branch signals) respectively supplied to the frequency demultipliers 68, 69 and 70. The frequency of the oscillation output signal applied to the frequency demultiplier 68 is changed by (1/a1) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 71a of the switch 71. Similarly, the frequency of the oscillation output signal applied to the frequency demultiplier 69 is changed to (1/a2) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 71b of the switch 71. Further, the frequency of the oscillation output signal applied to the frequency demultiplier 70 is changed into (1/a3) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 71c of the switch 71. In case of a switching state of the switch 71 of FIG. 7, the frequency of the oscillation output signal supplied to the frequency demultiplier 68 is changed to (1/a1) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the inverting input terminal of the phase comparator 64. By setting each of the frequency de-multiplication ratio (1/a1) of the frequency demultiplier 68, that (1/a2) of the frequency demultiplier 89 and that (1/a3) of the frequency demultiplier 70 as larger than that (1/M) of the frequency demultiplier 67, the frequency of the phase comparison signal outputted from the phase comparator 64 can be set as higher than that of the phase comparison signal outputted from the phase comparator 1. Thus, in case of this drum servo system C, effects of an abrupt change of a state of a drum servo circuit (namely, the phase control means) A, which are equivalent to effects of a radical disturbance from the outside, can be absorbed in the PLL controlled by the VCO 66 by changing the combination of switching states of the switches 63 and 71. The drum servo circuit can stably follow change in the rotating phase of the drum 5 occurring due to change in reference clock. Moreover, the third embodiment (namely, a third drum servo system D of FIG. 8) is constructed by employing a frequency comparator 81 in stead of the phase comparator 52 of the PLL of FIG. 6. As illustrated in FIG. 3, the third drum servo system D is composed of a phase control means (namely, a rotation control means) A for controlling a rotating phase (thus controlling a rotation) of a drum 5 on the basis of a phase comparison signal obtained by comparing a phase of an angle-of-rotation information signal determined according to an angle of rotation of the drum 5 with a phase of a control signal and a PLL, namely a comparison control means for outputting the control signal to be supplied to the phase control means A by performing phase comparison control by selecting and using a frequency de-multiplication signal obtained by effecting a frequency de-multiplication of a reference clock (namely, a reference signal) having a frequency higher than the frequency of the control signal. Further, the PLL is composed of a phase comparator 81, a loop filter 82, a VCO 83 and a frequency demultipliers 85. Incidentally, the frequency demultiplier 80 has the same structure as the frequency demultiplier 51 does. Similarly, the loop filter 65 is the same as the loop filter 53 or 65. Further, the VCO 83 is the same as the VCO 54 or 66. Moreover, the frequency demultiplier 84 is the same as the frequency demultiplier 55 or 67. Furthermore, the frequency demultiplier 85 is the same as the frequency demultiplier 56. In case of this drum servo system D. to change the frequency of the control signal for controlling the rotation of the drum 5, the frequency of a frequency comparison signal outputted from the frequency comparator 81 is changed. As shown in FIG. 8, a frequency de-multiplication signal obtained by changing the frequency of the reference clock into (1/A) thereof by the frequency demultiplier 60 is fed to the noninverting input terminal of the frequency comparator 81 of the PLL. Then the frequency comparator 81 outputs to the loop filter 82 a frequency comparison signal obtained by comparing the frequency of this frequency de-multiplication signal with that of another frequency de-multiplication signal supplied from the frequency demultiplier 85 (to be described later) to the inverting input terminal thereof. Thereafter, the loop filter 82 outputs to the VCO 83 a signal obtained by removing a high-frequency component of the frequency comparison signal supplied thereto. An oscillation output signal outputted from the VCO 83 is first bifurcated. The frequency of the oscillation output signal supplied to the frequency demultiplier 84 is changed to (1/M) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator 1 of the phase control means A. On the other hand, the other oscillation output signal is supplied to the frequency demultiplier 85. The frequency of the oscillation output signal applied to the frequency demultiplier 85 is changed to (1/a) thereof. Further, by setting the frequency de-multiplication ratio (1/a) of the frequency demultiplier 85 as larger than that (1/M) of the frequency demultiplier 84, the frequency of the frequency comparison signal outputted from the frequency comparator 81 can be set as higher than that of the phase comparison signal outputted from the phase comparator 1. Thus, in case of this drum servo system D, effects of an abrupt change of a state of a drum servo circuit (namely, the phase control means) A, which are equivalent to effects of a radical disturbance from the outside, can be absorbed in the PLL controlled by the VCO 83. Further, this can prevent a phase error occurring in the drum servo circuit from immediately reflecting change in the frequency of a frequency comparison signal. The drum servo circuit can stably follow change in the rotating phase of the drum 5 occurring due to change in reference clock. Incidentally, in FIGS. 6, 7 and 8, the switches 50, 63 and 71 are illustrated as mechanical switching devices. An electronic switching device, however, may be used as each of the switches 50, 63 and 71. Furthermore, in case of employing the above described embodiments, the following effects can be obtained. First, in case of the embodiment changing a control signal similarly as the conventional system, the drum servo circuit (namely, the phase control means) A can stably follow a change of a control signal because a transient phase error does not occur in the drum servo circuit by changing a reference clock. Further, in case of the embodiment changing the frequency of a control signal, effects of a step response at the time of changing the frequency of a control signal are absorbed in the PLL for generating a control signal. Thus a radical change in input control signal does not occur. Consequently, the drum servo circuit (namely, the phase control means) A can stably follow a change in the frequency of a control signal. Moreover, in cases of the above described embodiments, a phase comparison between low-frequency signals used in a VTR is performed by using a frequency de-multiplication signal obtained by effecting a frequency de-multiplication of a reference clock signal which is produced as a result of a frequency de-multiplication of a high-frequency signal. Thus even if the frequency or phase of the reference clock signal is changed, the drum servo circuit can stably follow the change in the frequency or phase of the reference clock signal. Furthermore, the PLL or comparison control means for generating a control signal performs a phase comparison between signals having a frequency higher than the frequency of the control signal. Thus, in case of changing the frequency of the control signal, the circuit of the comparison control means can quickly respond to the change of the control signal. Thereby, the drum servo circuit (namely, the phase control means) A, to which the control signal is supplied, can stably follow the change of the control signal. Hereinafter, other preferred embodiments (namely, other drum servo systems) of the present invention will be described by referring to FIGS. 9 and 10. Each of these drum servo systems is adapted to read time information relating to digital sound data represented by digital sound data signals, which are recorded onto, for example, video signal tracks on a magnetic tape in a superposing manner or on an independent signal track as will be described later, and to change the frequency of a control signal for controlling the number of rotations of a drum according to the time information by performing a phase comparison or a frequency comparison by using a signal having a frequency higher than the frequency. Thus, in each of these embodiments, a clock oscillation frequency of the control signal can be changed differently from the conventional drum servo system of FIG. 4 employing the reference clock generator 200. Hereinafter, these embodiments in case of simultaneously recording a video signal and a digital sound data signal will be described in detail. FIGS. 9 and 10 are schematic block diagrams respectively illustrating these embodiments (hereunder referred to as a fourth and fifth embodiments, respectively). Further, FIG. 11 is a diagram for illustrating the time information recorded on a recording medium. In FIGS. 9 and 10, like reference characters designate like composing elements of the above described drum servo systems. Therefore, the descriptions of such composing elements of the fourth and fifth embodiments are omitted herein. In FIGS. 9 and 10, reference numerals 100 and 300 denote drum servo systems; 110 an audio-sampling-frequency generator; 120, 130, 180, 230. 240, 250 and 260 frequency demultipliers respectively having frequencyde-multiplication ratios (1/s), (1/L), (1/N), (1/K), (1/a), (1/b) and (1/c); 140 and 270 selection switches (hereunderreferred to simply as switches); 140a, 140b, 270a, 270b and 270c stationary contacts; 140c and 270d movable contacts; 150 a phase comparator; 160 a loop filter; 170 a VCO; 2000 a time information reading circuit; 210 a magnetic tape; 220 a reference clock generator: fs an audio-sampling-frequency; and fv a video frequency. First, the time information will be described in detail hereinbelow. Generally, there is no synchronous relation between the video frequency fv of a video signal and the audio-sampling-frequency of a sound data signal. Hence, it is usual that these signals are simultaneously recorded by employing the following method. Namely, each of tracks serially formed on the magnetic tape 210 for recording digital sound data signals is divided or partitioned in the longitudinal direction thereof into five data blocks as illustrated in FIG. 11. These data blocks are classified according to the number of audio-sampling-data to be packed and recorded in each of these data blocks into two groups as follows. One is a small-data block group of data blocks - each (hereunder referred to as Small Data) having a predetermined number S of audio-sampling-data. The other is a large-data block group of data blocks - each (hereunder referred to as Large Data) having a predetermined number L, which is larger than the predetermined number S, of audio-sampling-data. After the data blocks are preliminarily classified into these groups, audio-sampling data represented by digital sound data signals are recorded in the data blocks. Incidentally, let X denote the average number of audio-sampling-data per data block in case where the video frequency fv is equal to a rated frequency. The numbers S and L are predetermined in such a manner to meet the following condition: S < X < L. The numbers of audio-sampling-data of Small Data and Large Data obtained by being sampled at the audio-frequency sampling frequency with what is called a crystal precision can be considered as precise information relating to time (namely, time information). Thus precise time information can be recorded by recording on the magnetic tape 210 information representing which of Small Data and Large data to be recorded is. Next, the fourth embodiment of the present invention will be described in detail hereinbelow. As illustrated in FIG. 9, the drum servo system 100 is composed of a drum servo circuit (namely, a comparison control means) 9 for controlling a rotation of a drum 5 on the basis of a phase comparison signal obtained as a result of comparing the phase of an angle-of-rotation signal obtained according to an angle of rotation of the drum 5 with that of a control signal indicating a rotational frequency of the drum 5, the time information reading circuit (namely, a time information reading means) 120 for outputting a time-information reading signal obtained by reading time information recorded on the magnetic tape (namely, a recording medium) 121 to be scanned by way of the drum 5 and the phase comparator (namely, a comparison control means) 150 for selecting a plurality of frequency de-multiplication signals obtained as a result of a frequency de-multiplication of a reference signal having an audio-sampling frequency fs, which is effected by using different frequency de-multiplication ratios (1/S) and (1/L), on the basis of at least the time information reading signal and for performing a control operation by effecting a phase comparison or a frequency comparison between signals having frequencies higher than the frequency of the control signal by use of the selected frequency de-multiplication signals. An operation of the drum servo system 100 constructed as above described will be explained in detail hereinbelow. First, in case where Large Data represent time information obtained from digital sound data signals recorded on the magnetic tape 210 by reproducing and scanning a track (or data blocks), on which the digital sound data signals are recorded, by means of the magnetic head loaded onto the drum 5, the time information reading circuit 2000 detects the Large Data and outputs to the switch 140 a time information reading signal indicating that the switch 140 should be placed in the position corresponding to the frequency demultiplier 130 (namely, the movable contact 140c should be connected to the stationary contact 140b). The switch 140 responds to the time information reading signal and is placed in the position corresponding to the frequency demultiplier 130. This results in that a frequency de-multiplication signal obtained by changing the audio-sampling frequency fs of an audio-sampling signal generated in the audio-sampling frequency generator 110 into (1/L) thereof by use of the frequency demultiplier 130 is supplied to the noninverting input terminal of the phase comparator 150 of the PLL. The frequency of the frequency de-multiplication signal from the frequency demultiplier 130 is substantially equal to and slightly less than five times the frequency fv of a video signal. Further, the frequency de-multiplication ratio (1/L) of the frequency demultiplier 130 is less than that (1/S) of the frequency demultiplier 120. Then, the phase comparator 150 outputs to the loop filter 160 a phase comparison signal obtained by comparing the frequency of this frequency de-multiplication signal with that of another frequency de-multiplication signal supplied from the frequency demultiplier 180 (to be described later) to the inverting input terminal thereof. Thereafter, the loop filter 160 outputs to the VCO 170 a signal obtained by removing a high-frequency component of the frequency comparison signal supplied thereto. The frequency (3fs) of an oscillation output signal outputted from the VCO 170 is three times the audio-sampling frequency fs. PLL is composed of this phase comparator 150, the loop filter 160, the VCO 170 and the frequency demultiplier 180. The oscillation output signal outputted from the VCO 170 is first bifurcated. The frequency of the oscillation output signal supplied to the frequency demultiplier 180 is changed to (1/N) thereof. Incidentally, N is a predetermined positive integer. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator 150. On the other hand, the other oscillation output signal is supplied to the frequency demultiplier 8. The frequency of the oscillation output signal applied to the frequency demultiplier 8 is changed to (1/M) thereof and as the consequence becomes equal to the video frequency fv. Thereafter, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator (not shown) of the drum servo circuit 9 as a control signal for controlling the drum servo circuit 9. Further, by setting the frequency de-multiplication ratio (1/N) of the frequency demultiplier 180 as larger than that (1/M) of the frequency demultiplier 190, the frequency (5fv) of the frequency comparison signal outputted from the frequency comparator 150 can be set as higher than that (fv) of the phase comparison signal outputted from the phase comparator 1. Next, in case where Small Data represent time information obtained by reproducing and scanning the track (or the data blocks) by means of the magnetic head loaded onto the drum 5, the time information reading circuit 2000 outputs to the switch 140 a time information reading signal indicating that the switch 140 should be placed in the position corresponding to the frequency demultiplier 120 (namely, the movable contact 140c should be connected to the stationary contact 140a). The switch 140 responds to the time information reading signal and is placed in the position corresponding to the frequency demultiplier 120. This results in that a frequency de-multiplication signal obtained by changing the audio-sampling frequency fs of an audio-sampling signal generated in the audio-sampling frequency generator 110 into (1/S) thereof by use of the frequency demultiplier 120 is supplied to the noninverting input terminal of the phase comparator 150. The frequency of the frequency de-multiplication signal from the frequency demultiplier 120 is substantially equal to and slightly larger than five times the frequency fv of a video signal. After this, the drum servo system operates similarly as in case where Large Data represent time information. Therefore, the description of the operation following this is omitted herein. Thereafter, when the time information becomes represented by Large Data, the same operation as in the above described case where Large Data represent time information is performed. Thus the drum servo system 100 of the fourth embodiment can change the frequency of the control signal for controlling the number of rotations of the drum by reading the time information recorded on the magnetic tape 210 and performing a phase comparison or a frequency comparison between signals having frequencies higher than the frequency of the control signal according to the time information. Next, another drum servo system embodying the present invention (namely, the fifth embodiment of the present invention) will be described in detail hereinbelow. As illustrated in FIG. 10, the drum servo system 300 is adapted to perform a frequency de-multiplication of a reference clock generated by the reference clock generator 220 by changing the frequency of the reference clock into (1/K) thereof and select one of frequency de-multiplication signals, which are obtained by changing the frequency of an output signal of the VCO 170 into (1/a), (1/b) and (1/c) thereof, respectively, according to time information, for the purpose of changing the rotational frequency of the drum. As shown in FIG. 10, the drum servo system 300 is comprised of a drum servo circuit (namely, a rotation control means) 9 for controlling a rotation of the drum 5 on the basis of a phase comparison signal obtained as a result of comparing the phase of an angle-of-rotation detecting signal obtained according to an angle of rotation of the drum 5 with the phase of a control signal prescribing a rotating frequency of the drum 5, the time information reading circuit (namely, a time information reading means) 20 for reading time information recorded on the magnetic tape (namely, a recording medium) to be scanned by way of the drum 5 and the phase comparator (namely, a comparison control means) 150 for selecting one of frequency de-multiplication signals respectively obtained by performing frequency de-multiplications of an output signal (namely, a reference signal) of the VCO 170 by using different frequency de-multiplication ratios (1/a), (1/b) and (1/c) according to at least the time information and effecting a phase comparison or a frequency comparison of a signal having a frequency higher than a frequency of the control signal by use of the selected frequency de-multiplication signal. Namely, in case of the drum servo system 300, the frequency demultipliers 120 and 130 of the drum servo system 100 of FIG. 9 is replaced with the frequency demultiplier 230 employing a frequency de-multiplication ratio (1/K). Further, a frequency de-multiplication signal outputted from the frequency demultiplier 230 is directly applied to the noninverting input terminal of the phase comparator 150. Moreover, the frequency demultipliers 240, 250 and 260 which employ the frequency de-multiplication ratios (1/a), (1/b) and (1/c), respectively, is used instead of the frequency demultiplier 180. Furthermore, each of frequency de-multiplication signals outputted from the frequency demultipliers 240, 250 and 260 can be selected by using the switch 270 in response to the time information reading signal. In addition, the output signal selected by the switch 270 is directly supplied to the noninverting input terminal of the phase comparator 150. Incidentally, in FIG. 10, like reference characters designate like composing elements of the drum servo system of FIG. 9. Therefore, the descriptions of such composing elements of the fifth embodiments are omitted herein. To change the frequency of a control signal for controlling the drum 5 in the drum servo system 300, the movable contact 270d of the switch 270 provided with the stationary contacts 270a, 270b and 270c, to which frequency de-multiplication signals obtained by changing the frequency of the output signals (namely, the reference signals) of the VCO 170 into (1/a), (1/b) and (1/c) thereof, respectively, on the basis of the frequency de-multiplication signal obtained by changing the frequency of a reference clock into (1/K) thereof by the frequency demultiplier 230 is connected to one of the stationary contacts 270a to 270c according to the time information signal outputted from the time information reading circuit 2000, In the state of the switch 270 as shown in FIG. 10, a frequency de-multiplication signal outputted from the frequency demultiplier 250 is fed to the noninverting input terminal of the phase comparator 250. Namely, a frequency de-multiplication signal obtained by changing the frequency of the reference clock into (1/K) thereof by the frequency demultiplier 230 is fed to the noninverting input terminal of the phase comparator 150. Then the phase comparator 150 outputs to the loop filter 160 a phase comparison signal obtained by comparing the phase of this frequency de-multiplication signal with that of another frequency de-multiplication signal supplied to the inverting input terminal thereof and selected by a switch 270 which will be described later. Thereafter, the loop filter 160 outputs to the VCO 170 a signal obtained by removing a high-frequency component of the phase comparison signal supplied thereto. An oscillation output signal outputted from the VCO 170 is first bifurcated. The frequency of the oscillation output signal supplied to the frequency demultiplier 8 is changed into by (1/M) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is fed to the noninverting input terminal of the phase comparator (not shown) of the drum servo circuit 9 as a control signal for controlling the drum servo circuit 9. On the other hand, the other oscillation output signal is further branched into three oscillation output signals (namely, branch signals) respectively supplied to the frequency demultipliers 240, 250 and 260. The frequency of the oscillation output signal applied to the frequency demultiplier 240 is changed to (1/a) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 270a of the switch 270. Similarly, the frequency of the oscillation output signal applied to the frequency demultiplier 250 is changed to (1/b) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 270b of the switch 270. Further, the frequency of the oscillation output signal applied to the frequency demultiplier 260 is changed to (1/c) thereof. Subsequently, a signal obtained as the result of this frequency de-multiplication is supplied to the stationary terminal or contact 270c of the switch 270. By setting each of the frequency de-multiplication ratios (1/a), (1/b) and (1/c) as larger than that (1/M), the frequency of the phase comparison signal outputted from the phase comparator 150 can be set as higher than that of the phase comparison signal outputted from the phase comparator 1. Thus, in cases of the drum servo systems 100 and 300, effects of an abrupt change of a state of a drum servo circuit of the phase control means A, which are equivalent to effects of a radical disturbance from the outside, can be absorbed in the PLL comprised of the phase comparator 150. the loop filter 160, the VCO 170 and the frequency demultipliers 180, 240, 250 and 260 by changing the combination of switching states of the switches 140 and 270. These drum servo circuit can stably follow change in the rotating phase of the drum 5 occurring due to change in reference clock. Further, when a phase comparison is performed in the phase comparator 150, a low-frequency signal obtained by effecting a frequency de-multiplication of a signal having the audio-sampling frequency fs or of a reference clock is supplied to the noninverting input terminal of the phase comparator 150, and on the other hand another low-frequency signal obtained by effecting a frequency de-multiplication of an oscillation output signal of the VCO 170 having a frequency (3fs), which is three times the audio-sampling frequency fs, is supplied to the inverting input terminal of the VCO 170. As the result, the phase comparison can be effected in a low-frequency region. Thus, even when the signal to be supplied to the noninverting input terminal of the phase comparator is selected from such low-frequency signals by the switches 140 and 270, the phase comparison can stably be performed without an abrupt phase variation or frequency variation. Further, the PLL for generating a control signal uses the frequency (namely, the audio-sampling frequency fs) higher than the frequency of the control signal (namely, the video frequency fv). Therefore, in case of effecting a frequency control by changing the value of the frequency of the control signal, the drum servo system can quickly respond to the change in the frequency of the control signal. Furthermore, when recording and reproducing, a drum servo operation is effected on the basis of a reference clock or a signal having the audio-sampling frequency fs with oscillation precision of a quartz-crystal oscillator. Thus a reproducing time is substantially equal to a recording time. Additionally, a sound signal recorded simultaneously with a video signal can be reproduced substantially simultaneously with the video signal. While preferred embodiments of the present invention have been described above, it is to be understood that the present invention is not limited thereto and that other modifications will be apparent to those skilled in the art. The scope of the present invention, therefore, is to be determined solely by the appended claims. A drum servo system provided with a rotation control device for controlling a rotation of a drum on the basis of a phase comparison signal obtained as a result of comparing the phase of an angle-of-rotation information signal obtained according to an angle of rotation of the drum with the phase of a control signal and a comparison control device for outputting the control signal to the rotation control device by performing a phase comparison or a frequency comparison by use of a frequency de-multiplication signal obtained by effecting a frequency de-multiplication of a reference signal having a frequency higher than a frequency of the control signal. Thus a radical change in the control signal, which occurs when the phase or frequency of the control signal is changed similarly as an abrupt disturbance from the outside, can preferably be absorbed in the comparison control device. Thereby, the rotation control means can always and stably follow the abrupt change occurring in the control signal.	A drum servo system having a drum (5), comprising: a rotation control means (A; 9) for controlling a rotation of the drum (5) on the basis of a phase comparison signal obtained as a result of comparing the phase of an angle-of-rotation information signal obtained according to an angle of rotation of the drum (5) with the phase of a control signal; and a comparison control means having a phase locked loop means (52, 53, 54, 56; 64, 65, 66, 68, 69, 70, 71; 81, 82, 83, 85; 150, 160, 170, 180; 150, 160, 170, 240, 250, 260, 270) for receiving an input signal which is based on a reference clock signal, for generating and outputting an oscillation output signal, and for performing a phase or frequency comparison between said input signal and the frequency divided oscillation output signal, said phase locked loop means having a phase or frequency comparator (52; 64; 81; 150) for performing said phase or frequency comparison, a loop filter (53; 65; 82; 160) for removing high frequency signal components, a VCO (54; 66; 83; 170) for generating and outputting said oscillation output signal, and a first frequency demultiplier means (56; 68, 69, 70, 71; 85; 180; 240, 250, 260, 270) for receiving the oscillation output signal and for generating and outputting to said phase or frequency comparator said frequency divided oscillation output signal, said frequency divided oscillation output signal having a frequency which is a first predetermined integral submultiple of the frequency of said oscillation output signal, characterized by a control signal generating means having a second frequency demultiplier means (55; 67; 84; 8) for receiving said oscillation output signal and for generating and outputting to said rotation control means said control signal, said control signal having a frequency which is a second predetermined integral submultiple of the frequency of said oscillation output signal, wherein the demultiplication ratio of said first frequency demultiplier means is larger than that of said second frequency demultiplier means. The drum servo system as set forth in claim 1, wherein said comparison control means further comprises: a selection switch means (50) for receiving at least two reference clock signals and for selecting and outputting one of the received reference clock signals; and a third frequency demultiplier means (51) for receiving the selected reference clock signal outputted from the selection switch means (50) and for generating and outputting to said phase comparator said input signal, said input signal having a frequency which is a predetermined integral submultiple of the frequency of the selected reference clock signal. The drum servo system as set forth in claim 1, wherein the comparison control means further comprises: a plurality of third frequency demultiplier means (60, 61, 62; 120, 130) for receiving said reference clock signal and for generating and outputting a plurality of frequency de-multiplication signals, said frequency de-multiplication signals having frequencies which are predetermined integral submultiples of the frequency of the reference clock signal, respectively; and a selection switch means (63; 140) for receiving at least said plurality of frequency de-multiplication signals and for selecting and outputting to said phase comparator one of the received signals as said input signal. The drum servo system as set forth in claim 1, wherein the comparison control means further comprises: a third frequency demultiplier means (80) for receiving said reference clock signal and for generating and outputting to said phase or frequency comparator said input signal, said input signal having a frequency which is a predetermined integral submultiple of the frequency of the reference clock signal. The drum servo system as set forth in claim 3, wherein a time information reading means (2000) is provided for reading time information recorded on a recording medium (210) to be scanned by way of the drum (5); and said selection switch means (63; 140) is adapted for selecting and outputting to said phase comparator one of the received signals as said input signal according to the time information. The drum servo system as set forth in claim 5, wherein the comparison control means comprises: a first third frequency demultiplier means (120) for receiving said reference clock signal and for generating and outputting a first frequency de-multiplication signal having a frequency which is a first predetermined integral submultiple of the frequency of the reference clock signal; and a second third frequency demultiplier means (130) for receiving said reference clock signal and for generating and outputting a second frequency de-multiplication signal having a frequency which is a second predetermined integral submultiple of the frequency of the reference clock signal, the second predetermined integral submultiple being less than the first predetermined integral submultiple; and wherein said selection switch means (63; 140) is adapted to select and output to said phase comparator the first frequency de-multiplication signal if the number of audio-sampling data to be recorded in each data block on a recording medium provided on the drum is equal to a first predetermined number, and to select and output to said phase comparator the second frequency de-multiplication signal if the number of audio-sampling data to be recorded in each data block on a recording medium provided on the drum is equal to a second predetermined number larger than the first predetermined number. The drum servo system as set forth in claim 4, wherein a time information reading means (2000) is provided for reading time information recorded on a recording medium (210) to be scanned by way of the drum (5); and said phase locked loop means comprises a plurality of first frequency demultiplier means (240, 250, 260) for receiving said oscillation output signal and for generating and outputting a plurality of frequency divided oscillation output signals having frequencies, which are predetermined integral submultiples of the frequency of the oscillation output signal, respectively, and a selection switch means (270) for selecting and outputting to said phase comparator (150) one of the plurality of frequency divided oscillation output signals according to the time information.	VICTOR COMPANY OF JAPAN; VICTOR COMPANY OF JAPAN, LIMITED	HIGURASHI SEIJI; OGASAWARA JIN; SHINDO TOMOYUKI; SUWA TETSUYA; HIGURASHI, SEIJI; OGASAWARA, JIN; SHINDO, TOMOYUKI; SUWA, TETSUYA
EP-0489379-B1	489,379	EP	B1	EN	19,980,715	1,992	20,100,220	new	C07D215	A61K31	A61K31, A61P25, C07D215	M07D215:38, C07D 215/38, M07D215:22B, C07D 215/227	5-amino-5,6,7,8-tetrahydroquinolines and related compounds, a process for their preparation and their use as medicaments	The present invention relates to tetrahydroquinolines and related compounds. More particularly, the present invention relates to 5-amino-5,6,7,8-tetrahydroquinolines of the formula wherein X-Y is a group of the formula wherein R is hydrogen, alkyl, alkenyl, alkynyl, or arylalkyl, or a group of the formula wherein R¹ is hydrogen, alkyl or arylalkyl; R² and R³ are independently hydrogen, alkyl, arylalkyl, diarylalkyl, cycloalkenylalkyl, alkoxy, arylalkoxy, or alkanoyl; R² and R³ taken together with the nitrogen atom to which they are attached form a group of the formula wherein p is 0 or 1, a group of the formula wherein Z is O, S, or a group of the formula NR⁶ wherein R⁶ is hydrogen, alkyl, or arylalkyl; R⁴ is hydrogen, alkyl or arylalkyl; R⁵ is hydrogen, alkyl or arylalkyl; and m is 0, 1, or 2, and n is 1 or 2; or geometrical and optical isomers thereof, or a pharmaceutically acceptable salt thereof, which are useful for relieving memory dysfunction, The invention relates further to a process for the preparation of these compounds and their use as medicaments.	The present invention relates to tetrahydroquinolines and related compounds. More particularly, the present invention relates to 5-amino-5,6,7,8-tetrahydroquinolines of the formula wherein X-Y is a group of the formula wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl, or a group of the formula wherein R1 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl; R2 and R3 are independently hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, di-phenyl-(C1-C6)-alkyl, (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, (C1-C6)-alkoxy, phenyl-(C1-C6)-alkoxy, or (C1-C6)-alkanoyl, or R2 and R3 taken together with the nitrogen atom to which they are attached form a group of the formula wherein p is 0 or 1, a group of the formula wherein Z is O, S, or a group of the formula NR6 wherein R6 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R4 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R5 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; wherein the phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl; m is 0, 1, or 2; and n is 1 or 2; with the proviso that when X-Y is and m is 1, then R2, R3, R4 and R5 are not hydrogen; the geometric and optical isomers thereof, or a pharmaceutically acceptable salt thereof, which are useful for relieving memory dysfunction, for example, memory dysfunction such as that associated with reduced cholinergic function in Alzheimer's disease alone or in combination with adjuvants.Subgeneric to the 5-amino-5,6,7,8-tetrahydroquinolines of the present invention are compounds wherein: a. X-Y is a group of the formula and m is 1; andb. X-Y is a group of the formula and m is 1.The present invention also relates to 5-hydroxy-5,6,7,8-tetrahydroisoquinolines of the formula wherein X-Y is a group of the formula wherein R is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, or phenyl-C1-C6-alkyl, or a group of the formula wherein R1 is C1-C6-alkyl or phenyl-C1-C6-alkyl; R4 is hydrogen, C1-C6-alkyl, or phenyl-C1-C6-alkyl; R5 is hydrogen, C1-C6-alkyl, or phenyl-C1-C6-alkyl, wherein the phenyl may in each case be substituted as indicated above; and m is 0, 1, or 2; and n is 1 or 2; or the geometric or optical isomers thereof, , which are useful as intermediates for the preparation of the present 5-amino-5,6,7,8-tetrahydroquinolines.US-A-4 942 168 discloses N-substituted 4-quinolinamines and 1,4-oxazino[2,3-c] or -[2,3-d] quinoline derivatives, which are useful for the treatment of memory dysfunctions.EP-A-0 361 489 discloses i. a. 4-aminoquinoline derivatives having an activity in accelerating mnemonic and learning performance.EP-A-0 258 755 discloses α-alkyl-4-amino-3-quinoline-methanols and 1-(4-aralkylamino-3-quinolinyl) alkanones, which are useful for enhancing memory.As used throughout the specification and appended claims, the term alkyl shall mean a straight or branched chain hydrocarbon group containing no unsaturation and having from 1 to 8 carbon atoms. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, neopentyl, tert-pentyl, hexyl, pentyl, and octyl, and the like. The term alkenyl shall mean a straight or branched chain hydrocarbon group containing one carbon to carbon double bond and having 3 to 8 carbon atoms. Examples of alkenyl groups are propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, and the like. The term alkynyl refers to a straight or branched chain hydrocarbon radical containing unsaturation in the form of a single carbon to carbon triple bond and having from 3 to 7 carbon atoms such as 2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 4-methyl-2-pentynyl, 4,4-dimethyl-2-butynyl and the like. The term cycloalkenyl refers to a hydrocarbon group having one carbocyclic ring of 4 to 6 carbon atoms and one carbon-to-carbon double bond. Examples of cycloalkenyl groups are cyclobutenyl, cyclopentenyl, and cyclohexenyl.The term alkanol refers to a compound formed by a combination of an alkyl group and a hydroxy radical. Examples of alkanols are methanol, ethanol, 1- and 2-propanol, 1,2-dimethylethanol, hexanol, octanol and the like. The term alkanoic acid refers to a compound formed by combination of a carboxyl group with a hydrogen atom or alkyl group. Examples of alkanoic acids are formic acid, acetic acid, propanoic acid, 2,2-dimethylacetic acid, hexanoic acid, octanoic acid and the like. The term halogen refers to a member of the family consisting of fluorine, chlorine, bromine or iodine. The term alkanoyl refers to the radical formed by removal of the hydroxyl function from an alkanoic acid. Examples of alkanoyl groups are formyl, acetyl, propionyl, 2,2-dimethylacetyl, hexanoyl, octanoyl and the like. The term alkoxy refers to a monovalent substituent which consists of an alkyl group linked through an ether oxygen and having its free valence bond from the ether oxygen such as methoxy, ethoxy, propoxy, butoxy, 1,1-dimethylethoxy, pentoxy, 3-methylpentoxy, 2-ethylpentoxy, octoxy. The term lower as applied to any of the aforementioned groups shall mean a group having a carbon skeleton containing up to and including 6 carbon atoms.The compounds of the present invention which lack an element of symmetry exist as optical antipodes and as the racemic forms thereof. The optical antipodes may be prepared from the corresponding racemic forms by standard optical resolution techniques, involving, for example, the separation of diastereomeric salts of those instant compounds characterized by the presence of a basic amino group and an optically active acid, or by synthesis from optically active precursors.The present invention comprehends all optical isomers and racemic forms thereof of the compounds disclosed and claimed herein and the formulas of the compounds shown herein are intended to encompass all possible optical isomers of the compounds so depicted.The novel 5-amino-5,6,7,8-tetrahydroquinolines and related compounds of the present invention are synthesized by the processes illustrated in Reaction Schemes A and B. The following discussion focuses on the tetrahydroquinoline series. The processes shown in the Reaction Schemes may be applied to the synthesis of the related compounds.To gain entry into the primary amino-5,6,7,8-tetrahydroquinoline system 1a/1b, i.e., to prepare a tautomeric 2-hydroxy-5,6,7,8-tetrahydroquinoline 1a/5,6,7,8-tetrahydro-2(1H)-quinolinone 1b, characterized by the presence of a primary amino group (NH2), a 5-oxo-5,6,7,8-tetrahydro-2(1H)-quinolinone 2 (shown as one tautomer), the preparation of which is described in L. Mosti, et al., Journal of Heterocyclic Chemistry, 22, 1503 (1985), is O-alkylated to a 2-alkoxy-(or -arylalkoxy)-5-oxo-5,6,7,8-tetrahydroquinoline 3, which is converted to a 2-alkoxy- (or -aryloxy)-5-hydroxy-5,6,7,8-tetrahydroquinoline 4 and aminated to a 5-alkanoylamino-2-alkoxy-(or arylalkoxy)-5,6,7,8-tetrahyroquinoline 5. In turn, a 5-alkanoylamino-2-alkoxy-(or arylalkoxy)-5,6,7,8-tetrahydroquinoline 5 is cleaved to a 5-alkanoylamino-2-hydroxy-5,6,7,8-tetrahydroquinoline 6a/5-alkanoylamino-5,6,7,8-tetrahydro-2(1H)-quinolinone 6b and hydrolyzed to a primary aminoquinoline 1a/1b.The O-alkylation is conveniently performed by treating a 2(1H)-quinolinone 2 with a halide of formula 11R1Hal 11 wherein R1 is C1-C6-alkyl or phenyl-C1-C6-alkyl, wherein the phenyl may be substituted as indicated above and Hal is halogen in an aromatic solvent such as, for example, benzene, toluene, xylene, mesitylene, and the like, in the presence of a base such as sodium carbonate, potassium carbonate, or silver carbonate. Toluene and silver carbonate are preferred. The alkylation proceeds readily at about ambient temperature (about 25°C). Reduced temperatures (about 0° to about 25°C) and elevated temperatures (about 25° to about 50°C) may be employed, however.The conversion of a 5-oxoquinoline 3 to a 5-hydroxyquinoline 4 wherein R4 is C1-C6-alkyl or phenyl-C1-C6-alkyl wherein the phenyl may be substituted as indicated above, is effected by the Grignard technique. Thus, treatment of a 5-oxoquinoline 3 with a Grignard reagent of formula 12R4MgHal 12 wherein R4 is C1-C6-alkyl or phenyl-C1-C6-alkyl wherein the phenyl may be substituted as indicated above and Hal is as above in an aromatic solvent (e.g., benzene, toluene, xylene, or mesitylene) or an ethereal solvent (e.g., diethyl ether, 2-methoxyethyl ether, tetrahydrofuran, and dioxan) at a reaction temperature of from about 0° to about 50°C provides a 5-hydroxyquinoline 4 wherein R4 is as above. An aromatic solvent is preferred; toluene is most preferred. The preferred reaction temperature is about 25°C. A 5-hydroxyquinoline 4 wherein R4 is hydrogen may be prepared by reduction of a 5-oxoquinoline 4 with, for example, an alkali metal borohydride such as sodium borohydride or potassium borohydride in an alkanol such as ethanol or 2-propanol under conventional conditions.The amination of a 5-hydroxy-5,6,7,8-tetrahydroquinoline 4 to a 5-alkanoylamino-5,6,7,8-tetrahydroquinoline 5 is accomplished by treating a carbinol 4 with a nitrile of formula 13R7CN 13 wherein R7 is alkyl in the presence of a strong acid. Included among strong acids are mineral acids, e.g., hydrochloride acid, hydrobromic acid, and sulfuric acid, and organic acids, e.g., sulfonic acids such as benzenesulfonic acid and para-toluenesulfonic acid, and carboxylic acids such as trifluoroacetic acid. Mineral acids are preferred; sulfuric acid is most preferred. The amination is generally performed in excess reactant 13, the nitrile acting both as the aminating agent and solvent. The reaction temperature is not narrowly critical and proceeds at a convenient rate at about 25°C (ambient temperature). Reduced temperatures within the range from about 0° to about 25°C and elevated temperatures within the range from about 25° to about 50°C may be employed, depending upon the specific reactants. The cleavage of a 2-arylalkoxy-5,6,7,8-tetrahydroquinoline 5 wherein R1 is phenylmethyl or substituted phenylmethyl to a 2-hydroxy-5,6,7,8-tetrahydroquinoline 6a/5,6,7,8-tetrahydro-2(1H)-quinolinone 6b is carried out at about 25°C, under hydrogenolysis conditions in an alkanol such as methanol, ethanol, or 1- or 2-propanol, ethanol being preferred, in the presence of a noble metal catalyst, supported or unsupported, such as palladium-on-carbon, platinum, rhodium-on-alumina, or ruthenium, 10% palladium-on-carbon, being preferred, under hydrogen pressure within the range of about 1.7 to about 6.0 bar (25 to 85 psi), about 3.85 bar (55 psi) of hydrogen being preferred. The hydrolysis of a 5-alkanoylamino-5,6,7,8-tetrahydroquinoline 6a/5-alkanoylamino-5,6,7,8-tetrahydro-2(1H)-quinolinone 6b to the ultimate primary 5-aminoquinoline 1a/5-amino-2(1H)-quinolinone 1b may be achieved by conventional basic hydrolysis (e.g., sodium hydroxide or potassium hydroxide in methanol or ethanol) or acidic hydrolysis (e.g., hydrochloric acid or sulfuric acid in ethanol or 2-propanol) methods.Alternatively, a tautomeric primary amino-5,6,7,8-tetrahydroquinoline 1a/1b is prepared by condensing a 5,6,7,8-tetrahydroquinolinol 4 with an alkoxyamine of formula 14R8CH2ONH2 14 wherein R8 is pheny or phenyl substituted by one or more halogen, alkoxy, alkyl, or trifluoromethyl groups to yield a methoxyamino-5,6,7,8-tetrahydroquinoline 7 which is first cleaved to a 5,6,7,8-tetrahydroquinolinamine 8 and then to a tautomeric aminoquinoline 1a/1b. The condensation, an amination, is achieved by contacting a tetrahydroquinolinol 4 with a methoxyamine 14, in the presence of a strong mineral or organic acid in an aromatic solvent. Included among strong mineral acids are hydrohalic acids, for example, hydrochloric acid, hydrobromic acid, and the like, and sulfuric acid, nitric acid, and phosphoric acid. Included among strong organic acids are dihaloalkanoic acids, for example, dichloroacetic acid, trihaloalkanoic acids, for example, trifluoroacetic acid, and arylsulfonic acids, for example, phenylsulfonic acid, 4-tolylsulfonic acid, 2-naphthalenesulfonic acid, and the like. Included among aromatic solvents are benzene, toluene, xylene, and mesitylene. Trifluoroacetic acid and toluene are the preferred strong acid and aromatic solvent. The amination is generally conducted at about 25°C. Higher (from about 25°C to the boiling point of the reaction mixture) and lower (from about 0°C to about 25°C) may be employed. An amination temperature of about 25°C is preferred.The first cleavage, i.e., the cleavage of the methoxyamino function of 7 to provide the primary amino function of 8 is accomplished in an ethereal solvent such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 2-methoxyethyl ether, and diethyl ether by means of a borane complex, for example, borane tetrahydrofuran complex. Elevated cleavage temperatures of about 50°C to about the reflux temperature are preferred.The second cleavage reaction, namely, the hydrogenolyis of the benzyl ether function of 8 to afford a tautomeric aminoquinoline 1a/1b is effected by the processes described above for the cleavage of a 2-arylalkoxyquinoline 5 to a tautomer 6a/6b.A 1-alkyl-, 1-alkenyl- or 1-arylalkyl-5-amino-5,6,7,8-tetrahydro-2(1H)-quinolinone 10 is constructed by alkylating a tautomeric 5-aminoquinoline 1a/1b with a halide of formula 15.R9Hal 15 wherein R9 is C1-C6-alkyl, C3-C6-alkenyl, or phenyl-C1-C6-alkyl wherein the phenyl may be substituted as indicated above and Hal is as before. The alkylation is performed by first abstracting a proton from the tautomer 1a/1b with, for example, an alkali metal hydride in an aprotic dipolar solvent, and treating the anion, so formed, with a halide 15. Suitable alkali metal hydrides include lithium hydride, sodium hydride, and potassium hydride. Suitable aprotic dipolar solvents include dimethylacetamide, dimethylformamide, dimethylsulfoxide, and hexamethylphosphoramide. An alkylation employing a C1-C6-alkyl C3-C6-alkenyl-, or phenyl-C1-C6-alkyl- (wherein the phenyl may be substituted as indicated above) iodide, i.e., a halide 15 wherein Hal is iodo, and sodium hydride in dimethylformamide is preferred. The alkylation of tautomer 1a/1b to a 1-substituted derivative 10 proceeds readily at about 25°C. Elevated temperatures within the range of about 25° to about 50°C and reduced temperatures within the range of about 5° to about 25°C may be employed to effect the desired transformation.To gain entry into the secondary amino-5,6,7,8-tetrahydroquinoline system 17a/17b, i.e., to prepare a tautomeric 2-hydroxy-5,6,7,8-tetrahydroquinoline 17a/5,6,7,8-tetrahydro-2(1H)-quinolinone 17b, characterized by the presence of a secondary amino group (NHR2), an arylmethoxy-5,6,7,8-tetrahydroquinolinamine 7 is alkylated to an N-alkyl-, (-or N-arylalkyl)- N-arylmethoxy-5,6,7,8-tetrahydroquinolinamine 9, which is first cleaved at the amino function to give an N-alkyl-, (or N-arylalkyl)-5,6,7,8-tetrahydroquinolinamine 16 and then at the oxygen function to yield a tautomeric 5,6,7,8-tetrahydroquinoline 17a/17b. The alkylation of an alkoxyamine 7 to an N-alkylalkoxyamine 9 is carried out by forming the amino anion with an organometallic, for example, an alkylalkali metal such as methyllithium or an arylalkali metal such as phenylithium in an ethereal solvent such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, 2-methoxyethyl ether, or combinations thereof, and treating the anion, so formed, with a halide 15. The anion formation is preferably carried out at a reduced temperature of about -78°C, while the alkylation of the anion is preferably performed at about 25°C.The cleavages of the N-arylmethoxy group of 9 and the O-arylalkyl group of 16 are achieved by processes substantially similar to those utilized for the conversions of 7 to 8 and 5 to 6a/6b, described above.In an alternative approach to a secondary amino-5,6,7,8-tetrahydroquinolinone 21 and a tautomeric 5,6,7,8-tetrahydroquinolinone/5,6,7,8,-tetrahydroquinoline 25a/25b, a 1-alkyl-5-oxo-5,6,7,8-tetrahydro-2(1H)-quinolinone 19, prepared according to the procedures outlined in R. Albrecht and E. Schröder, Arch. Pharmaz., 308, 588 (1975), is condensed with a primary amine of formula 22.R2R3NH 22 wherein R2 is C1-C6-alkyl or phenyl-C1-C6-alkyl wherein the phenyl may be substituted as indicated above, and R3 is hydrogen to provide an intermediate imine of formula 20 wherein the bond (-----) is between the C-5 carbon atom and the amino nitrogen which is reduced to a secondary 5-alkyl- or 5-arylalkylamino-5,6,7,8-tetrahydro-2(1H)-quinolinone 21. The condensation, providing an intermediate imine 20, is conducted in the presence of a strong carboxylic or sulfonic acid such as, for example, trifluoroacetic acid, or benzenesulfonic or para-toluenesulfonic acid in an aromatic solvent such as, for example, benzene or toluene, optionally with azeotropic removal of the water formed in the reaction. While the amount of strong acid used to promote the condensation is not critical, catalytic amounts are preferred. para-Toluenesulfonic acid and toluene are the preferred strong acid and aromatic solvent. The intermediate imine 20 is also prepared by condensing a 1-alkyl-5-oxo-5,6,7,8-tetrahydro-2(1H)-quinolinone 19 with primary amine 22 in the presence of titanium tetra-isopropoxide in a suitable solvent, for example, acetonitrile at a non-critical condensation temperature of about ambient temperature.The reduction of the intermediate imine 20, generally conducted without purification, is effected by, for example, an alkali metal borohydride such as lithium borohydride, sodium borohydride, or potassium borohydride in an alkanol such as methanol, ethanol, or 1- or 2-propanol at about 0° to about 50°C. The preferred reduction conditions are sodium borohydride in ethanol at about 25°C.Similarly, a tautomeric 5,6,7,8-tetrahydroquinolinone/5,6,7,8-tetrahydroquinoline 25a/25b is prepared by condensing a 2-aryalkyl-5-oxo-5,6,7,8-tetrahydroquinoline 23 wherein R is phenyl-C1-C6-alkyl wherein the phenyl may be substituted as indicated above and R5 and m are as before with a primary amine 22 to provide an imine 24 which is reduced and cleaved to a tautomeric 5-aminoquinoline 25a/25b, the process steps being performed by procedures substantially the same as those, for example, described hereinbefore for the respective conversions of 19 to 20 and 16 to 17a/17b.By employing a secondary amine, i.e., an amine of formula 22 wherein neither R2 or R3 is hydrogen, and the procedures hereindescribed for the conversion of 19 to 21 and 23 to 25a/25b, one may construct a 5-(tertiary)-amino-5,6,7,8-tetrahydro-2(1H)-quinolinone 21 or a tautomeric 5-(tertiary)-amino-5,6,7,8-tetrahydroquinoline 25a/-quinolinone 25b.By employing a aryloxyamine, i.e., a aryloxyamine of formula 22 wherein R2 is hydrogen and R3 is phenyl-C1-C6-alkoxy wherein the phenyl may be substituted as indicated above and the processes for the conversion of 23 to 25a/25b, one can prepare an N-arylalkoxy-5,6,7,8-tetrahydroquinoline 27 wherein R3 is arylalkyl via the intermediate oxime 26, which may be cleaved to a tautomeric primary amino-5,6,7,8-tetrahydroquinoline 25a/tetrahydroquinolinone 25b. In this approach, an O-arylalkylhydroxylamine is used in the form of its hydrohalide such as a hydrochloride in an alkanol such as ethanol in the presence of a weak base such as an alkali metal acetate, e.g., sodium acetate, at an elevated temperature of about the reflux temperature of the reaction medium, and the reduction is performed by an alkali metal cyanoborohydride such as sodium cyanoborohydride in an alkanoic acid such as acetic acid at a temperature of about 25°C. The cleavage of an O,N-diarylalkoxy-5,6,7,8-tetrahydroquinoline 27 to a tautomeric quinoline/quinolinone 25a/25b may be accomplished by following the directions for the cleavage of 7 to 8 and 8 to 1a/1b.Still another approach to 5-amino-5,6,7,8-tetrahydroquinolines and related compounds involves acylation of a N,2-bis(arylalkoxy)-5,6,7,8-tetrahydro-5-quinolinamine 27 to an amide 28 which may be converted, for example, to a tautomeric quinolinol 1a/quinolinone 1b by processes hereinbeforedescribed. The acylation is accomplished by treating a 5-quinolinamine 27 with an alkanoic acid anhydride of formula 29(R7CO)2O 29 in a halocarbon solvent such as dichloromethane or trichloroethane, dichloromethane being preferred, in the presence of a promoter such as a N,N-dialkylaminopyridine, for example, N,N-dimethylpyridine at a reaction temperature of from about 0° to 50°C, a reaction temperature of about 25°C being preferred.In addition to the procedures outlined in R. Albrecht and E. Schröder, Arch. Pharmaz., 308, 588 (1975) for the transformation of an N-unsubstituted quinolone 18 to a N-substituted, i.e., an N-alkyl, -alkenyl, or -phenylmethylquinolone 19, the conversion of 18 to 19 is performed by treating a quinolone 18 with a halide of formula 30RHal 30 wherein R is C1-C6-alkyl, C3-C6-alkenyl, or phenylmethyl in an aprotic dipolar solvent such as dimethylacetamide, dimethylformamide, hexamethylphosphoramide, or dimethylsulfoxide in the presence of an alkali metal hydride such as lithium hydride, potassium hydride or sodium hydride at a condensation temperture of about 0°C to about 50°C. The preferred reaction conditions are lithium hydride in dimethylformamide at a temperature of about 25°C.Substituents on the 5-amino-5,6,7,8-tetrahydroquinolines of the present invention may be modified by conventional methods. For example, an alkenyl group of aminoquinolinone 21 wherein R is C3-C6-alkenyl is reduced by hydrogen in the presence of palladium-on-carbon in ethanol at atmospheric pressure to an aminoquinolinone 21 wherein R is C3-C6-alkyl.The related compounds of the present invention may be prepared from the appropriate precursors by methods essentially the same as those hereinbeforedescribed.The 5-amino-5,6,7,8-tetrahydroquinolines and related compounds of the present invention are useful as agents for the relief of memory dysfunction, particularly dysfunctions associated with decreased cholinergic activity such as those found in Alzheimer's disease. Relief of memory dysfunction activity of the instant compounds is demonstrated in the dark avoidance assay, an assay for the determination of the reversal of the effects of scopolamine induced memory deficits associated with decreased levels of acetylcholine in the brain. In this assay, three groups of 15 male CFW mice were used, a vehicle/vehicle control group, a scopolamine/vehicle group, and a scopolamine/drug group. Thirty minutes prior to training, the vehicle/vehicle control group received normal saline subcutaneously, and the scopolamine/vehicle and scopolamine/drug groups received scopolamine subcutaneously (3.0 mg/kg, administered as scopolamine hydrobromide). Five minutes prior to training, the vehicle/vehicle control and scopolamine/vehicle groups received distilled water and the scopolamine/drug group received the test compound in distilled water.The training/testing apparatus consisted of a plexiglass box approximately 48 cm long, 30 cm high and tapering from 26 cm wide at the top to 3 cm wide at the bottom. The interior of the box was divided equally by a vertical barrier into a light compartment (illuminated by 25-watt reflector lamp suspended 30 cm from the floor) and a dark compartment (covered). There was a hole at the bottom of the barrier 2.5 cm wide and 6 cm tall and a trap door which could be dropped to prevent an animal from passing between the two compartments. A Coulbourn Instruments small animal shocker was attached to two metal plates which ran the entire length of the apparatus, and a photocell was placed in the dark compartment 7.5 cm from the vertical barrier and 2 cm off the floor. The behavioral session was controlled by PDP 11/34 minicomputer.At the end of the pretreatment interval, an animal was placed in the light chamber directly under the light fixture, facing away from the door to the dark chamber. The apparatus was then covered and the system activated. If the mouse passed through the barrier to the dark compartment and broke the photocell beam within 180 seconds, the trap door dropped to block escape to the light compartment and an electric shock was administered at an intensity of 0.4 milliamps for three seconds. The animal was then immediately removed from the dark compartment and placed in its home cage. If the animal failed to break the photocell beam within 180 seconds, it was discarded. The latency in seconds for each mouse was recorded.Twenty-four hours later, the animals were again tested in the same apparatus except that no injections were made and the mice did not receive a shock. The test day latency in seconds for each animal was recorded and the animals were then discarded.The high degree of variability (due to season of the year, housing conditions, and handling) found in one trial passive avoidance paradigm is well known. To control for this fact, individual cutoff (CO) values were determined for each test, compensating for interest variability. Additionally, it was found that 5 to 7% of the mice in the scopolamine/vehicle control groups were insensitive to scopolamine at 3 mg/kg, sc. Thus, the CO value was defined as the second highest latency time in the control group to more accurately reflect the 1/15 expected control responders in each test group. Experiments with a variety of standards repeated under a number of environmental conditions led to the development of the following empirical criteria: for a valid test, the CO value had to be less than 120 sec and the vehicle/vehicle control group had to have at least 5/15 animals with latencies greater than CO. For a compound to be considered active the scopolamine/compound group had to have at least 3/15 mice with latencies greater than CO.The results of the dark avoidance test are expressed as the number of animals per group (%) in which this scopolamine induced memory deficit is blocked as measured by an increase in the latency period. Relief of memory dysfunction activity for representative compounds of the present invention is presented in the Table. CompoundDose (mg/kg, sc)Percent of Animals with Scopolamine Induced Memory Deficit ReversalN-(1,2,5,6,7,8-hexahydro-5-methyl-2-oxo-5-quinolinyl)acetamide0.16201-methyl-5-[(2-phenylethyl)amino]-5,6,7,8-tetrahydro-2(1H)-quinolinone1.033N-(phenylmethoxy)-N-[2-(phenylmethoxy)-5-5,6,7,8-tetrahydroquinolinyl]acetamide1.0205-[[2-(4-methoxyphenyl)ethyl]amino]-1-methyl-5,6,7,8-tetrahydro-2(1H)-quinolinone0.3275-[[2-(3,4-dichlorophenyl)-ethyl]amino]-1-methyl-5,6,7,8-tetrahydro-2(1H)-quinolinone1.021physostigmine0.3120Relief of memory dysfunction activity is also demonstrated in the in vitro inhibition of actylcholinesterase activity, an assay for the determination of the ability of a drug to inhibit the inactivation of acetylcholine, a neurotransmitter implicated in the etiology of memory dysfunction and Alzheimer's dementia. In this assay, a modification of a test described by G. L. Ellman, et al., Biochem. Pharmacol., 7, 88 (1961), the following reagents are prepared and employed:1. 0.05M Phosphate Buffer (pH 7.2)A solution of monobasic sodium phosphate monhydrate (6.85 g) in distilled water (100 ml) is added to a solution of dibasic sodium phosphate heptahydrate (13.4 g) and distilled water (100 ml) until a pH of 7.2 was attained. The solution was diluted 1 to 10 with distilled water.2. Substrate In BufferThe 0.05M Phosphate Buffer (pH 7.2) was added to acetylthiocholine (198 mg) to a total volume of 100 ml, i.e., a quantity sufficient (gs) to 100 ml.3. 5,5-Dithiobisnitrobenzoic Acid in BufferThe 0.05M Phosphate Buffer (pH 7.2) was added to 5,5-dithiobisnitrobenzoic acid to a total volume of 100 ml, i.e., a quantity sufficient (gs) to 100 ml.4. Stock Solution of DrugA 2 millimolar stock solution of the test drug is prepared in a quantity sufficient of a suitable solvent, either acetic acid or dimethyl sulfoxide to volume with 5,5-Dithiobisnitrobenzene Acid in Buffer. Stock Solution of Drug is serially diluted (1:10) so that the final cuvette concentration is 10-4 molar.Male Wistar rats are decapitated, brains rapdily removed, corpora strita dissected free, weighed and homogenized in 19 volumes (approximately 7 mg potein/ml) of 0.05M phosphate Buffer (pH 7.2) using a Potter-Elvehjem homogenizer. A 25 µl aliquot of this suspension is added to 1 ml of the vehicle or various concentrations of the test drug and preincubated for 10 minutes at 37°C. Enzyme activity is measured with a Beckman DU-50 spectrophotometer with the following software and instrument settings: 1. Kinetics Soft-Pac™ Module #598273;2. Program #6 Kindata; 3. Source - Vis;4. Wavelength - 412 nm;5. Sipper - none;6. Cuvettes - 2 ml cuvettes using auto 6-sampler;7. Blank - 1 for each substrate concentration;8. Interval time - 15 seconds (15 or 30 seconds for kinetics);9. Total time - 5 minutes (5 or 10 minutes for kinetics);10. Plot - yes;11. Span - autoscale;12. Slope - increasing;13. Results - yes (gives slope); and14. Factor - 1.Reagents are added to the blank and sample cuvettes as follows: 1. Blank:0.8 ml 5,5-Dithiobisnitrobenzoic Acid 0.8 ml Substrate in Buffer2. Control:0.8 ml 5,5-Dithiobisnitrobenzoic Acid/Enzyme 0.8 ml Substrate in Buffer3. Drug:0.8 ml 5,5-Dithiobisnitrobenzoic Acid/Drug/Enzyme 0.8 ml Substrate in BufferBlank values are determined for each run to control for non-enzymatic hydrolysis of substrate and these values are automatically subtracted by the Kindata program available on kinetics soft-pac module. This program also calculates the rate of absorbance change for each cuvette.For IC50DeterminationsSubstrate concentration is 10 millimolar diluted 1:2 in assay yielding final concentration of 5 millimolar. 5,5-Dithiobisnitrobenzoic Acid concentration is 0.5 millimolar yielding 0.25 millimolar final concentration. % Inhibition = Slope Control - Slope drugSlope Control x 100 IC50 values are calculated from log-probit analysis CompoundsInhibition of Acetylcholinesterase Activity IC50 (µM)5-[[2-(4-chlorophenyl)ethyl)amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinone6.65,6,7,8-tetrahydo-5-[[2-(4-methoxyphenyl)ethyl]amino]-1-methyl-2(1H)-quinolinone9.65-[[2-(3,4-dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinone2.95,6,7,8-tetrahydro-5-[(2-phenylethyl)amino]-1-propyl-2(1H)-quinolinone fumarate3.1Physostigmine0.13Memory deficit and scopolamine induced memory deficit reversal is achieved when the present 5-amino-5,6,7,8-tetrahydroquinolines and related compounds are administered to a subject requiring such treatment as an effective oral, parenteral or intravenous dose of from 0.01 to 100 mg/kg of body weight per day. A particularly effective amount is about 25 mg/kg of body weight per day. It is to be understood, however, that for any particular subject, specific dosage regimens should be adjusted according to the individual need and the professional judgment of the person administering or supervising the administration of the aforesaid compound. It is to be further understood that the dosages set forth herein are exemplary only and that they do not, to any extent, limit the scope or practice of the invention. Included among the compounds of the present inventions are: a. 5-[[2-(4-hydroxyphenyl)ethyl]amino-1-methyl-5,6,7,8-tetrahydro-2(1H)-quinolinone;b. N-[2-methoxy-5,6,7,8-tetrahydro-5-quinolinyl]-N-methoxypropionamide;c. 1-(2-phenylethyl)-5-(1-propoxyamino)-5,6,7,8-tetrahydro-2(1H)-quinolinone;d. 1,5-dimethyl-5-(1-piperidinyl)-5,6,7,8-tetrahydro-2(1H)-quinolinone;e. 2-hydroxy-5-methyl-5-(1-piperazinyl)-5,6,7,8-tetrahydroquinoline;f. 1,5-dimethyl-5-(4-morpholinyl)-5,6,7,8-tetrahydro-2(1H)-quinolinone; andg. 2-hydroxy-5-methyl-5-(4-thiomorpholinyl-5,6,7,8-tetrahydroquinoline.h. 1,5-dimethyl-5-[3-(propynyl)amino]-5,6,7,8-tetrahydro-2(1H)-quinolinone.i. 5-amino-1,5,6,7-tetrahydro-1,5-dimethyl-2H-1-pyridin-2-one.Effective amounts of the compounds of the invention may be administered to a subject by any one of various methods, for example, orally as in capsules or tablets, parenterally in the form of sterile solutions or suspensions, and in some cases intravenously in the form of sterile solutions. The free base final products, while effective themselves, may be formulated and administered in the form of their pharmaceutically acceptable addition salts for purposes of stability, convenience of crystallization, increased solubility and the like.Preferred pharmaceutically acceptable addition salts include salts of mineral acids, for example, hydrochloric acid, sulfuric acid, nitric acid and the like, salts of monobasic carboxylic acids such as, for example, acetic acid, propionic acid and the like, salts of dibasic carboxylic acids such as, for example, maleic acid, fumaric acid, oxalic acid and the like, and salts of tribasic carboxylic acids such as, for example, carboxysuccinic acid, citric acid and the like.The active compounds of the present invention may be administered orally, for example, with an inert diluent or with an edible carrier. They may be enclosed in gelatin capsules or compressed into tablets. For the purpose of oral therapeutic administration, the aforesaid compounds may be incorporated with excipients and used in the form of tablets, troches, capsules, elixirs, suspensions, syrups, wafers, chewing gums and the like. These preparations should contain at least 0.5% of active compound, but may be varied depending upon the particular form and may conveniently be between 4% to about 75% of the weight of the unit. The amount of present compound in such composition is such that a suitable dosage will be obtained. Preferred compositions and preparations according to the present invention are prepared so that an oral dosage unit form contains between 1.0-300 mgs of active compound.The tablets, pills, capsules, troches and the like may also contain the following ingredients: a binder such as microcrystalline cellulose, gum tragacanth or gelatin; an excipient such as starch or lactose, a disintegrating agent such as alginic acid, Primogel, corn starch and the like; a lubricant such as magnesium stearate or Sterotes; a glidant such as colloidal silicon dioxide; and a sweetening agent such as sucrose or saccharin or a flavoring agent such as peppermint, methyl salicylate, or orange flavoring may be added. When the dosage unit is a capsule, it may contain, in addition to materials of the above type, a liquid carrier such as a fatty oil. Other dosage unit forms may contain other various materials which modify the physical form of the dosage unit, for example, as coatings. Thus tablets or pills may be coated with sugar, shellac, or other enteric coating agents. A syrup may contain, in addition to the active compounds, sucrose as a sweetening agent and certain preservatives, dyes and colorings and flavors. Materials used in preparing these various compositions should be pharmaceutically pure and non-toxic in the amounts used.For the purposes of parenteral therapeutic administration, the active compounds of the invention may be incorporated into a solution or suspension. These preparations should contain at least 0.1% of the aforesaid compound, but may be varied between 0.5 and about 50% of the weight thereof. The amount of active compound in such compositions is such that a suitable dosage will be obtained. Preferred compositions and preparations according to the present invention are prepared so that a parenteral dosage unit contains between 0.5 to 100 mgs of the active compound.The solutions or suspensions may also include the following components: a sterile diluent such as water for injection, saline solution, fixed oils, polyethylene glycols, glycerine, propylene glycol or other synthetic solvents; antibacterial agents such as benzyl alcohol or methyl parabens; antioxidants such as ascorbic acid or sodium bisulfite; chelating agents such as ethylenediaminetetraacetic acid; buffers such as acetates, citrates or phosphates and agents for the adjustment of tonicity such as sodium chloride or dextrose. The parenteral preparation can be enclosed in ampoules, disposable syringes or multiple dose vials made of glass or plastic.The following Examples are for illustrative purposes only and are not to be construed as limiting the invention.EXAMPLE 15,6,7,8-Tetrahydro-5-oxo-2-(phenylmethoxy)quinolineA suspension of 5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (33.0 g), silver carbonate (35.0 g), benzyl bromide (44.4 g), and toluene (400 ml) was stirred at room temperature for 72 hrs. The mixture was filtered and the filtrate was concentrated. Trituration of the residue with petroleum ether gave 45.6 g (83%) of product.EXAMPLE 25,6,7,8-Tetrahydro-5-hydroxy-5-methyl-2-(phenylmethoxy)quinolineMethylmagnesium bromide (3.0 M in diethyl ether, 47 ml) was added dropwise to a solution of 5,6,7,8-tetrahydro-5-oxo-2-(phenylmethoxy)quinoline (29.6 g) and toluene (1 ℓ) at 0°C. The reaction mixture was allowed to warm to room temperature, with stirring. The reaction mixture was then quenched with saturated ammonium chloride solution, the layers were separated, and the aqueous phase was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to provide 31.7 g (92.0%) of product.EXAMPLE 35,6,7,8-Tetrahydro-5-methyl-2-(phenylmethoxy)-5-quinolinamine hemifumarateTrifluoroacetic acid (17.4 g) was added in one portion to a solution of 5,6,7,8-tetrahydro-5-methyl-2-(phenylmethoxy)-quinolin-5-ol (41 g), phenylmethoxyamine (47 g), and toluene (770 ml) at room temperature. The solution was stirred at room temperature for 24 hrs, and then quenched with concentrated ammonium hydroxide solution. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over potassium carbonate, filtered, and the filtrate was concentrated. Purification by high performance liquid chromatography (silica gel, elution with ethyl acetate-hexanes) gave 44.2 g (77%) of 5,6,7,8-tetrahydro-5-methyl-N,2-bis(phenylmethoxy)-5-quinolinamine.A portion of the 5,6,7,8-tetrahydro-5-methyl-N,2-bis(phenylmethoxy)quinolinamine (30.3 g) in tetrahydrofuran (120 ml) was treated dropwise with borane-tetrahydrofuran complex (1M in tetrahydrofuran, 243 ml) at 0°C. The solution was heated under reflux for 2 hrs, cooled to 0°C, and water (30 ml) was added. The mixture was concentrated in vacuo, 20% potassium hydroxide solution (50 ml) was added, and the mixture was heated under reflux for 1.5 hrs. The mixture was cooled, acidified with 6N hydrochloric acid and washed with diethyl ether. The aqueous phase was basified with potassium hydroxide solution and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated.A 2.9 g-portion of the residue (19.6 g) was dissolved in ethyl acetate, and the solution was treated with an equivalent amount of fumaric acid. The precipitate was collected; yield 2.68 g (68%) of product, mp 189-190°C. ANALYSIS:Calculated for C19H22N2O369.92%C6.79%H8.58%NFound69.59%C6.73%H8.55%NEXAMPLE 45,6,7,8-Tetrahydro-5-amino-5-methyl-2(1H)-quinolinone hydrochloride5,6,7,8-Tetrahydro-5-methyl-2-(phenylmethoxy)-5-quinolinamine dihydrochloride (9.5 g) and 10% palladium-on-carbon (730 mg) in absolute ethanol (500 ml) were shaken on a Parr hydrogenation apparatus, starting at 55 psi of hydrogen, until hydrogen uptake ceased. The catalyst was removed by filtration, and the filtrate was neutralized with 4-polyvinylpyridine and concentrated. The residue was suspended in hot methanol and the solid was collected. The solid was combined with the material that crystallized from the methanol to afford 3.36 g (56%) of product, mp 214-216°C (dec). ANALYSIS:Calculated for C10H15N2O55.94%C7.04%H13.05%NFound55.71%C7.02%H12.91%NEXAMPLE 55,6,7,8-Tetrahydro-5-amino-1,5-dimethyl-2(1H)-quinolinoneA mixture of sodium hydride (50% in oil, 2.9 g), 5-amino-5,6,7,8-tetrahydro-5-methyl-2(1H)-quinolinone hydrochloride (5.43 g), and dimethylformamide (370 ml) was stirred at room temperature for 1.5 hrs. Methyl iodide (3.97 g) was added, and the mixture was allow to stand at room temperature for 20 hrs. The reaction mixture was concentrated in vacuo, and the residue was washed with dichloromethane. The washings were concentrated, the residue was dissolved in a mixture of ethyl acetate and methanol and treated with 0.5 equivalents of fumaric acid. The precipitate (2.65 g) was combined with a 1.9 g-sample obtained in another experiment, and the combined material was treated with 5% sodium hydroxide solution and extracted with dichloromethane. The extract was concentrated. Recrystallization of the residue from ethyl acetate gave 2.1 g (23%) of product, mp 166-167.5C. ANALYSIS:Calculated for C11H16N2O68.72%C8.39%H14.57%NFound68.68%C8.37%H14.52%NEXAMPLE 6N,2-Bis(phenylmethoxy)-5,6,7,8-tetrahydro-N,5-dimethyl-5-quinolinamineMethyllithium (1.4 M in diethyl ether, 37.7 ml) was added dropwise over 20 min to a solution of N,2-bis(phenylmethoxy)-5,6,7,8-tetrahydro-5-methyl--5-quinolinamine (18.1 g) and tetrahydrofuran (20 ml) at -78°C. The mixture was allowed to warm to room temperature over 2 hrs and was stirred at room temperature for an additional 1 hr. The solution was quenched with saturated ammonium chloride solution and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous potassium carbonate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, elution with ethyl acetate-hexanes) to provide 12.3 g (65%) of product.EXAMPLE 75,6,7,8-Tetrahydro-N,5-dimethyl-2-(phenylmethoxy)-5-quinolinamine5,6,7,8-Tetrahydro-N,5-dimethyl-N,2-bis(phenylmethoxy)-5-quinolinamine (12.3 g) in tetrahydrofuran (160 ml) at 0°C was treated dropwise with borane-tetrahydrofuran complex (1M in tetrahydrofuran, 63.4 ml). The solution was heated under reflux for 3 hrs, cooled to 0°C, and water (30 ml) was added. The reaction mixture was concentrated in vacuo, 20% potassium hydroxide solution (60 ml) was added, and the mixture was heated at reflux for 2 hrs. The mixture was cooled, acidified with conc hydrochloric acid, and washed with diethyl ether. The aqueous phase was basified with 20% potassium hydroxide solution and extracted with dichloromethane. The combined organic layers were washed with brine, dried over potassium carbonate, filtered, and the filtrate was concentrated to afford 6.3 g (92%) of product.EXAMPLE 85,6,7,8-Tetrahydro-5-methyl-5-(methylamino)-2(1H)-quinolinone hydrochloride5,6,7,8-Tetrahydro-N,5-dimethyl-2-(phenylmethoxy)-5-quinolinamine (6.3 g) in ethanol (500 ml) was acidified to ca pH2 with a solution of hydrochloric acid in 2-propanol. 10% Palladium-on-carbon (315 mg) was added and the mixture was shaken on Parr hydrogenation apparatus, starting at 55 psi of hydrogen, until hydrogen uptake ceased. The catalyst was collected and the filtrate was neutralized with 4-polyvinylpyridine. The solution was concentrated in vacuo to a volume of about 75 ml and diethyl ether was added. The precipitate was collected and recrystallized first from methanol and then from water/2-propanol to afford 1.3 g (25%) of product, mp 190-195°C (dec). ANALYSIS:Calculated for C11H17ClN2O57.77%C7.49%H12.25%NFound57.36%C7.46%H12.11%NEXAMPLE 95,6,7,8-Tetrahydro-5-hydroxy-2-(phenylmethoxy)-5-(phenylmethyl)quinolineBenzylmagnesium chloride (1.0 M in diethyl ether, 175 ml) was added dropwise to a solution of 5,6,7,8-tetrahydro-5-oxo-2-(phenylmethoxy)quinolinone (37.0 g) and 1.4 ℓ of toluene at 0°C. The mixture was allowed to warm to room temperature and saturated ammonium chloride solution was added. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to provide 50.0 g of product.EXAMPLE 105,6,7,8-Tetrahydro-2-(phenylmethoxy)-5-(phenylmethyl)-5-quinolinamineTrifluoroacetic acid (16.6 g) was added in one portion to a solution of 5,6,7,8-tetrahydro-5-hydroxy-2-(phenylmethoxy)-5-(phenylmethyl)quinoline (50 g), phenylmethoxyamine (44.8 g), and toluene (600 ml) at room temperature. The solution was stirred at room temperature for 19 hrs, and the reaction mixture was quenched with conc ammonium hydroxide solution. The layers were separated and the aqueous phase was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over potassium carbonate, filtered, and the filtrate was concentrated. Purification by high performance liquid chromatography (silica gel, elution with ethyl acetate-hexanes) gave 40.0 g (61%) of 5,6,7,8-tetrahydro-N,2-bis(phenylmethoxy)-5-(phenylmethyl)-5-quinolinamine.5,6,7,8-Tetrahydro-N,2-bis(phenylmethoxy)-5-(phenylmethyl)-5-quinolinamine (40.0 g) in tetrahydrofuran (90 ml) was treated dropwise with borane-tetrahydrofuran complex (1M in tetrahydrofuran, 267 ml) at 0°C. The solution was heated under reflux for 3 hrs, cooled to 0°C and water (30 ml) was added. The reaction mixture was concentrated in vacuo, 20% potassium hydroxide solution (60 ml) was added, and the mixture was heated under reflux for 8 hours. The mixture was cooled, acidified with conc hydrochloric acid, and washed with diethyl ether. The aqueous phase was basified with 20% potassium hydroxide solution and extracted with dichloromethane. The combined organic layers were washed with brine, dried over potassium carbonate, filtered, and the filtrate was concentrated to afford 19.1 g (37.0%) of product.EXAMPLE 115-Amino-5,6,7,8-tetrahydro-5-(phenylmethyl)-2(1H)-quinolinone hydrochlorideA mixture of 5,6,7,8-tetrahydro-5-(phenylmethyl)-2-(phenylmethoxy)-5-quinolinamine (19.1 g) and 10% palladium-on-carbon (1.5 g) in ethanol (1 ℓ) was acidified to about pH 2-3 with 2-propanol/hydrochloric acid solution. The mixture was shaken on Parr hydrogenation apparatus, starting at 55 psi of hydrogen, until hydrogen uptake ceased. The catalyst was removed by filtration, the filtrate was neutralized with 4-polyvinylpyridine and concentrated. The residue was triturated with a mixture of methanol and ethyl acetate. The precipitate was collected and recrystallized form water/methanol/ethyl acetate to afford 4.6 g (28%) of product, mp 235-238°C (dec), in two crops. ANALYSIS:Calculated for C16H19ClN2O66.09%C6.59%H9.63%NFound65.83%C6.68%H9.56%NEXAMPLE 12N-[5,6,7,8-Tetrahydro-5-methyl-2-(phenylmethoxy)-5-quinolinyl]acetamideConc sulfuric acid (70 ml) was added dropwise over 45 mins to a solution of 5,6,7,8-tetrahydro-5-hydroxy-5-methyl-2-(phenylmethoxy)quinoline (14.0 g) and acetonitrile (200 ml) at 0°C. The solution was stirred at room temperature for 18 hrs, poured over ice, and basified to pH 8 with 50% sodium hydroxide solution. The aqueous phase was extracted with ethyl acetate, and the combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by column chromatography (silica gel, elution with ethyl acetate). The appropriate fractions were collected and evaporated. Recrystallization (twice) of the residue from ethyl acetate/hexanes gave 2.60 g (16%) of product, mp 153-154°C. ANALYSIS:Calculated for C19H22N2O273.52%C7.14%H9.02%NFound73.88%C7.12%H9.02%NEXAMPLE 13N-(1,2,5,6,7,8-Hexahydro-5-methyl-2-oxo-5-quinolinyl)acetamide5,6,7,8-Tetrahydro-N-[5-methyl-2-(phenylmethoxy)-5-quinolinyl]acetamide hydrochloride (4.5 g) and 10% palladium-on-carbon (225 mg) in absolute ethanol (250 ml) were shaken on a Parr hydrogenation apparatus at an initial pressure of 55 psi of hydrogen, until hydrogen uptake ceased. The catalyst was removed by filtration, the filtrate was neutralized with 4-polyvinylpyridine, and the mixture was concentrated. The residue was combined with a 1.79 g sample obtained in another experiment. Recrystallization from absolute ethanol gave 2.81 g (60%) of product, mp 235-237°C (dec). ANALYSIS:Calculated for C12H16N2O265.43%C7.32%H12.72%NFound65.02%C7.27%H12.54%NEXAMPLE 145,6,7,8-Tetrahydro-5-[(2-phenylethyl)amino]-2(1H)-quinolinone hydrochlorideA mixture of phenethylamine (5.0 g), 5,6,7,8-tetrahydro-2-(phenylmethoxy)-5-oxoquinoline (10.0 g), and a catalytic amount of para-toluenesulfonic acid (206 mg) was heated under reflux in toluene (200 ml) with azeotropic removal of water for 36 hrs. The solution was cooled and washed with water. The aqueous phase was extracted with dichloromethane, and the combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Sodium borohydride (1.4 g) was added to a solution of the residue and ethyl alcohol (125 ml) and the mixture was stirred at room temperature for 3 hrs. The reaction mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to afford 12.5 g (92%) of 5,6,7,8-tetrahydro-5-(2-phenethylamino)-2-(phenylmethoxy)quinoline.5,6,7,8-Tetrahydro-5-(2-phenethylamino)-2-(phenylmethoxy)quinoline (12.5 g) was converted into its hydrochloride. The hydrochloride and 10% palladium-on-carbon (830 mg) in methanol (1 ℓ) were shaken on a Parr hydrogenation apparatus, starting at 55 psi of hydrogen, until hydrogen uptake ceased. The catalyst was removed by filtration, the filtrate was neutralized with 4-polyvinylpyridine, and concentrated. Recrystallization of the residue from methanol/ethyl acetate afforded 2.68 g of product, mp 200-202°C (dec). An additional 2.2 g of product was obtained from the other liquors; overall yield 42%. ANALYSIS:Calculated for C17H21ClN2O66.99%C6.94%H9.19%NFound66.85%C6.96%H9.12%NEXAMPLE 155,6,7,8-Tetrahydro-1-methyl-5-[(2-phenylethyl)amino]-2(1H)-quinolinone dihydrochloride monohydrateA mixture of phenethylamine (6.0 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (8.0 g) and a catalytic amount of para-toluenesulfonic acid was heated in toluene (90 ml) under reflux for 18 hrs, with azeotropic removal of water. The solution was cooled and washed with water. The aqueous phase was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was washed with hexanes and the solvent was decanted. Sodium borohydride (0.82 g) was added to a solution of the residue in ethyl alcohol (160 ml) and the mixture was stirred at room temperature for 0.5 hr. The reaction mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was dissolved in methanol and treated with ethereal hydrogen chloride. The mixture was concentrated in vacuo and the residue was dissolved in ethanol. Ethyl acetate was added, the precipitate was collected, and the precipitate was recrystallized twice from ethanol-ethyl acetate to afford 4.0 (24%) of product, mp 163-166°C (softens at 142°C). ANALYSIS:Calculated for C18H26Cl2N2O257.91%C7.02%H7.50%NFound57.97%C6.93%H7.47%NEXAMPLE 165,6,7,8-Tetrahydro-N,2-bis(phenylmethoxy)-5-quinolinamine5,6,7,8-Tetrahydro-5-oxo-2-(phenylmethoxy)quinoline (20 g), O-benzylhydroxylamine hydrochloride (19 g), and sodium acetate (9.8 g) in a 1/1-mixture of ethanol and water (200 ml) were heated under reflux for 3 hrs. The solvent was decanted and the residue was purified by high performance liquid chromatography (silica gel, elution with 5% ethyl acetate/hexanes). The appropriate fractions were collected and evaporated to give 21.5 (76%) of 5,6,7,8-tetrahydro-5-oxo-2-(phenylmethoxy)quinoline oxime benzyl ether.5,6,7,8-Tetrahydro-5-oxo-2-(phenylmethoxy)quinoline oxime benzyl ether (20.3 g) in acetic acid (280 ml) was treated with sodium cyanoborohydride (14.2 g) at room temperature. After 16 hrs, the mixture was cooled to 0°C and acidified with 6N hydrochloric acid. The reaction mixture was concentrated in vacuo. The residue was dissolved in water, basified with potassium hydroxide solution, and the mixture was extracted with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, elution with 20% ethyl acetate/hexanes). The appropriate fractions were collected and evaporated to give 12.0 g (60%) of product.EXAMPLE 17N-(Phenylmethoxy)-N-[5,6,7,8-tetrahydro-2-(phenylmethoxy)-5-quinolinyl]acetamide hydrochlorideAcetic anhydride (3.77 g) was added to a solution of N,N-dimethylaminopyridine (0.2 g), N,2-bis(phenylmethoxy)-5,6,7,8-tetrahydro-5-quinolinamine (12.1 g) and dichloromethane (170 ml) at room temperature. The mixture was stirred at room temperature for 48 hrs, diluted with dichloromethane, and extracted with saturated sodium bicarbonate solution. The combined extracts were washed with water, brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was dissolved in methanol and acidified with 2-propanol/hydrochloric acid solution. The mixture was evaporated and the residue was recrystallized from ethanol/ethyl acetate to give 7.64 g (52%) of product, mp 125-126°C. ANALYSIS:Calculated for C25H27ClN2O368.41%C6.20%H6.38%NFound68.33%C6.20%H6.37%NEXAMPLE 185,6,7,8-Tetrahydro-5-[(2-phenylethyl)amino]-1-(2-propenyl)-2(1H)-quinolinoneA mixture of 5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (20.0 g), lithium hydride (1.57 g), and dimethylformamide (800 ml) was stirred for 3 hrs at 25°C, under nitrogen. 3-Bromopropene (15.5 g) was added and the mixture was stirred for an additional eighteen hrs. The reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was triturated with petroleum ether to afford 15.7 g (63%) of 5,6,7,8-tetrahydro-5-oxo-1-(2-propenyl)-2(1H)-quinolinone.A mixture of phenethylamine (6.1 g), 5,6,7,8-tetrahydro-5-oxo-1-(2-propenyl)-2(1H)-quinolinone (10.0 g), and a catalytic amount of para-toluenesulfonic acid was heated in refluxing toluene (150 ml), with azeotropic removal of water, for 18 hrs. The solution was cooled and washed with water. The aqueous phase was extracted with dichloromethane, and the combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Sodium borohydride (1.8 g) was added to the residue in ethyl alcohol (150 ml) and the resulting mixture was stirred at room temperature for 0.5 hr. The mixture was concentrated in vacuo, and the residue was quenched with water. The mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with methanol/ethyl acetate) to afford 13.6 g (89%) of product. Recrystallization from diethyl ether/petroleum ether provided the analytical sample, mp 60-62°C. ANALYSIS:Calculated for C20H24N2O77.89%C7.84%H9.08%N Found78.06%C7.65%H9.10%NEXAMPLE 195-[[2-(3,4-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-(2-propenyl)-2(1H)-quinolinone fumarateA mixture of 2-(3,4-dichlorophenyl)ethylamine (3.8 g), 5,6,7,8-tetrahydro-5-oxo-1-(2-propenyl)-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (225 mg) was heated in refluxing toluene (50 ml), with azeotropic removal water, for 24 hrs. An additional 1 g of the amine was added, and the mixture was heated for an additional 24 hrs. The solution was cooled, and the mixture was concentrated in vacuo. Sodium borohydride (0.56 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the resulting mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, and the residue was quenched with water. The mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with 5% methanol/ethyl acetate) to provide 4.03 g (73%) of basic product. The product was dissolved in ethanol, treated with an equivalent amount of fumaric acid, and the mixture was concentrated in vacuo. The residue was recrystallized from ethanol to provide the analytical sample, mp 160-161°C. ANALYSIS:Calculated for C24H26Cl2N2O558.43%C5.31%H5.68%NFound58.41%C5.61%H5.67%NEXAMPLE 205,6,7,8-Tetrahydro-5-[(2-phenylethyl)amino]-1-propyl-2(1H)-quinolinone fumarateA mixture of 5,6,7,8-tetrahydro-5-[(2-phenylethyl)amino]-(2-propenyl)-2(1H)-quinolinone (4.68 g) and 10% palladium-on-carbon (0.47 g) in ethanol (100 ml) was stirred under hydrogen at atmospheric pressure for 3 hrs. The mixture was filtered through celite, and the filtrate was concentrated. The residue solidified upon standing. The solid was dissolved in ethanol and treated with an equivalent amount of fumaric acid. The mixture was evaporated, and the residue was recrystallized twice, first from ethanol/ethyl acetate, and then from ethanol to provide 4.63 g (71%) of product, mp 151-153°C. ANALYSIS:Calculated for C24H30N2O567.59%C7.09%H6.57%NFound67.61%C7.09%H6.59%NEXAMPLE 215-[[2-(3,4-Dichlorophenyl)ethyl]amino]-5, 6,7,8-tetrahydro-1-(phenylmethyl)-2(1H)-quinolinone fumarateA mixture of 5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (5.0 g), lithium hydride (0.37 g), and dimethylformamide (200 ml) was stirred at 25°C for 3 hrs. Benzyl bromide (5.5 g) was added and the mixture was stirred for 20 hrs. Water was added, and the mixture was concentrated under reduced pressure. The residue was partitioned between ethyl acetate and water. The layers were separated and combined organic phase was washed with water, brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was triturated with hexanes to provide 4.5 (58%) of 5,6,7,8-tetrahydro-5-oxo-1-phenylmethyl-2(1H)-quinolinone.A mixture of 2-(3,4-dichlorophenyl)ethylamine (2.7 g), 5,6,7,8-tetrahydro-5-oxo-1-phenylmethyl-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (180 mg) was heated in 50 ml of refluxing toluene, with azeotropic removal of water, for 25 hrs. An additional 1 g of the amine was added, and the mixture was heated for an additional 63 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (0.45 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the product was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with methanol/ethyl acetate) to afford 4.0 g (80%) of basic product. The basic product was dissolved in hot ethanol and treated with an equivalent amount of fumaric acid. The solvent was removed and the residue was recrystallized from ethanol/ethyl acetate to provide 3.0 g of the analytical sample, mp 176-178°C. ANALYSIS:Calculated for C26H28Cl2N2O561.88%C5.19%H5.15%NFound61.59%C5.16%H5.07%NEXAMPLE 225,6,7,8-Tetrahydro-1-methyl-5-[(phenylmethyl)amino]-2(1H)-quinolinone fumarateA mixture of benzylamine (2.2 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (0.13 g) was heated in refluxing toluene (50 ml), with azeotropic removal of water, for 40 hrs. An additional 0.98 g of amine and 0.1 g of para-toluenesulfonic acid were added. The reaction mixture was heated under reflux for an additional 24 hrs, and then cooled. The mixture was concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with methanol/ethyl acetate) to give 3.1 g (69%) of basic product. The basic product was dissolved in ethanol and treated with 1.34 g of fumaric acid to give the fumarate, mp 159-161°C. ANALYSIS:Calculated for C21H24N2O5:65.61%C6.29%H7.29%NFound65.23%C6.32%H7.11%N EXAMPLE 23 5-[[2-(4-Trifluoromethylphenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinone A mixture of 2-(4-trifluoromethylphenyl)ethylamine (4.1 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (256 mg) was heated in refluxing toluene (50 ml), with azeotropic removal or water, for 40 hrs. An additional 2.0 g of the amine was added and the mixture was refluxed for 36 hr. The solution was cooled, and the mixture was concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the resulting mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was recrystallized from ethyl acetate/hexanes to provide, in two crops, 3.8 g (65%) of product, mp 104-106°C. ANALYSIS:Calculated for C19H21F3N2O65.13%C6.04%H7.99%NFound65.13%C6.16%H7.97%NEXAMPLE 245,6,7,8-Tetrahydro-1-methyl-5-[[2-(4-nitrophenyl)ethyl]amino] -2(1H)-quinolinoneA mixture of 2-(4-nitrophenyl)ethylamine (3.4 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (256 mg) was heated in refluxing toluene (70 ml), with azeotropic removal of water, for a total of 72 hrs. An additional 1.0 g of the amine was added at 24 and 48 hrs. The resulting solution was cooled and concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in ethyl alcohol (70 ml). The resulting mixture was stirred at room temperature for 1 hr, and the mixture was concentrated in vacuo. The residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with methanol/ethyl acetate) to provide 3.8 g (69%) of product. Recrystallization from ethyl acetate afforded the analytical sample, mp 138-139°C, ANALYSIS:Calculated for C18H21N3O366.04%C6.47%H12.84%NFound65.82%C6.19%H12.66%NEXAMPLE 255-[[2-(4-Chlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinoneA mixture of 2-(4-chlorophenyl)ethylamine (5.8 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (5.5 g), and a catalytic amount of para-toluenesulfonic acid was heated in refluxing toluene (90 ml), with azeotropic removal of water, for 40 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (1.1 g) was added to a solution of the residue in ethyl alcohol (90 ml), and the mixture was stirred at room temperature for 2 hrs. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Recrystallization of the residue from ethyl acetate/hexanes provided 6.55 g (67%) of product, mp 110-112°C. ANALYSIS:Calculated for C18H21N2O68.24%C6.68%H8.84%NFound68.36%C6.74%H8.78%NEXAMPLE 265,6,7,8-Tetrahydro-5-[[2-(4-methoxyphenyl)ethyl]amino]-1-methyl-2(1H)-quinolinoneA mixture of 2-(4-methoxyphenyl)ethylamine (5.6 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (5.5 g), and a catalytic amount of para-toluenesulfonic acid was heated in refluxing toluene (90 ml), with azeotropic removal of water, for 39 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (1.1 g) was added to a solution of the residue in ethyl alcohol (90 ml), and the mixture was stirred at room temperature for 2 hrs. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was washed with diethyl ether to afford 7.8 g (81%) of product. Recrystallization from ethyl acetate/hexanes provided the analytical sample, mp 97-99°C. ANALYSIS:Calculated for C19H24N2O273.05%C7.74%H8.97%NFound73.38%C7.48%H9.01%NEXAMPLE 275,6,7,8-Tetrahydro-1-methyl-5-[[2-(4-methylphenyl)ethyl]amino]-2(1H)-quinolinone fumarateA mixture of 2-(4-methylphenyl)ethylamine (2.7 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (0.13 g) was heated in refluxing toluene (50 ml), with azeotropic removal of water, for 42 hrs. The mixture was cooled and concentrated in vacuo. Sodium borohydride (0.64 g) was added to a solution of the residue in 50 ml of ethyl alcohol, and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was dissolved in ethanol, treated with 1.9 g of fumaric acid, and the salt was allowed to crystallize. Recrystallization from ethanol/2-isopropyl ether gave 3.87 g (56%) of product, mp 158-161°C. ANALYSIS:Calculated for C23H28N2O566.97%C6.84%H6.79%NFound67.05%C6.88%H6.78%NEXAMPLE 285-[[2-(2,4-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinoneA mixture of 2-(2,4-dichlorophenyl)ethylamine (3.8 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (256 mg) was heated in refluxing toluene (50 ml), with azeotropic removal of water, for 40 hrs. An additional 2.0 g of the amine was added and the mixture was refluxed for 36 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in 50 ml of ethyl alcohol, and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Recrystallization of the residue from ethyl acetate/hexanes provided 2.5 g (42%) of product, mp 102-103°C. ANALYSIS:Calculated for C18H20Cl2N2O61.55%C5.74%H7.97%NFound61.66%C5.86%H8.03%NEXAMPLE 295-[[2-(3,4-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinoneA mixture of 2-(3,4-dichlorophenyl)ethylamine (3.8 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (130 mg) was heated in refluxing toluene (50 ml), with azeotropic removal of water, for 41 hrs. An additional 1 g of the amine and 0.1 g of para-toluenesulfonic acid were added, and the mixture was heated for an additional 24 hrs. The solution was cooled and the precipitate was collected. Sodium borohydride (0.6 g) was added to a solution of the precipitate in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was dissolved in hot ethanol and treated with an equivalent amount of fumaric acid. The solid was collected and recrystallized from ethanol to provide 3.8 g (48%) of product, mp 172-173°C. ANALYSIS:Calculated for C22H24Cl2N2O556.54%C5.18%H5.99%NFound56.45%C5.04%H5.91%NEXAMPLE 305,6,7,8-Tetrahydro-1-methyl-5-[[2-(2,2-diphenyl)ethyl]amino]-2(1H)-quinolinoneA mixture of 2,2-diphenylethylamine (4.3 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (256 mg) was heated in 70 ml of refluxing toluene, with azeotropic removal of water, for 24 hrs. An additional 2.0 g of the amine was added, and the mixture was refluxed for 24 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in ethyl alcohol (70 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Recrystallization of the residue from ethyl acetate/hexanes provided 3.4 g (57%) of product, mp 110-112°C. ANALYSIS:Calculated for C24H26N2O80.41%C7.31%H7.81%NFound80.42%C7.44%H7.63%NEXAMPLE 315,6,7,8-Tetrahydro-1-methyl-5-[(3-phenylpropyl)amino]-2(1H)-quinolinone fumarateA mixture of 3-phenylpropylamine (2.7 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (130 mg) was heated in refluxing toluene (50 ml), with azeotropic removal of water, for 24 hrs. An additional 1 g of the amine and 0.1 of para-toluenesulfonic acid were added, and the mixture was heated for an additional 18 hrs. The solution was cooled and concentrated in vacuo. Sodium borohydride (0.6 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was washed with hexanes, dissolved in hot ethanol, and treated with an equivalent amount of fumaric acid to provide 5.5 g (80%) of product. Recrystallization from ethanol gave the analytical sample, mp 171-173°C. ANALYSIS:Calculated for C23H28N2O566.97%C6.84%H6.79%NFound66.77%C6.78%H6.78%NEXAMPLE 325-[[2-(4-Chlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1,7,7-trimethyl-2(1H)quinolinone fumarateA mixture of 5,6,7,8-tetrahydro-7,7-dimethyl-5-oxo-2(1H)-quinolinone (15.0 g), methyl iodide (12.3 g), potassium carbonate (21.6 g), and dimethylformamide (230 ml) was stirred at room temperature for 21 hrs. The reaction mixture was filtered, and the filtrate was concentrated. Ethyl acetate was added to the residue, and the mixture was filtered. The filtrate was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to give 8.1 g (50%) of 5,6,7,8-tetrahydro-5-oxo-1,7,7-trimethyl-2(1H)-quinolinone.A mixture of 5,6,7,8-tetrahydro-2-(4-chlorophenyl)ethylamine (3.6 g), 1,7,7-trimethyl-5-oxo-2(1H)-quinolinone (4.0 g), and para-toluenesulfonic acid (0.11 g) was heated in refluxing toluene (60 ml), with azeotropic removal of water, for 48 hrs, at which time an additional 3.6 g of amine and 0.1 g of para-toluenesulfonic acid were added. The mixture was refluxed for a total of 72 hrs. The mixture was cooled and concentrated in vacuo. Sodium borohydride (1.0 g) was added to a solution of the residue in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, eluted with methanol/ethyl acetate). The appropriate fractions were collected and evaporated. The residue was dissolved in methanol and treated with 0.74 g of fumaric acid. The mixture was evaporated, and the residue triturated with ethyl acetate to give 2.8 g (31%) of product. Recrystallization from ethanol give the analytical sample, mp 155-156°C. ANALYSIS:Calculated for C24H29ClN2O562.54%C6.34%H6.08%NFound62.32%C6.21%H6.43%NEXAMPLE 335-[[2-(3,4,-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-propyl-2(1H)-quinolinoneA mixture of 2-(3,4-dichlorphenyl)ethylamine (4.2 g) 5,6,7,8-tetrahydro-1-propyl-5-oxo-2(1H)-quinolinone (3.5 g), and para-toluenesulfonic acid (257 mg) was heated in refluxing toluene (70 ml), with azeotropic removal of water, for 40 hrs. An additional 1 g of the amine was added after 40 and 64 hrs. The mixture was heated for a total of 88 hrs. The solution was cooled and evaporated in vacuo.Sodium borohydride (0.60 g) was added to a solution of the residue in ethyl alcohol (70 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was evaporated in vacuo. The residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography on silica gel (elution with methanol/ethyl acetate to afford 4.8 g (75%) of product. Recrystallization from ethyl acetate/hexanes provided the analytical sample, mp 105-107°C. ANALYSIS:Calculated for C20H24Cl2N2O63.33%C6.38%H7.38%NFound63.10%C6.22%H7.36%NEXAMPLE 345,6,7,8-Tetrahydro-1-methyl-5-[[2-(1-napthyl)ethyl]amino]-2(1H)-quinolinone fumarateA mixture of 2-(1-naphthyl)ethylamine (3.7 g), 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g), and para-toluenesulfonic acid (256 mg) was heated in refluxing toluene (70 ml), with azeotropic removal of water, for 24 hrs. An additional 2 g of the amine was added, and the mixture was heated for an additional 24 hrs. The solution was cooled and evaporated in vacuo.Sodium borohydride (0.60 g) was added to a solution of the residue in ethyl alcohol (70 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was evaporated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated. The residue was purified by high performance liquid chromatography on silica gel (elution with methanol/ethyl acetate) to afford 4.59 g (82%) of product. The product was dissolved in methanol and treated with an equivalent amount of fumaric acid. The solution was evaporated in vacuo, and the residue was recrystallized from methanol. The solid was stirred in hot methanol, and the mixture was filtered to provide the analytical sample, mp 189-191°C. ANALYSIS:Calculated for C26H28N2O569.33%C6.29%H6.25%NFound69.38%C6.39%H6.21%NEXAMPLE 355-[[2-(4-Chlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-(2-propenyl)-2(1H)-quinolinone hydrochlorideA mixture of 2-(4-chlorophenyl)ethylamine (5.5 g), 5,6,7,8-tetrahydro-5-oxo-(2-propenyl)-2(1H)-quinolinone (6.0 g), and para-toluenesulfonic acid (450 mg) was heated in refluxing toluene (100 ml), with azeotropic removal of water, for 24 hrs. An additional 2 g of the amine was added, and the mixture was heated for an additional 48 hrs. The solution was cooled and evaporated in vacuo.Sodium borohydride (1.12 g) was added to a solution of the residue in ethyl alcohol (100 ml), and the resulting mixture was stirred at room temperature for 1 hr. The mixture was evaporated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography on silica gel (elution with 5% methanol/ethyl acetate to provide 8.50 g (85%) of product. A portion of product was dissolved in methanol and treated with ethereal hydrogen chloride. The mixture was evaporated in vacuo, and the residue was crystallized from methanol/isopropyl ether to provide the analytical sample, mp 175-177°C. ANALYSIS:Calculated for C20H24Cl2N2O63.33%C6.38%H7.38%NFound63.00%C6.53%H7.03%NEXAMPLE 365-[[2-(4-Chlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-propyl-2(1H)-quinolinone fumarateA mixture of 5-[[2-(4-chlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-(2-propenyl)-2(1H)-quinolinone (4.5 g) and 10% palladium-on-carbon (0.45 mg) in ethanol (100 ml) was stirred under an atmosphere of hydrogen for 3 hrs. The mixture was filtered through celite, and the filtrate was concentrated. The residue was filtered through silica gel (elution with ethyl acetate/methanol), and the filtrate was evaporated. The residue was dissolved in ethanol, treated with an equivalent amount of fumaric acid, and the salt was allowed to crystallize. The precipitate was collected to provide 3.0 g (50%) of product, mp 166-168°C. ANALYSIS:Calculated for C24H29ClN2O562.54%C6.34%H6.08%NFound62.73%C6.19%H6.05%NEXAMPLE 375-[[2-(3,4-Dichlorophenyl)ethyl]amino]-1-hexyl-5,6,7,8-tetrahydro-2(1H)-quinolinone fumarateA mixture of 5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (10.0 g), lithium hydride (0.78 g), and dimethylformamide (400 ml) was stirred for 3 hrs at 25°C, under nitrogen. 1-Bromohexane (10.6 g) was added and the mixture was stirred for an additional eighteen hrs. The reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography (silica gel, two columns, eluted with 50% ethyl acetate/hexane). The appropriate fractions were collected and evaporated to give 4.6 (31%) of 1-hexyl-5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone.Titanium tetra-isopropoxide (11.6 g) was rapidly added dropwise to a suspension of 1-hexyl-5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (4.6 g) and 3,4-dichlorophenethylamine (7.0 g) in acetonitrile (38 ml). The mixture was stirred at room temperature for 20 hrs and water and dichloromethane were added. The layers were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were filtered, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated.Sodium borohydride (706 mg) was added to a solution of the residue in ethyl alcohol (80 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was evaporated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography on silica gel (elution with 5% methanol/ethyl acetate) to provide 5.8 g (74%) of product. The product was dissolved in ethanol and treated with an equivalent amount of fumaric acid. The mixture was concentrated in vacuo, ethyl acetate was added, and the product was allowed to crystallize to provide the analytical sample, mp 160-162°C. ANALYSIS:Calculated for C27H34Cl2N2O560.34%C6.38%H5.21%NFound60.01%C6.26%H5.05%NEXAMPLE 385-[[2-(3,4-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-(3-methyl-2-butenyl)-2(1H)-quinolinone maleateA mixture of 5,6,7,8-tetrahydro-5-oxo-(2(1H)-quinolinone (10.0 g), lithium hydride (0.79), and dimethylformamide (400 ml) was stirred for 3 hrs at 25°C, under nitrogen. 3-Methylbutenyl bromide (10.6) was added and the mixture was stirred for an additional eighteen hrs. The reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was triturated with petroleum ether to afford 10.5 g (74%) of 5,6,7,8-tetrahydro-1-(3-methyl-2-buteneyl)-5-oxo-2(1H)-quinolinone.A mixture of 3,4-dichlorophenethylamine (7.9 g), 5,6,7,8-tetrahydro-1-(3-methyl-2-butenyl)-5-oxo-2(1H)-quinolinone (8.0 g), and para-toluenesulfonic acid (526 mg) was heated in refluxing toluene (100 ml), with azeotropic removal of water, for 18 hrs. An additional 2 g of the amine was added, and the mixture was heated for an additional 68 hrs. The solution was cooled and evaporated in vacuo.Sodium borohydride (1.3 g) was added to a solution of the residue in ethyl alcohol (100 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was evaporated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was purified by high performance liquid chromatography on silica gel (elution with methanol/ethyl acetate) to afford 11.5 g (82%) of product as an oil. The product was dissolved in hot ethanol and treated with an equivalent amount of maleic acid. The solution was allowed to cool, the precipitate was collected to provide the analytical sample, mp 103-107°C. ANALYSIS:Calculated for C26H30Cl2N2O559.89%C5.80%H5.37%NFound59.35%C5.51%H5.32%NEXAMPLE 395,6,7,8-Tetrahydro-1-methyl-5-[[2-(2-napthyl)ethyl]amino]-2(1H)-quinolinoneTitanium tetra-isopropoxide (10.5 g) was rapidly added to a solution of 5,6,7,8-tetrahydro-1-methyl-5-oxo-2(1H)-quinolinone (3.0 g) and 2-(2-napthyl)ethylamine (5.8 g) in acetonitrile (35 ml). The mixture was stirred at room temperature for 20 hrs and dichloromethane and water were added. The mixture was filtered, the layers of the filtrate were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated.Sodium borohydride (600 mg) was added to a solution of the residue in ethyl alcohol (100 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was recrystallized twice from ethyl acetate to provide 2.5 g (45%) of product, mp 113-115°C. ANALYSIS:Calculated for C22H24N2O79.48%C7.28%H8.43%NFound79.66%C7.43%H8.48%NEXAMPLE 405-[[2-(3,4-Dichlorophenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-(2-phenylethyl)-2(1H)-quinolinoneA mixture of 5,6,7,8-tetrahydro-5-oxo-2(1H)-quinolinone (7.5 g), lithium hydride (0.59 g), and dimethylformamide (300 ml) was stirred for 3 hrs at 25°C, under nitrogen. 2-Phenylethyl bromide (9.36 g) was added and the mixture was stirred for an additional eighteen hrs. The reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. The residue was triturated with petroleum ether to afford 3.0 g (24%) of 5,6,7,8-tetrahydro-5-oxo-1-(2-phenylethyl)-2(1H)-quinolinone.Titanium tetra-isopropoxide (7.0 g) was rapidly added to a solution of 5,6,7,8-tetrahydro-5-oxo-1-(2-phenylethyl)-2(1H)-quinolinone (3.0 g), and 2-(3,4-dichlorophenyl)ethylamine (5.8 g) in acetonitrile (25 ml). The mixture was stirred at room temperature for 20 hrs and dichloromethane and water were added. The mixture was filtered, the layers of the filtrate were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Sodium borohydride (420 mg) was added to a solution of the residue in ethyl alcohol (50 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated. Recrystallization of the residue from ethyl acetate/hexanes provided 2.6 g (52%) of product, mp 120-122°C. ANALYSIS:Calculated for C25H26Cl2N2O68.03%C5.94%H6.35%NFound68.01%C5.81%H6.27%NEXAMPLE 415-[[2-(1-Cyclohexenyl)ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinoneTitanium tetra-isopropoxide (21.0 g) was rapidly added to a solution of 5,6,7,8-tetrahydro-5-oxo-1-methyl)-2(1H)-quinolinone (6.0 g) and 2-(1-cyclohexenyl)ethylamine (8.4 g) in acetonitrile (70 ml). The mixture was stirred at room temperature for 20 hrs and dichloromethane and water were added. The mixture was filtered, the layers of the filtrate were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated.Sodium borohydride (1.2 mg) was added to a solution of the residue in ethyl alcohol (150 ml), and the mixture was stirred at room temperature for 1 hr. The mixture was concentrated in vacuo, the residue was carefully quenched with water, and the mixture was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate concentrated. Recrystallization or the residue from ethyl acetate/hexanes provided 3.5 g (32%) of product, mp 184-187°C. ANALYSIS:Calculated for C18H26N2O75.48%C9.15%H9.78%NFound75.69%C9.32%H9.79%N	Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, IT, LI, LU, NL, SEA compound of the formula 1 wherein X-Y is a group of the formula wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl, or a group of the formula wherein R1 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl; R2 and R3 are independently hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl, (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, (C1-C6)-alkoxy, phenyl-(C1-C6)-alkoxy, or (C1-C6)-alkanoyl, or R2 and R3 taken together with the nitrogen atom to which they are attached form a group of the formula wherein p is 0 or 1, a group of the formula wherein Z is O, S, or a group of the formula NR6 wherein R6 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R4 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R5 is hydrogen, (C1-C5)-alkyl, or phenyl-(C1-C6)-alkyl; wherein the phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl; m is 0, 1, or 2; and n is 1 or 2; with the proviso that when X-Y is and m is 1, then R2, R3, R4 and R5 are not hydrogen; the geometric and optical isomers thereof, or a pharmaceutically acceptable salt thereof. A compound according to claim 1, wherein m is 1.A compound according to claim 2, wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, or phenyl-(C1-C6)-alkyl; R1 is (C1-C6)-alkyl; R2 and R3 are independently hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, or phenyl-(C1-C6)-alkoxy, wherein the phenyl may be substituted once or two times with chloro, trifluoromethyl, nitro or (C1-C6)-alkoxy or R2 and R3 are independently naphthyl, or (C1-C6)-alkanoyl; R4 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R5 is hydrogen or (C1-C6)-alkyl and n is 1 or 2.A compound according to claim 2, wherein X-Y is a group of the formula where R is (C1-C6)-alkyl R2 is hydrogen or benzyloxy, R3 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkanoyl or phenyl-(C1-C6)-alkyl, wherein the phenyl may be substituted once or two times with chloro, trifluoromethyl, nitro or (C1-C6)-alkoxy; R4 is hydrogen or (C1-C6)-alkyl, R5 is hydrogen and n is 1.The compound according to claim 1 which is N-(1,2,5,6,7,8-hexahydro-5-methyl-2-oxo-5-quinolinyl) acetamide or a pharmaceutically acceptable salt thereof.The compound according to claim 1 which is 1-methyl-5-[(2-phenylethyl)amino]-5,6,7,8-tetrahydro-2-(1H)-quinolinone or a pharmaceutically acceptable salt thereof.The compound according to claim 1 which is 5-[[2-(4-methoxyphenyl)ethyl]-amino]-1-methyl-5,6,7,8-tetrahydro-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof.The compound according to claim 1 which is 5-[[2-(3,4-dichlorophenyl)-ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof.The compound according to claim 1 which is 5,6,7,8-tetrahydro-5-[(2-phenylethyl)amino]-1-propyl-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof.A compound of the formula wherein X-Y is a group of the formula wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl, or a group of the formula wherein R1 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl; R4 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R5 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl where phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl; m is 0, 1, or 2; and n is 1 or 2; with the proviso that when X-Y is and m is 1, then R4 and R5 are not hydrogen; or the geometric or optical isomer thereof.A compound according to claim 10 wherein m is 1.A pharmaceutical composition which comprises as the active ingredient a compound according to claim 1 and a suitable carrier therefor.Use of a compound according to claim 1 for the preparation of a medicament having memory dysfunction relieving activity. A process for the preparation of a compound according to claim 1, which comprises a) contacting a compound of the formula 2 where R, R5, m and n are as defined in claim 1 with a compound of the formula R2NH2, where R2 is hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl(C1-C6)-alkyl, (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, (C1-C6)-alkoxy, or phenyl-(C1-C6)-alkoxy, where the phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl, to provide an imine of the formula and reducing the imine obtained with an alkali metal borohydride to provide a compound of the formula 1 wherein X-Y is the group wherein R, R5, m and n are as defined in claim 1, R1 and R4 are hydrogen and R2 is as defined above, orb) treating a compound of the formula 4 wherein R1 is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R4 is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, where phenyl may in each case be substituted as indicated instep (a), R5, m and n are as defined in claim 1 with a nitrile of the formula R7CN, wherein R7 is (C1-C6)-alkyl to provide a compound of the formula 1 wherein X-Y is R2 is hydrogen, R3 is COR7, R1 and R4 are as defined, and R5, m and n are as defined in claim 1.c) optionally hydrogenating a compound of the formula 1 as obtained in step b) in the presence of a noble metal catalyst, to provide a compound of the formula 1, wherein X-Y is the group and R2, R3, R4, R5, m and n are as defined in step b), ord) condensing a compound of the formula 4 wherein R1, R4, R5, m and n are as defined in step b), with an alkoxyamine of the formula R8CH2ONH2, wherein R8 is phenyl or phenyl substituted with one or more halogen, alkoxy, alkyl, or trifluoromethyl groups, to provide a compound of the formula 1, wherein R1, R4, R5, m and n are as defined in step b), R2 is hydrogen, and R3 is -OCH2R8, where R8 is as defined,e) optionally treating a Compound of the formula 1 as obtained in step d) with a borane complex to provide a compound of the formula 1, wherein X-Y is the group R2 and R3 are hydrogen and R1, R4, R5, m and n are as defined in step b),f) optionally hydrogenating a compound of the formula 1 as obtained in step e) in the presence of a noble metal catalyst to provide a compound of the formula 1 where X-Y is the group R2 and R3 are hydrogen and R1, R4, R5, m and n are as defined in step b),g) optionally alkylating a compound of the formula 1, where X-Y is the group and R2, R3, R4, R5, m and n are as defined in claim 1, with a halide of the formula R Hal, wherein R is (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl where phenyl may be substituted as indicated in step (a), to provide a compound of the formula 1 wherein X-Y is the group where R is as defined and R2, R3, R4, R5, m and n are as defined in claim 1,h) optionally alkylating a compound of the formula 1, wherein X-Y is the group R1 is as defined in claim 1 except hydrogen, R2 is hydrogen, R3 is -OCH2R8, where R8 is phenyl or phenyl substituted with one or more halogen, alkoxy, alkyl or trifluoromethyl groups and R4, R5, m and n are as defined in claim 1, by first forming the amino anion with an alkyl- or arylalkali metal and treating the anion, so formed, with a halide of the formula R2Hal, where R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl or (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, to provide a compound of the formula 1, wherein X-Y, R1, R3, R4, R5, m and n are as defined and R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl or (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, where phenyl may in each case be substituted as indicated in step (a),i) optionally cleaving the group OCH2R8 from a compound of the formula 1 as obtained in step h) by means of a borane complex, to provide a compound of the formula 1, wherein X-Y is the group R1 is as defined in claim 1 except hydrogen, R2 is as defined in step h), R3 is hydrogen and R4, R5, m and n are as defined in claim 1, i) optionally hydrogenating a compound of the formula 1 as obtained in step i) to provide a compound of the formula 1 wherein X-Y is the group or R2 is as defined in step h), R3 is hydrogen and R4, R5, m and n are as defined in claim 1, ork) condensing a compound of the formula 23 wherein R is phenylalkyl and phenyl may be substituted as indicated in step (a), and R5, m and n are as defined in claim 1, with a primary amine of the formula R2R3NH, wherein R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl or (C1-C6)-alkoxy or phenyl-(C1-C6)-alkoxy and R3 is hydrogen, to provide an imine of the formula 24 and reducing the compound obtained with an alkali metal borohydride to provide a compound of the formula 1 wherein R, R2 and R3 are as defined, R4 is hydrogen and R5, m and n are as defined in claim 1,I) optionally hydrogenating a compound of the formula 1 as obtained in step k) to provide a compound of the formula 1 wherein R2, R3, R4, R5, m and n are as defined in claim 1 and X-Y is the group or m) optionally acylating a compound of the formula 1, wherein X-Y is where R is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R2 is phenyl-(C1-C6)-alkoxy, R3 is hydrogen, R4 is hydrogen, R5, m and n are as defined in claim 1, with a compound of the formula (R7CO)2O, where R7 is (C1-C6)-alkyl, to provide a compound of the formula 1, where X-Y, R, R2, R4, R5, m and n are as defined and R3 is R7CO.Claims for the following Contracting States : ES, GRA process for the preparation of a compound of the formula 1 wherein X-Y is a group of the formula wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl, or a group of the formula wherein R1 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-akyl; R2 and R3 are independently hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl, (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, (C1-C6)-alkoxy, phenyl-(C1-C6)-alkoxy, or (C1-C6)-alkanoyl, or R2 and R3 taken together with the nitrogen atom to which they are attached form a group of the formula wherein p is 0 or 1, a group of the formula wherein Z is O, S, or a group of the formula NR6 wherein R6 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R4 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R5 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; wherein the phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl; m is 0, 1, or 2; and n is 1 or 2; with the proviso that when X-Y is and m is 1, then R2, R3, R4 and R5 are not hydrogen; the geometric and optical isomers thereof, or a pharmaceutically acceptable salt thereof, which comprises a) contacting a compound of the formula 2 where R, R5, m and n are as defined in claim 1 with a compound of the formula R2NH2, where R2 is hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl, (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, (C1-C6)-alkoxy, or phenyl-(C1-C6)-alkoxy, where the phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl, to provide an imine of the formula and reducing the imine obtained with an alkali metal borohydride to provide a compound of the formula 1 wherein X-Y is the group wherein R, R5, m and n are as defined in claim 1, R1 and R4 are hydrogen and R2 is as defined above, orb) treating a compound of the formula 4 wherein R1 is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R4 is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, where phenyl may in each case be substituted as indicated instep (a), R5, m and n are as defined in claim 1 with a nitrile of the formula R7CN, wherein R7 is (C1-C6)-alkyl to provide a compound of the formula 1 wherein X-Y is R2 is hydrogen, R3 is COR7, R1 and R4 are as defined, and R5, m and n are as defined in claim 1.c) optionally hydrogenating a compound of the formula 1 as obtained in step b) in the presence of a noble metal catalyst, to provide a compound of the formula 1, wherein X-Y is the group and R2, R3, R4, R5, m and n are as defined in step b), ord) condensing a compound of the formula 4 wherein R1, R4, R5, m and n are as defined in step b), with an alkoxyamine of the formula R8CH2ONH2, wherein R8 is phenyl or phenyl substituted with one or more halogen, alkoxy, alkyl, or trifluoromethyl groups, to provide a compound of the formula 1, wherein R1, R4, R5, m and n are as defined in step b), R2 is hydrogen, and R3 is -OCH2R8, where R8 is as defined,e) optionally treating a Compound of the formula 1 as obtained in step d) with a borane complex to provide a compound of the formula 1, wherein X-Y is the group R2 and R3 are hydrogen and R1, R4, R5, m and n are as defined in step b),f) optionally hydrogenating a compound of the formula 1 as obtained in step e) in the presence of a noble metal catalyst to provide a compound of the formula 1 where X-Y is the group R2 and R3 are hydrogen and R1, R4, R5, m and n are as defined in step b),g) optionally alkylating a compound of the formula 1, where X-Y is the group and R2, R3, R4, R5, m and n are as defined in claim 1, with a halide of the formula R Hal, wherein R is (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl where phenyl may be substituted as indicated in step (a), to provide a compound of the formula 1 wherein X-Y is the group where R is as defined and R2, R3, R4, R5, m and n are as defined in claim 1,h) optionally alkylating a compound of the formula 1, wherein X-Y is the group R1 is as defined in claim 1 except hydrogen, R2 is hydrogen, R3 is -OCH2R8, where R8 is phenyl or phenyl substituted with one or more halogen, alkoxy, alkyl or trifluoromethyl groups and R4, R5, m and n are as defined in claim 1, by first forming the amino anion with an alkyl- or arylalkali metal and treating the anion, so formed, with a halide of the formula R2Hal, where R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl or (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, to provide a compound of the formula 1, wherein X-Y, R1, R3, R4, R5, m and n are as defined and R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, diphenyl-(C1-C6)-alkyl or (C4-C6)-cycloalkenyl-(C1-C6)-alkyl, where phenyl may in each case be substituted as indicated in step (a),i) optionally cleaving the group OCH2R8 from a compound of the formula 1 as obtained in step h) by means of a borane complex, to provide a compound of the formula 1, wherein X-Y is the group R1 is as defined in claim 1 except hydrogen, R2 is as defined in step h), R3 is hydrogen and R4, R5, m and n are as defined in claim 1, i) optionally hydrogenating a compound of the formula 1 as obtained in step i) to provide a compound of the formula 1 wherein X-Y is the group or R2 is as defined in step h), R3 is hydrogen and R4, R5, m and n are as defined in claim 1, ork) condensing a compound of the formula 23 wherein R is phenylalkyl and phenyl may be substituted as indicated in step (a), and R5, m and n are as defined in claim 1, with a primary amine of the formula R2R3NH, wherein R2 is (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl or (C1-C6)-alkoxy or phenyl-(C1-C6)-alkoxy and R3 is hydrogen, to provide an imine of the formula 24 and reducing the compound obtained with an alkali metal borohydride to provide a compound of the formula 1 wherein R, R2 and R3 are as defined, R4 is hydrogen and R5, m and n are as defined in claim 1,I) optionally hydrogenating a compound of the formula 1 as obtained in step k) to provide a compound of the formula 1 wherein R2, R3, R4, R5, m and n are as defined in claim 1 and X-Y is the group or m) optionally acylating a compound of the formula 1, wherein X-Y is where R is (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R2 is phenyl-(C1-C6)-alkoxy, R3 is hydrogen, R4 is hydrogen, R5, m and n are as defined in claim 1, with a compound of the formula (R7CO)2O, where R7 is (C1-C6)-alkyl, to provide a compound of the formula 1, where X-Y, R, R2, R4, R5, m and n are as defined and R3 is R7CO.A process according to claim 1, wherein m is 1.A process according to claim 2, wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, or phenyl-(C1-C6)-alkyl; R1 is (C1-C6)-alkyl; R2 and R3 are independently hydrogen, (C1-C6)-alkyl, phenyl-(C1-C6)-alkyl, or phenyl-(C1-C6)-alkoxy, wherein the phenyl may be substituted once or two times with chloro, trifluoromethyl, nitro or (C1-C6)-alkoxy or R2 and R3 are independently naphthyl, or (C1-C6)-alkanoyl; R4 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl, R5 is hydrogen or (C1-C6)-alkyl and n is 1 or 2.A process according to claim 2, wherein X-Y is a group of the formula where R is (C1-C6)-alkyl R2 is hydrogen or benzyloxy, R4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkanoyl or phenyl-(C1-C6)-alkyl, wherein the phenyl may be substituted once or two times with chloro, trifluoromethyl, nitro or (C1-C6)-alkoxy; R4 is hydrogen or (C1-C6)-alkyl, R5 is hydrogen and n is 1.The process according to claim 1 wherein N-(1,2,5,6,7,8-hexahydro-5-methyl-2-oxo-5-quinolinyl) acetamide or a pharmaceutically acceptable salt thereof is prepared.The process according to claim 1 wherein 1-methyl-5-[(2-phenylethyl)-amino]-5,6,7,8-tetrahydro-2-(1H)-quinolinone or a pharmaceutically acceptable salt thereof is prepared.The process according to claim 1 wherein 5-[[2-(4-methoxyphenyl)-ethyl]-amino]-1-methyl-5,6,7,8-tetrahydro-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof is prepared.The process according to claim 1 wherein 5-[[2-(3,4-dichlorophenyl)-ethyl]amino]-5,6,7,8-tetrahydro-1-methyl-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof is prepared.The process according to claim 1 wherein 5,6,7,8-tetrahydro-5-[(2-phenylethyl)amino]-1-propyl-2(1H)-quinolinone or a pharmaceutically acceptable salt thereof is prepared.A compound of the formula wherein X-Y is a group of the formula wherein R is hydrogen, (C1-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl, or phenyl-(C1-C6)-alkyl, or a group of the formula wherein R1 is hydrogen, (C1-C6)-alkyl or phenyl-(C1-C6)-alkyl; R4 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl; R5 is hydrogen, (C1-C6)-alkyl, or phenyl-(C1-C6)-alkyl where phenyl may in each case be substituted by one or more of the groups: chloro, bromo, fluoro, methoxy, C1-C8-alkyl, nitro, hydroxy, or trifluoromethyl; m is 0, 1, or 2; and n is 1 or 2; with the proviso that when X-Y is and m is 1, then R4 and R5 are not hydrogen; or the geometric or optical isomer thereof. A compound according to claim 10 wherein m is 1.Use of a compound of the formula 1 according to claim 1 for the preparation of a medicament having memory dysfunction relieving activity.	HOECHST MARION ROUSSEL INC; HOECHST MARION ROUSSEL, INC.	EFFLAND RICHARD CHARLES; FINK DAVID M; EFFLAND, RICHARD CHARLES; FINK, DAVID M.
EP-0489385-B1	489,385	EP	B1	EN	19,970,319	1,992	20,100,220	new	H04N7	null	H04N7	H04N 7/16E2, H04N 7/16E3	System for the transmission and reception of encoded television signals	The present invention refers to a system for the transmission and reception of encoded television signals, in which a television signal is encoded in order not to be received and reproduced in the normal way by normal television receivers, but only by receivers equipped with a suitable decoder, and in which the decoder includes a control circuit that periodically receives a secret code, by telephone from a central computer. The secret code is necessary for the decoding operation. The main characteristics of the invention consist in the fact that such secret code is transmitted by means of a ciphered procedure, at non fixed intervals, and in the fact that such system provides that the control circuit, the memory associated to it, a telephone modem and a battery pad be contained in one card, extractable from the decoder and linkable to the telephone line and that said decoder be individualized with an identification number.	The present invention refers to a system for transmitting and receiving encoded television signals, in which a television signal is encoded in order not to be received and reproduced in the normal way by normal television receivers, but only by receivers equipped with a suitable decoder, and in which the decoder includes a control circuit that receives periodically by telephone, a secret code, from a central computer. The secret code is necessary for the decoding operation. It is known that distribution systems for television programs upon payment are used, in which the programs are distributed for example by cable, and in which the television signal undergoes coding during transmission, thus modifying the characteristics; in order to receive such signals in a satisfactory way, a receiver equipped with an opportune decoder is needed that restores the signal to its original characteristics, in order to permit that the visual and audio reproduction be realized in a satisfactory way. A system of the type known is described by the U.S. patent US-A-4,916,737; it provides that a central computer be connected once a month by telephone with the decoder having an identification number and a table for decoding, to communicate a new identification number and a new table to it. As the decoding table is valid for one month, and written in EAROM, this system can be easily subject to actions of piracy, such as copying the table. This allows to avoid payment of the quote due for any number of other abusive decoders. In the patent it is suggested that the EAROM be obtained in the same substratum of the microprocessor, in order to make copying more difficult. This means a high increase in the cost of the apparatus, because the component must practically be manufactured by order, so in a limited number, on which the cost of the tooling is a heavy burden, and is unavoidably subjected to a high incidence of rejects. Another inconvenient of the known system is that the telephone line must be permanently connected to the decoder upstream the normal telephone apparatus, restricting the different ways of arranging the decoder and/or of such telephone set. The international patent application WO-A-8503830 describes a method of controlling the deciphering of an enciphered signal wherein an order call from subscriber unit is sent via a telephone line and the deciphering key is sent back on that line for storage in that unit without requiring the subscriber to identify itself; the deciphering key delivered via the telephone may itself be enciphered. The aim of the present invention is therefore to indicate a transmission and reception system for encoded television signals like the type described, not having a high cost, not being inconvenient for the user and presenting a high safety degree against the possibility of actions of piracy. In order to achieve such aims, the object of the present invention consists of a system for the transmission and reception of the encoded television signals, characterized by the fact that said system provides that the control circuit, the memory associated to it, a telephone modem and a battery pad be contained in one card, extractable from the decoder and linkable to the telephone line and that said decoder be individualized by an identification number. Further aims and advantages of the present invention will result clear in the following detailed description and enclosed drawings, supplied only as an explicative and non limiting example, in which: Figure 1 schematically represents a system according to the invention; Figure 2 represents a block diagram of a part of the system according to invention; Figure 3 represents a variant of the represented system in Figure 1; Figure 4 represents a further variant of the represented system in Figure 1; Figure 5 schematically represents the logic flow of a part of the functioning of the system of Figure 1. In Figure 1, that schematically represents a possible realization of the system according to the invention, reference symbol A indicates an aerial for receiving the television signal; a television signal receiver is indicated with the symbol TV; with the CB symbol, the circuital block is indicated, making part of the television receiver TV. The block CB is removable from the television receiver TV, to which it is connected by means of a certain number of known electric connectors necessary for the exchange of feeding tensions and signals. The receiver TV is mainly of a conventional type; it includes a signal tuner, amplifier signal blocks, detectors, deflection signal generators, an image visualizer apparatus (for example a classic colour picture-tube with shadow mask), a power supply section, etc.. The CB block, that is represented in more detail in Figure 2, includes an auxiliary feeding battery pad, indicated with the reference symbol B, necessary for supplying the other circuits of the block CB when it is not connected to the receiver TV or to an other circuital block provided with a power supply circuit. The block CB also includes a circuital control block, indicated with the symbol CPU, that represents a central process unit and can contain, in one of the preferred versions of the invention, a microprocessor; said central process unit contains at least one inside register, capable of retaining, typically, a binary data of 32 bit. The block CB also includes a non-volatile memory circuit, for example a ROM (read only memory), indicated with the reference symbol M; and a telephone modem, indicated with the reference symbol MD. The battery B is connected to all the three other blocks (CPU, M and MD); the CPU is connected to the modem MD and to the memory M ; the modem MD is naturally linkable to the telephone line PH. The block CB can be made, in a preferred form of realization of the invention, on a printed circuit card, extractable in the known way from the TV receiver and insertable in another block, indicated in Figure 1 with the reference symbol BT, which will be dealt with later. In Figure 1 the reference symbol CC indicates a central control computer, situated in a different location from that of the receiver TV and the circuit BT. The central computer CC is connected to the telephone PH line. The circuit BT is also connected to the telephone line PH; it is also connected to a normal domestic telephone set, indicated with reference symbol T; as already said, the circuit BT is linkable to the circuitry block CB. As mentioned above, Figure 2 represents a block diagram of a part of the system according to the invention, and precisely of the circuitry block CB. The television receiver TV can receive an encoded television signal (scrambled) in such a way that it can not be received and reproduced in a normal way by normal television receivers, but only by receivers equipped with a suitable decoder; the decoder is contained in the block, and, more precisely, is made utilizing the microprocessor (for example of the 16 bit type 8086, but with some registers at 32 bit) that represents the substantial part of the central process unit CPU. The instructions for operating the microprocessor are contained in the memory M, with one or more conversion tables (look up tables) that are necessary for decoding the program to be received. The reception of the encoded programs is possible by paying a fee (that can be measured by time, for example daily, weekly or monthly) or from program to program. To carry out the decoding operation, the microprocessor must know a secret code, that is supplied only to the users up-to-date with their payments. Said secret code can, for example, be the address of the memory M where there is the special conversion table to be utilized for the decoding of the program to be received. The secret code, for safety reasons, is periodically changed (for example daily, in a preferred version of the invention); the central computer CC provides to call the user by phone to communicate the secret code valid up to the time of the next call. In the version represented in Figure 1, the central computer calls the user every night, between 01,00 o'clock and 5,30 A.M.; the time of the call is not known, but it is fixed every night by the computer on the bases of the sequence of the pseudocasual numbers; in this way two goals are acheived: firstly, making it difficult to try to intercept the call, and secondly, not occupying the user's telephone line during the hours in which he may need to to use the phone. If the user's line is occupied, the main computer recalls again twice, with a 15 minute interval one from to the other. The user, every evening, before going to bed, provides to extract the card CB from the television receiver and insert it in the circuit BT connected to the telephone line, so the computer CC reaches the microprocessor of the CPU unit. The circuit BT is similar to the one described in the Italian patent application n. 67032-A/86 (IT-A-1 187 057); the computer in order to be recognised by the circuit BT effects its call in a conventional way; precisely it effects only one ring and then closes; it then leaves a 5 second space of time and then recalls; considering that the dialing of the number takes about 10 seconds, the peripheral terminal will receive the second call about 15 seconds after the first. Therefore the conversation with the circuit BT starts. The circuit BT, that in this type of solution includes an incorporated CMOS technology made timer to be fed by the same telephone doubled wire, on its own account, starts at 1 o'clock to disconnect for 5 seconds the telephone apparatus T every time it receives a call. In such a way the telephone bell T does not function when the computer CC calls, and the user is not disturbed; if on the other hand someone calls the user during such an interval of time, between 1,00 o'clock and 5,30, it is prepared to make the telephone ring for a long time, so the loss of one or, maximum, two rings has insignificant effects. As soon as the circuit BT detects the the computers CC call (recognizable because it stops after only one ring), it disconnects once again the phone T from the line PH and prepares itself to receive the next call from the central computer. During the second call, the computer asks the CPU unit its identification number, recorded in the memory M and necessary to distinguish that particular CPU from the other similar peripheral units; after having verified that the identification corresponds to a user up-to-date with payments, and that such user has not yet received the new secret code, the central computer transmits the new code and, as soon as the peripheral unit has confirmed the reception, it closes the transmission; the circuit BT then reconnects the user's telephone. The logic flow of the call by the central computer is schematically represented in Figure 5. Block 1 is the starting block of the calling operation to such a particular user; the checking goes on to the next block 1A. The block 1A is a check block; it checks whether a timer has accomplished its count (that is, whether it is time to recall a user previously busy); in the affirmative case the user should be recalled. Therefore the control operation goes on to a non represented block, as not making part of this operation; in the negative case the control goes over to block 2 (in all the check blocks the lower exit is the YES exit; the lateral exit is the NO exit). Block 2 provides to dial the telephone number of the first user on list to which the new secret code is to be communicated. Block 3 is a check block; it checks whether the number called is free; in the affirmative case the control passes to block 4; in the negative case the control goes over to block 13. Block 4 provides to close the call ( to interrupt the line) after one ring; furthermore block 4 zeros the second-counter of the timer; so the control goes over to the successive block 5. Block 5 is a check block; it checks whether 5 seconds have passed; in the affirmative case the control goes over to the successive block 6; in the negative case the control returns to block 5. Block 6 provides to dial the number of the user again for the second call; the control therefore goes on to block 7. Block 7 is a check block; it checks whether the number called is free; in the affirmative case the control goes over to block 8; in the negative case the control goes over to block 13. Block 8 provides to ask the peripheral station its identification number; after receiving it, it memorizes the number and passes the control to block 9. Block 9 is a check block; it checks whether the received number is up to date with its payments; in the affirmative case the control goes over to block 10; in the negative case the control goes to block 14. Block 10 is a check block; it checks whether the number received hasn't yet received its secret code; in the affirmative case (code not yet received) the control goes on to block 11; in negative case (code already received) the control goes to block 14. Block 11 provides to transmit the new secret code, and to record in its memory that the identification number has received the new code; then the control goes over to block 12. Block 12 is a check block; it waits for the confirmation of receipt by the peripheral station; in the affirmative case (occured reception) the control goes over to block 14; in the negative case (reception not yet occured) the control goes back to block 12. Block 13 is a check block; it checks in its memory whether the user found busy before has already received another two calls; in the affirmative case the control goes to block 14; in the negative case the control goes to block 13A. Block 13A provides to add to the memory the number of calls made to that user and starts a timer that will count up to 15 minutes and, at expiry of that time, it raises a flag (cfr.block 1A). Block 14 is the conventional end of operation block. For security reasons the code is transmitted in a ciphered form so that a telephone interception not be sufficient to break the secrecy; the CPU unit provides in real time to decipher the code, by means of a memorized key in the memory M, and stores the new deciphered secret code in the interior register R. Since the interior register R is more difficult to accede to than an external memory CPU like the memory M, the secret code is, in such a way, more protected from actions of piracy; in fact a pirate needs to intercept a telephone call (being difficult as the time of call is unknown to him) and to read the memory M in order to know the decoding key of the transmitted code. On the other hand, the fact that the central computer transmits the code only once to each user, is meant to avoid the possibility that a pirate may obtain the code by knowing an identification number in order with payments. In one variation of the invention, represented in Figure 3, the circuit CB can be incorporated in the television receiver TV; in such a case even the battery B is useless; but a permanent connection is necessary between the circuit commutator BT and the circuit CB, i.e. the television receiver, to bring the telephone line to the modem incorporated within it; for the user this version is easier as he does not have to move the circuit CB between television and circuit BT, with the disadvantage that he must provide a double wire between the television and the circuit BT. Figure 4 represents a further variation of the system represented in Figure 1; it provides that the circuit CB be equipped with a normal three-pin telephone plug and that the user detaches the telephone every night and connects in its place the circuit BT; the commutation circuit BT is in such a case useless. This version has the drawback that the user cannot utilize the telephone at night, and therefore it may not be acceptable. An alternative is that the circuit CB, and more precisely the CPU, be able to dial the telephone number of the central computer; this way the user can move the circuit CB, connecting it to the telephone line; call the central computer, activating the call by means of a special button, in order to get the new code, and then replace the circuit CB and reconnect the telephone to the line socket. In this last version security is decreased, due to the lack of, for the user, the uncertainty of the connection time between the central computer and the peripheral unit; so the fact that the computer transmits the code only once to each user is of vital importance. It can be suitable that the number of the central computer be a toll free number and that the memory M, associated to said microprocessor already contains said toll free number to call the central computer and obtain the new secret code from it. It can also be provided that said microprocessor controls a visual indicator ( display ) indicating whether for that day the new secret code has already been inserted and for how long it will be valid; in such a case the microprocessor, besides memorizing the new code, also provides to memorize the date and the expiry time. Naturally it is advisable not to constantly change the secret code at fixed intervals. The characteristics of the described system become clear from the description outlined and from the annexed drawings. In the outlined description the advantages of the system object of the present invention are also clear. In particular they are represented by the fact that the secretness of the code is protected in the best way possible.	A system for the transmission and reception of encoded television signals, in which a television signal is encoded in order not to be received and reproduced in the normal way by normal television receivers, but only from receivers equipped with a suitable decoder, and in which the decoder includes a control circuit and receives, by telephone, a secret code from a central computer, the secret code being necessary for the decoding operation, characterized by the fact that said system provides that the control circuit (CPU), the memory (M) associated to it, a telephone modem (MD) and a battery feeding pad (B) be contained in a container (CB), extractable from the decoder and linkable to the telephone line (PH). A system for the transmission and reception of encoded television signals, according to claim 1, characterized by the fact that said decoder is individualized by an identification number. A system for the transmission and reception of encoded television signals, according to claim 2, characterized by the fact that said central computer (CC), once in contact with the control circuit (CPU) and before transmitting the new secret code, requires said identification number and checks if the holder of the decoder is up to date with his payments and whether that day the decoder individualized with that particular number has already received the new secret code. A system for the transmission and reception of encoded television signals, according to claim 3, characterized by the fact that said microprocessor (CPU) is provided to be in the position to call said central computer ( CC ) to get the new secret code. A system for the transmission and reception of encoded television signals, according to claim 4, characterized by the fact that in the memory (M) associated to said microprocessor (CPU) the toll free number is already contained in order to call said central computer (CC) and to obtain the new secret code. A system for the transmission and reception of encoded television signals, according to claim 4, characterized by the fact that said microprocessor (CPU) controls a visual indicator (display) that indicates whether for that day, the new secret code has been already inserted and for how long it will be valid. A system for the transmission and reception of encoded television signals, according to claim 6, characterized by the fact that said microprocessor (CPU), besides memorizing the new code, also provides to memorize the date and the expiry time of said code. A system for the transmission and reception of encoded television signals, according to one of the previous claims from 1 to 7, characterized by the fact that said secret code is changed at non fixed intervals. An apparatus for the reception of encoded television signals, according to the system of any of the previous claims.	EDICO SRL; EDICO S.R.L.	DINI ROBERTO ING; FARINA ATTILIO ING; ZAPPALA GIUSEPPE DR; DINI, ROBERTO, ING.; FARINA, ATTILIO, ING.; ZAPPALA', GIUSEPPE, DR.
EP-0489386-B1	489,386	EP	B1	EN	19,981,014	1,992	20,100,220	new	H04N7	H04N5	H04N7	H04N 7/088B	Method for receiving teletext transmissions	It is described an improved receiver for an information transmission system represented by a plurality of pages, each of which can be selected by the user, from those available, by giving the receiver a command signal that generates a sequence of figures which locates a specific page, comprising command means that provide a plurality of keys, operable by the user to generate command signals and control means connected to the command means to generate, in reply to the cited command signals, the previously cited sequence of figures and a circuit decoder connected to the said control means which are able to receive, to select and acquire the information pages after the reception of said sequence of figures. The main characteristics consist in that said control means gives the opportunity, during the search for the acquisition of the indicated page, to suspend the search and to pass on to the acquisition of the page nearest to the one indicated.	The present invention relates to a method for receiving teletext transmissions represented by a plurality of pages, each of which can be selected by the user, from those available, by sending the receiver a command signal that generates a sequence of figures that locates an indicated page and lets control means start a search of the indicated page.It is known that in many European countries, among which Italy, various systems (generically known with the English word teletext , and more specifically called televideo in Italy and Videotext in West Germany)are used that consent the transmission, together with the normal television signals, of additional information inserted in the video signal (such as digital encoded signals) in some of the free horizontal lines during the period of vertical return.These encoded signals, upon command of the user, are revealed by a specific decoder circuit, known and normally made with integrated monolithic circuits, inserted in the circuits of the television, in order to consent the visualization, on the television screen, of one of the transmitted information pages containing texts or graphics.The pages transmitted are usually several hundred, grouped in subjects (for example: news: Pages. 110-125, sport: Pages. 150-162, politics: Pages. 210-222, games: Pages. 315-345, Etc); on the first page (page 100) there is usually the general index of the subjects, and on several of the following pages, the table of contents for each subject with the numbers of the relative pages.Every time he wishes to receive a certain page, the user has to press three numerical keys in sequence in order to complete the number of three figures relative to the page he is looking for; the decoder begins to receive the pages transmitted, one after the other, by the sender; as soon as the one located by the sequence of figures introduced by the user is transmitted, the decoder acquires it.However it could happen that the page located by the formulated sequence of figures is not actually transmitted; in such a case the decoder waits for an indefinite period of time for it to arrive; in practice the decoder is blocked until the user notices the problem and modifies the order.This drawback usually happens with sets equipped with the so called 'next' key that automatically generates, when said button is pressed, the number of the three figures following the one of the page being visualized in that moment.A set of this type is, for example, the one described in the Italian patent application N.67521/A86 corresponding to DE-A-3 721 614.The aim of the present invention is to realize an improved receiver for Teletext transmission systems that easily avoids the previously mentioned drawbacks. It is known from DE-A-3622308 a method for receiving teletext transmissions of the above said type, wherein if the user inputs a page number, said number is compared with a stored list of received pages; if the input page number does not occur in said list, the next page in the list is acquired.The implementation of such method, however, requires that previously all the numbers of the receivable pages have been stored. The situation therefore cannot be updated in real time .In order to realise the mentioned aims, the subject of the present invention is a method having the characterising feacures indicated in claim 1.The characteristics and the advantages of the method for receiving Teletext transmissions according to this invention are indicated in the following description, carried out referring to the enclosed drawings, that are provided as a non-limiting example, wherein: Figure 1 represents the block diagram of the circuit part according to the invention of a Teletext signal receiverFigure 2 schematically represents the command unit of the receiver shown in Figure 1;Figure 3 represents the logic flow of the operation of a first realizing form of the control unit of the receiver as shown in Figure 1; Figure 4 represents the logic flow of the operation of a second realizing form of the control unit of the receiver as shown in Figure 1;Figure 5 represents the logic flow of the operation of a third realizing form of the control unit of the receiver as shown in Figure 1.In Figure 1, the reference number 1 indicates the command unit, number 2 the control unit, number 3 a small read and write memory (of the type commonly called RAM (Random Access Memory)) to memorize at least two, but preferably four page numbers; the mentioned memory can also be included in the control unit 2. Number 4 indicates the Teletext decoder, number 5 the page memory (eventually, of four or eight pages), number 6 indicates the visual system of the contents of the indicated page, and number 7 an additional display device to visualize the page number. Finally number 8 indicates a clamper which recognizes the teletext signal in video frequency. The command unit 1 can be of a known type, for example the keyboard of a remote control; it shall contain the usual keys numbered 0 to 9 and the other usual buttons for the command of the receiver, among which two buttons marked with the symbols + and - or with other equivalent symbols, such as rewind and forward , and a button to enable Teletext reception (that can be marked with the letter T or with an equivalent symbol); In Figure 2, that schematically represents the keyboard of a possible command unit, where the above-mentioned keys are exactly indicated.The control unit 2 according to the invention will be described later. The decoder 4, the page memory 5 and the display device 6 can be of the known type normally used with the well-known Teletext receivers; the display device 6 is normally represented by the picture-tube of the television set.The visual system 7 can be a seven segment LED display of the type known.Figure 3 represents, in a simplified form, and for the part of interest concerning the present invention, the logic flow that connects the logic blocks of a first realizing form of the control unit 2; such control unit can be realized indifferently with wired logic blocks or with a microprocessor system (programmed logic); the two systems are perfectly equivalent from a functional point of view.Block 10 is the initial block of operations; block 11 is a block that checks whether the T key has been pressed on the command unit 1; in the check blocks, in Figure 3, the exit in the bottom refers to the answer YES , the side exit refers to the answer NO . Thus if the answer is YES , i.e. if the T button has been pressed, block 11 gives the control to the following block 12; on the contrary, the control returns to block 11.Block 12 executes the following operations: clears a figures N counter;zeros the display of page number 7;arranges for the memory 3 to be written;passes the control to the following block 13.Block 13 adds a unit to the counter N and passes the control to the following block 14.Block 14 checks whether a numbered button has been pressed on the command unit 1; if so it passes the control to the following block 15, if not control returns to block 14.Block 15 sends to the display device 7 the number of the pressed key that is then visualized; the following block 16 sends the same number,appropriately encoded, to the addressed cell N of the memory 3, where it is memorized.Block 17 checks whether the counter N has reached number 3, i.e. it checks whether the three figure number of the indicated page has been completed; we will call such memorized number of three figures NO; in the affirmative case the control goes to the following block 18; otherwise the control returns to block 13.Block 18 arranges for the memory 3 to be read ( READ ), zeros the counter N and passes the control to block 19.Block 19 increments the counter N by one unit; block 20 extracts from the memory 3 the number memorized in the address cell N and sends it to the decoder 4.Block 21 checks whether the counter N has reached number 3; in the affirmative case it passes the control to the following block 22, on the contrary the control returns to block 19.Block 22 memorizes in the memory 3, the addresses following those previously used for the number NO and precisely to the addresses 4,5 and 6, the numbered sequence 999; we will call P this second number stored in the memory 3; it zeros a seconds recording timer; starts the operation for the search of the requested page and passes the control to the following block 23.Block 23 checks whether the timer registers less than 30 seconds; in the affirmative case it passes the control to block 23A; otherwise it passes the control to block 26A.Block 23A gradually acquires the numbers of the page transmitted and received one after the other; the number of the presently received page (unless it is a service page, whose number cannot be visualized), is transmitted to the following block 24.Block 24 checks whether the received number is smaller than the number NO stored in the memory 3; in the affermative case it gives the control back to block 23; on the contrary control passes to block 25 .Block 25 checks whether the received number is the same as the number NO stored in the memory 3; in the affirmative case the control passes to block 26, on the contrary the control passes to block 27.Block 26 acquires the page transmitted in that moment and shows it on the display device 6; it then passes the control to block 29. Block 26A acquires the page located by the second sequence (P) of figures stored in memory 3; it shows such sequence on the display device 7 and the page content on display 6; it then passes the control to block 29.Block 27 checks whether the second number (P) contained in memory 3 is higher than the received number; in the affirmative case it passes the control to block 28; otherwise it gives the control back to block 23.Block 28 stores the number received in the memory 3 as a new number P and gives the control back to block 23.Block 29 is the end operations block; in practice, it can give the control back to the initial block 10 or to any other block apt to a new cycle of operations.The functioning of the described circuit is the following. The control unit accepts from the command unit a three figured number (N0) and stores it in the memory 3; then it begins to gradually compare the numbers transmitted with the memorized one; if it finds the required number, it acquires and shows the relative page; every time that it finds a number higher than that required, it confronts it with the second number (P) in the memory, where 999 is initially written; every time that it finds a number higher than that required (N0), but lower than the one already stored in the memory (F), the new, lower one is memorized; if after 30 seconds it cannot find the required number, it concludes that it is not transmitted and it acquires and shows the page nearest to the required one, whose number (P) is in the memory. Of course, rather than just memorize the number which is nearest to the required one, it is also possible to memorize, in a special page memory, the content of the page located by such a nearest number, so that, at the end of the search, that page itself can be immediately viewed.For simplicity the functioning has been demonstrated in the case of the search of the following page ('next' function); the search of the preceding page works in the same way; it is sufficent to go to 000 with the second memory and to reverse the test of the block 27.With the described system we need, in the case of a vain search, to wait for at least 30 seconds to obtain the viewing of the nearest page; the system that will now be described, with reference to Figure 4, allows, in propitious cases, to considerably shorten the dely; however, such a system assures the result only if, in any three-fold of numbers transmitted in the cycle, more than a repeated page is ever contained.Figure 4 represents, in a simplified form, and regards the part of interest concerning the aims of the present invention, the logic flow that connects the logic blocks of a second realizing form of control unit 2.The blocks from 1 to 21 are the same as those of Figure 3; thus, they are neither represented nor described.Block 30 receives the control from the block 21 of Figure 3; it zeros the three boxes of the memory following the one occupied by the current page number (NO); for clarity sake we will indicate these three boxes with the symbols N1, N2 and N3; block 30 also zeros a flag F and then passes the control to block 31.Block 31 acquires the number of the page in transmission.Furthermore, Block 31 always recopies the content of the memory cell N2 in cell N1; the content of cell N3 in cell N2 and memorizes the number of the current page received (unless it is a service page, whose number cannot be visualized), in memory cell N3; the control passes to the following block 32.Block 32 checks if the number memorized in the N1 box of the memory is different from zero; in the affirmative case control passes to block 33; otherwise it returns to block 31. Block 33 checks whether there is a double condition: i.e. if N1 is higher than N2 and N1 is lower than N3; if both are satisfied, it means that number N2 corresponds to a repeated page and control returns to block 31; if at least one of the two is not satisfied, the control passes to block 34.Block 34 checks whether there is a double condition: i.e. if N2 is higher than N3 and N1 is lower than N3; if both are satisfied,it means that number N2 corresponds to a repeated page and control returns to block 31; if at least one of the two is not satisfied, control passes to block 35.Block 35 checks whether the indicated number N0 is the same as N2; in the affirmative case control passes to block 39; otherwise to block 36.Block 36 checks whether N0 is higher than N2; in the affirmative case control passes to block 37; otherwise it passes to block 38.Block 37 raises a flag F and passes the control to block 38.Block 38 checks whether there is a double condition: i.e. if N0 is lower than N2 and if the flag F is raised; if both are satisfied, it means that the NO number is not transmitted and N2 is the one nearest to it; the control passes to block 39; if at least one of the two is not satisfied, the control returns to block 31.Block 39 acquires the page located by the sequence of figures stored in the memory box N2; shows such sequence on display device 7 and the page content on display device 6; then passes the control to block 40.Block 40 is the end of operations block; in practice it can give the control back to the initial block 10 or to another block apt for a new cycle of operations.The functioning of the described circuit is the following. An analysis of all the consecutive threefold of page numbers received is gradually carried out; for this purpose the numbers (N1,N2) are memorized that locate the two previous pages received before the one that is in transmission (N3), therefore making an analysis of the series of three numbers (N1, N2, N3) being located if the.page (N2) preceding the one in transmission is a repeated page. If the page looked for (NO) is not found, but, after the number of a preceding, not repeated page (N2), lower than the indicated number (NO), the number of a preceding, not repeated page, (N2) higher than the indicated one (N0) is received, the search of the indicated page (NO) is interrupted and the page (N2) preceding the one in transmission is acquired instead of it, as the page nearest to the indicated one (NO).It is decided that the page (N2) preceding the one in transmission is a repeated page when the relationship (N1 less than N3), and one of the two relationships: (N1 higher than N2) or (N2 higher than N3) are simultaneously fulfilled.Of course also in this case the fact that the content of the N2 page is already stored in a special page memory when the control circuit decides to acquire such N2 page, is advantageous because in that case no further time is wasted; this is practicable; it is only necessary that the circuit stores, during the search, the content of the current page and keeps it for at least one turn; therefore two page memories to be used alternatively are needed; one contains the current page (N3), and the other the preceding page (N2).Also in this case, for simplicity, the functioning has been demonstrated in the case of search of the succeeding page ('next' function); the case of search of the preceding page is analogous; it is sufficent to appropriately modify the tests.The system described with reference to Figure 4 does not operate if the user, by mistake, indicates a page number that is out of range; for example the pages located by the numbers between 100 and 799 are usually transmitted; if the user indicates page 813 as the page to be looked for, it is not found and the system of Figure 4 is not able to realise that it does not exist as it cannot find numbers higher than that indicated.To obviate this drawback it is possible to make the control circuit locate and memorize, for instance when switching on the receiver, the highest page number actually transmitted; the process used can be analogous and very similar to that used in Figure 3 to find the nearest number to the indicated one.After that, if the indicated page to look for is of a number higher than said highest number, the control circuit does not make the search, and in such a case, it advises the user, for example by showing on the display device 7 the maximum number posible.Figure 5 represents the logic flow of the functioning of a third realizing form of the control unit of the receiver in Figure 1.The blocks from 1 to 21 are the same as those of Figure 3; thus they are neither represented nor described.Block 50 receives the control from Block 21 of Figure 3; it initiates the 4 boxes of the memory following that occupied by the current page number (N0); for simplicity sake we will indicate these 4 boxes with the symbols N1, N2, N3 and N4; block 50 writes 999 in box N1, and in box N3, and 000 in boxes N2 and N4; then passes control to block 51.Block 51 acquires the number of the page in transmission (that we will call NT from here in advance) and passes the control to block 52.Block 52 checks whether the.indicated number NO is the same as the number NT of the page in transmission; in the affirmative case control passes to block 59; otherwise it returns to block 53.Block 53 checks whether the number NT is the same as the memorized number N2; in the affirmative case it passes the control to block 55; otherwise to block 54.Block 54 checks whether the number NT is higher than the memorized number N2; in the affirmative case it passes the control to block 60; otherwise to block 61.Block 55 checks whether the number NO is higher than the memorized number N2; in the affirmative case it passes the control to block 58; otherwise to block 56.Block 56 checks whether the number NO is lower than the memorized numberN1; in the affirmative case it passes the control to block 58; otherwise to block 57.Block 57 sets N0=N3 if the search is for the following page ( next ) or N0=N4 if the search is for the preceding page; the control passes to block 68.Block 58 sets N0-N2 if the search is for the following page ( next ) or N0=N1 if the search is for the preceding page; the control passes to block 68.Block 59 acquires the page located by the sequence of figures stored in the memory box NO; it shows such sequence on the display device 7 and the content of the page on display device 6, and passes the control to block 68.Block 60 sets N2=NT, i.e. memorizes the number of the page in transmission in the memory N2; then it passes the control to block 61.Block 61 checks whether the number NT is lower than the memorized number N1; in the affirmative case it passes the control to block 62; otherwise to block 63.Block 62 sets N1=NT, or stores the number of the page in transmission in the memory N1; then it passes the control to block 63.Block 63 checks whether the number NT is lower than the indicated number NO; in the affirmative case it passes the control to block 64; otherwise to block 65.Block 64 checks whether the number NT is higher than the memorized number N4; in the affirmative case it passes the control to block 66; otherwise the control returns to block 51.Block 65 checks whether the number NT is lower than the memorized number N3; in the affirmative case it passes the control to block 67; otherwise the control returns to block 51.Block 66 sets N4=NT, i.e. it stores the number of the page in transmission in the memory N4; then it passes the control back to block 51.Block 67 sets N3=NT, i.e. it stores the number of the page in transmission in the memory N3; then passes the control back to block 51.Block 68 is the end of operations block; in practice it can give the control back to the initial block 10 or to any other block apt for a new cycle of operations.The functioning of the described circuit is the following. An analysis of all the page numbers received in at least one complete cycle is carried out; the lowest number received is found at the end of memory N1; in the memory N2 the highest number received; the lowest number received of all the numbers higher than the one originally indicated (NO) is found in memory N3; in memory N4 the number received that is the highest of all those lower than the number indicated in the beginning (NO) is found; at this point N3 is selected and shown, if the search was for the following number (or N4 if the search was for the preceding number); in case that the indicated number is out of range, N2 (or respectively N1) is selected and shown.The described system operates independently from the order in which the pages are transmitted in the cycle and by the fact that there are repeated pages or not.As it appears from the above description, the improved receiver for Teletext transmissions, according to the present invention, avoids the drawback of the endless search of a page which is not included in the ones transmitted.For the sake of simplicity, we have described the case of search and selection due to the introduction of the three figure sequence locating the required page; and it has been supposed that such a sequence is that immediately higher than the page being viewed in that moment; of course, the same search mechanism is valid and applicable also in cases in which the sequence of figures is automatically produced by the control unit itself, following a known proceeding, after the activating the 'next' button for the search of the page (or of a certain number, e.g. 4, pages) following the one being viewed; such following page (or pages) are usually stored in special memories to be shown on command; it is also natural to apply to such pre-storing search (or searches) the technique according to the described invention, so that the pages can be actually found and stored and the apparatus does not waste time in a useless search of a page that is not in the cycle.In the same way the described technique can be used, with simple and intuitive modifications, when the required page is that immediately before the visualized one.It is obvious that, maintaining the principle of the invention, many variants to the characteristics of construction of the improved receiver for Teletext transmissions described as an example are possible, without for this reason exceeding the limits of the present invention.For example, as normally the decoder 4 already includes a microprocessor, a variant to the described receiver can be realized integrating the control unit 2 with the decoder 4 in a single functional unit, whose operating is controlled by a single microprocessor, with an evident saving of means and therefore of cost.	Method for receiving teletext transmissions, represented by a plurality of pages, each of which can be selected by the user, from those available, by sending to the receiver a command signal that generates a sequence of figures that locates an indicated page and lets control means start a search of the indicated page, characterized by the following features: during the search of the indicated page (N0), said control means (2) memorize the numbers that locate the two pages received (N1, N2) preceding the one in transmission (N3),analyze the series of the three numbers (N1,N2,N3) so as to specify whether the page (N2) preceding the page in transmission is a repeated page,interrupt the search of the indicated page (N0) and acquire the page preceding the one in transmission as the nearest page to the indicated one, as soon as, after the number of a preceding, not repeated page (N2), smaller than the indicated number (N0), the number of a preceding, not repeated page (N2), higher than the indicated number (N0), is received.Method for receiving teletext transmissions, according to claim 1, characterized by the fact that, during the search of the indicated page (NO), said control means (2) acquire and memorize in one special page memory the content of the page (N2) preceding the one in transmission, so that, when the search of the indicated page (N0) is interrupted, the content of such preceding page (N2) is available for immediate viewing.Method for receiving teletext transmissions, according to claim 1, characterized by the fact that, during the search of the indicated page (NO), said control means (2), analyze the series of the three numbers (N1,N2,N3) and assume that the page (N2) preceding the one in course of transmission is a repeated page when the relation N1 less than N3, and one of the two relations: N1 greater that N2 or N2 greater than N3, are simultaneously satisfied.Method for receiving teletext transmissions, according to claim 1, characterized by the fact that, said control means (2) determine, for instance when switching on the receiver, the highest number of pages actually transmitted in the cycle, and that if the said indicated page (N0) is located by a number higher than that one, the cited control means do not carry out the search. Method for receiving teletext transmission, according tp any one of the preceding claims, characterized by the fact that said control means (2) interrupt the search of the sequence of figures generated by said command signal and begins the search of the nearest page also in case that said sequence of figures is not directly generated by the user but is automatically generated by a so called next command or a similar command.Method for receiving teletext transmissions, according to any one of the preceding claims, characterized by the fact that, during the search of the indicated page (N0), said control means (2), every time that a page is received, store its content, if it appears to be nearer to the one indicated (N0) than the last stored page.	EDICO SRL; EDICO S.R.L.	DINI ROBERTO ING; FARINA ATTILIO ING; ZAPPALA GIUSEPPE DR; DINI, ROBERTO, ING.; FARINA, ATTILIO, ING.; ZAPPALA, GIUSEPPE, DR.
EP-0489387-B1	489,387	EP	B1	EN	19,970,402	1,992	20,100,220	new	H04N7	H04N5	H04N7, H04N5	H04N 7/088B, H04N 5/45	Improved receiver of teletext transmissions	The present invention relates to a teletext transmissions receiver comprising means to receive a television signal, decoder means for obtaining also the associated teletext signal and display means to show a first chosen page; the main characteristic of the invention consists in that the receiver includes an additional means to also show simultaneously a second chosen page different from the first.	The present invention relates to a teletext transmissions receiver comprising means to receive a television signal, decoder means for obtaining also the associated teletext signal and display means to show a first chosen page. There are known teletext transmissions receivers that include means to receive a television signal and obtain the relative video signal, destined to be shown by means of a special image reproducing apparatus, and also comprising decoder means for obtaining also the eventual signal (known in Italy as RAI televideo) associated to it. This signal consists of a library of numbered pages that are transmitted in sequence during some lines of the field blanking of the television signal; said pages are opportunely encoded and for their reception a special decoder is necessary. The decoder allows to show one page, selected by the user among those transmitted, alternatively to or superimposed on the normal television image. There are also known television signals receivers that are able to show simultaneously on the screen, images that belong to two or more different television channels. Generally the image or the additional images are of a minor dimension than that of the main one; for example a second image is typically reproduced in one angle of the main image, with a reduced size of about a third; in many cases it is possible to vary the sizes of such a second image. This procedure is commonly designated with the initial P.I.P. taken from the English words Picture In Picture. Said known receivers do not however consent to show two pages simultaneously. Document EP-A-0 343 636 discloses a teletext receiver wherein a plurality of different teletext pages can be simultaneously displayed on a screen. Document EP-A-0 376 376 discloses a picture in picture receiver wherein two tuners generate the television signals to be displayed. The invention is based on the recognition of the fact that in certain cases it would be very useful to be able to consult simultaneously two teletext pages, for example to be able to consult a specific page without losing sight of the index page. The aim of the present invention is therefore to indicate a teletext transmission receiver more flexible than those known, able to satisfy the needs of the user not satisfied with the known receivers. The present invention achieves this aim by a teletext transmission receiver as set out in claim 1. Further aims and advantages of the present invention will result clear from the description that follows and from the annexed drawings, supplied as an explicit and non limitative example, in which: The figure schematically represents the diagram of a receiver of teletext transmission according to the invention. In the figure the reference letter A indicates the aerial, connected to the receiver in order to pick up teletext transmission available. Said aerial is connected to two conventional tuners indicated respectively with the reference numbers 1 and 4; to said tuners two signals amplifiers follow of intermediate frequency, also conventional, indicated respectively with the numbers 2 and 5. The amplifier 2 is connected in its output to a video detector 3; the amplifier 5, on its part, is connected in output to a video detector 6. The detector circuit 3 is connected to a block 14 that contains a teletext signal decoder, of a known type, and, downstream, a converter circuit from RGB signals to composite video PAL signals (for example a type integrated circuit MC 1377 of the firm Motorola); the detector circuit 3 and the block 14 are then connected to a commutation circuit video of signals 8; the video detector 6, on its part, is connected to a block 16, equal to the block 14; the detector 6 and the block 16 are connected to the commutation circuit 17, equal to the circuit 8; the two commutators 8 and 17 are both controlled from a processor 10, comprising a microprocessor circuit of known type, that provides, depending of the cases, to control -them in order to assure that at their output are present the signals of the normal images, or the teletext pages. The exit of the two commutators 8 and 17 are connected to circuit 7 signals manipulator comprising also a memory, so called, of the control board; in its turn connected with the processor 10. The circuit 7 is of a known type (for example the part that acts as a signals commutator, can be made using an integrated circuit 2014) and is able to combine and to memorize the relative video signals to one or more images and, under the control of the processor 10, is thus possible to send to the successive video circuit amplifier 9, a combined image (of the designated type exactly P.I.P.) containing for example a main image (corresponding to the video signal coming from the chain 4, 5, 6) and a second different image of reduced size situated in an angle of the first (corresponding to the video signal coming from chain 1, 2, 3 ). Such combined image is then shown by the television image reproducer indicated with the letter C, represented for example by a normal colour picture-tube, or other image display of type known. The circuit 11 is a normal audio signal amplifying chain, driving an acoustic reproducer 13; the circuit 12 is a normal signal generation block of deflection for the image reproducer C. Naturally provided, even if not represented in the figure, for simple reasons, are known means of selecting signals, associated to the main chain (4, 5, 6) as to that of the secondary (1, 2, 3), preferably of the type to synthesis of frequency with two P.L.L. (for example of the type TSA 5510 by Philips), inserted respectively in the syntonizers 1 and 4 and commanded through the I2C bus of the microprocessor 10. Appropriately commanding the commutators 8 and 17 and the mixer 7, it is possible to obtain on the screen of the image reproducer C various images: the television image of the main channel (1,2,3); a Teletext page of the main channel: the television image of the main channel together with the reduced television image of the secondary channel (4,5,6); a Teletext page of the main channel, together with the reduced image of a Teletext page of the secondary channel; the television image of the main channel together with the reduced image of a Teletext page of the secondary channel; a Teletext page of the main channel, together with the reduced television image of the secondary channel. Acting also on the syntonization of the two tuners, and precisely tuning them both to the same television signal, two other combinations are possible: the television image of the main channel together with the reduced image of a Teletext page of the same signal; a Teletext page of the main channel, together to the reduced image of another Teletext page of the same signal. In the case in which the reduced secondary image is that of a teletext page, it is advisable,so as to guarantee the legibility, that its dimensions are equal to about half of those of the main image. The microprocessor receives the appropriate command signals from the user through a telecontrol device of the type known (TC/RC); among such command signals there will also be one to decide whether there has to be shown on the screen the television image of the main channel or the Teletext pages of the same; and another to decide in analog order regarding the secondary channel. Such command signals will for example be obtained by means of one or more dedicated buttons of said telecontrol. Naturally to manage the video reproduction there shall be provided an analog command system of the processor 7; to decide whether or not to also show the secondary video signal (as in any normal receiver of the type P.I.P.). It is also provided a system of auxiliary visualization, indicated with the reference number 15, that serves to show the relative Teletext information (number of the requested page, number of the page received, Etc), useful particularly during the acquisition phase, in the case of superimposing a signal withdrawn from the secondary signal on the television image of the main signal. In fact in such a case and during the acquisition such information cannot be shown in the normal way, for the incompatibility of the pertinent synchronism signals to the two different television channels. Such system of auxiliary visualization can consist of a separate conventional display, or could also be obtained with the known method O.S.D. (on screen display) on the main screen. The characteristics of the receiver of teletext transmissions described are made clear by the description and the annexed drawings. From the description the advantages of receiver Teletext transmissions object of the present invention are also clear. In particular they consist in that it is possible to consult simultaneously two different pages. It is clear that the receiver of Teletext transmissions described is more flexible of than those known; it is also clear that numerous variants can be supplied by man skilled in the art, to the receiver of Teletext transmissions described as an example, without leaving the principles of novelty pertinent to the invention.	A teletext transmission receiver comprising means to receive a television signal, decoder means to also obtain the associated teletext signal and display means to simultaneously show a plurality of chosen teletext pages, characterised in that the receiver includes: a plurality of television signal tuner means (1, 4); a plurality of teletext decoder means (14, 16) respectively coupled to said television signal tuner means; a processor means (10); a combining and memorising means (7) coupled to said display means (C); a plurality of switching means (8, 17) controlled by said processor means (10), for selectively connecting said plurality of teletext decoder means (14, 16) to said combining means (7). A Teletext transmissions receiver, according to claim 1, characterized in that said combining and memorising means includes a device of the type P.I.P. (7) to show the second page with reduced dimensions, in the place of a part of the first. A Teletext transmissions receiver, according to claim 1, characterized in that said combining and memorising means includes a second page memory (16) and a commutator (17). A Teletext transmissions receiver, according to claim 2, characterized in that said receiver includes commutation means of the video signal (8,17) in order to visualize and select one of the following combinations: the television image of a main channel (1,2,3); a Teletext page of a main channel (1,2,3) the television image of a main channel together with the reduced television image of a secondary channel (4,5,6); a Teletext page of a main channel (1,2,3), together with the reduced image of a Teletext page of the secondary channel (4,5,6); the television image of a main channel (1, 2, 3) together with a reduced image of a Teletext page of the secondary channel (4,5,6); a Teletext page of a main channel (1,2,3), together with the reduced television image of a secondary channel (4,5,6). the television image of a main channel (1,2,3) together with the reduced image of a Teletext page of the same signal; a teletext page of a main channel (1,2,3), together with a reduced image of another teletext page of the same signal. A Teletext transmissions receiver, according to claim 4, characterized in that said receiver includes a telecontrol device (TC,RC) associated to said processor (10). A Teletext transmissions receiver, according to one of the previous claims, characterized in that said receiver includes a visualisation device (15) to show the number of said second teletext page.	EDICO SRL; EDICO S.R.L.	DINI ROBERTO; FARINA ATTILIO; DINI, ROBERTO; FARINA, ATTILIO
EP-0489391-B1	489,391	EP	B1	EN	19,970,205	1,992	20,100,220	new	C08L83	null	C08K3, C08L83	C08L 83/04+B4S	Extrudable curable organosiloxane compositions	The tear strength of cured organosiloxane elastomers can be increased and the compression set value reduced without adversely affecting other physical properties if the composition used to prepare the elastomer is curable by a platinum-catalyzed hydrosilation reaction and contains a mixture of two liquid diorganoalkenylsiloxy terminated polydiorganosiloxanes, one of which constitutes from 96 to 99.5 percent by weight of said mixture and contains the alkenyl radicals only at the terminal positions. The second polydiorganosiloxane contains both terminal alkenyl radicals and from 1 to 5 mole percent of alkenyl radicals on non-terminal repeating units.	This invention relates to extrudable organosiloxane compositions. More particularly, this invention relates to extrudable organosiloxane compositions that can be cured by a platinum-catalyzed hydrosilation reaction to form elastomers exhibiting superior physical properties, particularly tear strength and compression set value, without sacrificing other desirable properties such as tensile strength and processability of the curable composition. The present inventors have now discovered how to increase the tear strength of silicone elastomers prepared by curing silica-filled compositions comprising a diorganoalkenylsiloxy terminated polydiorganosiloxane, an organohydrogensiloxane as the curing agent and a platinum group metal-containing hydrosilation catalyst. They have accomplished this by incorporating up to 4 percent of a polydiorganosiloxane B, based on the total weight of polydiorganosiloxanes containing ethylenically unsaturated hydrocarbon radicals. From 1 to 5 mole percent of the silicon atoms of polyorganosiloxane B contain ethylenically unsaturated hydrocarbon radicals. An objective of this invention is to define a class of liquid curable organosiloxane compositions that yield elastomers exhibiting a combination of high tear strength with compression set values less than 35%. A preferred class of the present compositions can be transported by pumping using conventional equipment. The present compositions are cured using a platinum-catalyzed hydrosilation reaction. This invention provides a curable organosiloxane composition comprising the product obtained by mixing to homogeneity: (A) from 96 to 99.5 weight percent, based on the total weight of (A) and (B), of a first diorganoalkenylsiloxy terminated polydiorganosiloxane exhibiting a viscosity of 5 to 20 Pa·s at 25°C. and containing essentially no alkenyl radicals bonded to non-terminal silicon atoms; (B) from 0.5 to 4 weight percent, based on the combined weights of (A) and (B), of a second diorganoalkenylsiloxy terminated polydiorganosiloxane that is miscible with said first polydiorganosiloxane and exhibits a viscosity of from 0.1 to 20 Pa·s at 25°C., where from 1 to 5 percent of the non-terminal repeating units of said second diorganoalkenylsiloxy-terminated polydiorganosiloxane contain an alkenyl radical; (C) an amount sufficient to cure said composition of an organohydrogensiloxane that is miscible with (A) and (B) and contains an average of more than two silicon-bonded hydrogen atoms per molecule, (D) a hydrosilation catalyst comprising a metal from the platinum group of the periodic table or a compound of said metal, the amount of said catalyst being sufficient to promote curing of said composition at a temperature of from ambient to 250°C., and (E) from 10 to 60 weight percent, based on the weight of said composition, of a reinforcing silica filler that is treated with at least one organosilicon compound, a portion of which is sym-tetramethyldivinyldisilazane, where the organic radicals bonded to the silicon atoms of (A), (B) and (C) are monovalent hydrocarbon or halogenated hydrocarbon radicals, wherein the ingredients (A), (B), and (C) are miscible with each other and wherein the molar ratio of silicon-bonded hydrogen atoms to ethylenically unsaturated hydrocarbon radicals in the composition is 0.8 to 3. The present inventors discovered that the preferred silica treating agent further reduces the compression set values of the cured elastomer. The ingredients of the present compositions will now be discussed in detail. The inventive feature considered responsible for the unique combination of physical properties, particularly the high tear strength and low compression set, exhibited by elastomers prepared from the present curable composition is the presence in the composition of two specific types of miscible diorganoalkenylsiloxy-terminated polydiorganosiloxanes in a specified range of relative concentrations. The first of the two polydiorganosiloxanes, referred to hereinafter as ingredient A, exhibits a viscosity of from 5 to 20 Pa·s, contains vinyl or other ethylenically unsaturated radicals only at the terminal positions of the molecule and constitutes from 96 to 99.5 percent of combined weight of the two polydiorganosiloxanes A and B. The second of the two diorganoalkenylsiloxy-terminated polydiorganosiloxanes, referred to hereinafter as ingredient B, contains alkenyl radicals on from 1 to 5 mole percent of the non-terminal repeating siloxane units. Cured elastomers prepared using preferred compositions of this invention exhibit tear strength values of 35-45 kilonewtons/meter. Experimental data for these preferred elastomers demonstrates that the tear strength reaches a maximum as the concentration of ingredient B approaches about 3 weight percent, based on the combined weight of ingredients A and B and decreases with increasing concentration of ingredient B beyond the 3 percent level. The alkenyl radicals present in ingredients A and B contain from 2 to 10 carbon atoms. Preferred alkenyl radicals are terminally unsaturated and include but are not limited to vinyl, allyl and 5-hexenyl. The silicon-bonded organic groups present in ingredients A and B, in addition to alkenyl radicals, are the monovalent hydrocarbon or substituted hydrocarbon radicals described in detail in the following portions of this specification. The term essential absence of non-terminal ethylenically unsaturated radicals used to describe ingredient A means that the only ethylenically unsaturated hydrocarbon radicals present on the non-terminal silicon atoms of this ingredient result from impurities present in the reactants used to prepare this ingredient or from undesired rearrangements occurring during preparation of this ingredient. Ingredient A is a diorganoalkenylsiloxy-terminated polydiorganosiloxane and can be represented by the average general formula YR1 2SiO(R2 2SiO)xSiR1 2Y where Y represents an alkenyl radical containing from 2 to 10 carbon atoms, R1 and R2 are individually monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals containing from 1 to 20 carbon atoms, R1 and R2 are substantially free of ethylenic unsaturation and x represents a degree of polymerization equivalent to a viscosity of up to 20 Pa·s at 25°C. In preferred embodiments, the viscosity of ingredient A is from 5 to 15 Pa·s. The R1 and R2 radicals can be identical or different. Because ingredient A is an extrudable liquid at 25°C., at least one of the R2 radicals on each of the non-terminal silicon atoms is lower alkyl, most preferably methyl. The remaining R2 radical can be alkyl such as methyl or ethyl; substituted alkyl such as chloromethyl, 3-chloropropyl or 3,3,3-trifluoropropyl; cycloalkyl such as cyclohexyl; or aryl such as phenyl. Any R1 and R2 radicals other than methyl are preferably phenyl or 3,3,3-trifluoropropyl, this preference being based on the availability of the intermediates used to prepare these polydiorganosiloxanes and the properties of cured elastomers prepared by curing compositions containing these polymers. The alkenyl radical represented by Y have been defined in a preceding section of this specification. Methods for preparing the liquid polydiorganosiloxanes used as ingredients A and B of the present compositions by hydrolysis and condensation of the corresponding halosilanes or cyclic polydiorganosiloxanes are sufficiently disclosed in the patent and other literature that a detailed description in this specification is not necessary. Ingredient B is a liquid diorganoalkenylsiloxy-terminated polydiorganosiloxane that can be represented by the average general formula Y'R3 2SiO(R4 2SiO)y(Y'R4SiO)zSiR3 2Y'In this formula, Y' represents an alkenyl radical as defined for the Y radical of ingredient A, R3 and R4 are selected from the same group of monovalent hydrocarbon radicals and substituted monovalent substituted hydrocarbon radicals as R1 and R2. Because ingredients A and B should be miscible with one another, the silicon-bonded hydrocarbon radicals present in these ingredients should be selected from the same class, i.e. lower alkyl. These hydrocarbon radicals, including Y and Y' are preferably identical. The degree of polymerization represented by the sum of y and z is equivalent to a viscosity of from 0.1 to 10 Pa·s, preferably from 0.1 to 1 Pa·s and the ratio z/(y+z) is from 0.01 to 0.05, which specifies the requirement for this ingredient that from 1 to 5 mole percent of the non-terminal repeating units contain a vinyl radical. The degree of polymerization of Ingredient B is preferably less than the degree of polymerization of Ingredient A. Preferred embodiments of ingredient A include but are not limited to dimethylvinylsiloxy-terminated polydimethyl-siloxanes, dimethylvinylsiloxy-terminated polymethyl-3,3,3-trifluoropropylsiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane/3,3,3-trifluoropropylmethylsiloxane copolymers and dimethylvinylsiloxy-terminated dimethylsiloxane/methylphenylsiloxane copolymers. Preferred embodiments of ingredient B encompass all of the preferred polydiorganosiloxanes for ingredient A with the addition of from 1 to 5 mole percent of non-terminal organoalkenylsiloxane units, where the preferred organic group are alkyl containing from 1 to 4 carbon atoms, fluoroalkyl such as 3,3,3-trifluoropropyl and aryl such as phenyl. The vinyl radicals present in preferred embodiments of ingredients A and B can be replaced by other alkenyl radicals such as allyl and hexenyl. The organosiloxane compositions of this invention are cured by a platinum-catalyzed hydrosilation reaction. The curing agent is an organohydrogensiloxane containing an average of more than two silicon-bonded hydrogen atoms per molecule. The organohydrogensiloxane contains from as few as four silicon atoms per molecule up to an average of 20 or more and can have a viscosity of up to 10 Pa·s or higher at 25°C. The repeating units of this ingredient include but are not limited to HSiO1.5, R5HSiO and/or R52HSiO0.5 in addition to one or more of monoorganosiloxy, diorganosiloxane, triorganosiloxy and SiO4/2 units. In these formulae, R5 represents a monovalent hydrocarbon or halocarbon radical as defined hereinabove for the R2 radical of ingredient A. One preferred class of organohydrogensiloxanes are copolymers consisting essentially of the repeating units R53SiO1/2, R52SiO, R5HSiO and R5SiO3/2 units, where the RSiO3/2 units constitute from 0.5 to 50 mole percent of the copolymer. Copolymers of this type can prepared by a controlled hydrolysis of a mixture comprising the corresponding organosilicon halides, such as the chlorides or the corresponding alkoxides. These and other methods for preparing the preferred organohydrogensiloxanes of this invention are sufficiently well known that a detailed description is not required in this specification. A second preferred class of organohydrogen siloxanes contain repeating units represented by the formulae R52HSiO1/2 and SiO4/2. The concentration of R52HSiO1/2 units is equivalent to a concentration of silicon-bonded hydrogen atoms in the copolymer of from 0.5 to 5 weight percent. Proper curing of the present compositions requires that ingredients A, B and C be miscible with one another. To ensure sufficient miscibility the silicon-bonded hydrocarbon radicals that are present in the highest concentration in these ingredients should be selected from the same class, e.g. alkyl radicals. These hydrocarbon radicals are preferably identical. In particularly preferred compositions, these hydrocarbon radicals are methyl or combinations of methyl with either 3,3,3-trifluoropropyl or phenyl. The molar ratio of silicon-bonded hydrogen atoms to vinyl or other ethylenically unsaturated hydrocarbon radicals in compositions curable by a hydrosilation reaction is critical with respect to the properties of the cured elastomer. The optimum ratio for the present curable compositions will be determined at least in part by the molecular weights of ingredients A and B, the type of curing agent and the concentration of any resinous organosiloxane copolymer described hereinafter. For compositions of this invention, this ratio is from 0.8 to 3. The optimum range of this ratio for other curable compositions of this invention can readily be determined by those skilled in the art with a minimum of experimentation. For particularly preferred compositions of this invention, the molar ratio of silicon-bonded hydrogen atoms to vinyl or other ethylenically unsaturated hydrocarbon radicals is between 1 and 2. Hydrosilation reactions are typically conducted in the presence of a catalyst (Ingredient D) that is a metal from the platinum group of the periodic table or a compound of such a metal. Platinum, rhodium and compounds of these metals have been shown to effectively catalyze hydrosilation reactions. Platinum compounds such as hexachloroplatinic acid and particularly complexes of these compounds with relatively low molecular weight vinyl-containing organosiloxane compounds are preferred catalysts because of their high activity and compatibility with the organosiloxane reactants. These complexes are described in U.S. Patent No. 3,419,593. Complexes with low molecular weight organosiloxanes wherein the silicon-bonded hydrocarbon radicals are vinyl and either methyl or 3,3,3-trifluoropropyl are particularly preferred because of their ability to catalyze a rapid curing of the elastomer at temperatures of at least about 70°C. The platinum containing catalyst can be present in an amount equivalent to as little as one part by weight of platinum per one million parts of curable composition. Catalyst concentrations equivalent to from 5 to 50 parts of platinum per million of curable composition are preferred to achieve a practical curing rate. Higher concentrations of platinum provide only marginal improvements in curing rate and are therefore economically unattractive, particularly when the preferred catalysts are used. Mixtures of the aforementioned vinyl-containing reactants, curing agents and platinum-containing catalysts may begin to cure at ambient temperature. To obtain a longer working time or pot life , the activity of the catalyst under ambient conditions can be retarded or suppressed by addition of a suitable inhibitor. Known platinum catalyst inhibitors include the acetylenic compounds disclosed in U.S. Patent No. 3,445,420, which issued on May 20, 1969 to Kookootsedes et al. Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors that will suppress the activity of a platinum-containing catalyst at 25°C. Compositions containing these catalysts typically require heating at temperatures of 70°C. or above to cure at a practical rate. If it is desired to increase the pot life of a curable composition under ambient conditions, this can be accomplished using an olefinically substituted siloxane of the type described in U.S. Patent No. 3,989,667, which issued on November 2, 1976 to Lee and Marko. Cyclic methylvinylsiloxanes are preferred. Inhibitor concentrations as low as one mole of inhibitor per mole of platinum will in some instances impart satisfactory storage stability and cure rate. In other instances inhibitor concentrations of up to 500 or more moles of inhibitor per mole of platinum are required. The optimum concentration for a given inhibitor in a given composition can readily be determined by routine experimentation and does not constitute part of this invention. To achieve the high levels of tear strength and other physical properties that characterize cured elastomers prepared using the compositions of this invention, the compositions must contain a reinforcing silica filler. This type of filler is typically treated with one or more of the known silica treating agents to prevent a phenomenon referred to as creping or crepe hardening during processing of the curable composition. Any finely divided form of silica can be used as the reinforcing filler. Colloidal silicas are preferred because of their relatively high surface area, which is typically at least 50 square meters per gram. Fillers having surface areas of at least 300 square meters per gram are preferred for use in the present method. Colloidal silicas can be prepared by precipitation or a fume process. Both of these preferred types of silica are commercially available. The amount of finely divided silica used in the present compositions is at least in part determined by the physical properties desired in the cured elastomer. Liquid or pumpable polyorganosiloxane compositions typically contain from 10 to 60 percent by weight of silica, based on the weight of polydiorganosiloxane. This value is preferably from 30 to 50 percent. Silica treating agent are typically low molecular weight organosilicon compounds containing silicon-bonded hydroxyl groups or groups that can be hydrolyzed to hydroxyl groups in the presence of water. Typical hydrolyzable groups include halogen atoms such as chlorine amino and other groups containing a silicon-bonded nitrogen atom. Preferably, at least a portion of the silicon-bonded hydrocarbon radicals present on the treating agent are alkenyl radicals and the remainder are identical to a majority of the hydrocarbon radicals present in ingredients A and B. The present inventors discovered that when a symtetraalkyldivinyldisilazane constitutes a portion of the silica treating agent used to treat the reinforcing silica portion of the present curable compositions, cured elastomers prepared from these compositions exhibit lower values of compression set relative to elastomers prepared from curable compositions employing other conventional silica treating agents such as low molecular weight hydroxyl-terminated polydiorganosiloxanes. In preferred compositions, the alkyl groups on the silazane are methyl. Compression set is typically determined using ASTM test method D395. In accordance with this procedure, a sample of cured elastomer of known thickness, typically 1.25 cm., is compressed to 75 percent of its initial thickness in a suitable clamping device and then heated at a temperature of 177°C. for twenty-two hours. The sample is then allowed to stand for 0.5 hour under ambient conditions, at which time its thickness is measured. Compression set is calculated using the formula (A-C)/(A-B)x100, where A is the initial thickness of the sample, B is the thickness to which the sample is compressed during the test and C is the thickness of the final sample following compression and relaxation. Low values of compression set are required for certain end-use applications during which the cured elastomer is compressed between two mating surfaces to serve as a seal or gasket. In addition to the vinyl-containing polydiorganosiloxanes, curing agent, catalyst and silica filler the organosiloxane compositions of this invention can contain one or more additives that are conventionally present in curable compositions of this type. These materials are added to impart or enhance certain properties of the cured elastomer or facilitate processing of the curable composition. A small amount of water can be added together with the silica treating agent(s) as a processing aid. Typical additives include but are not limited to pigments, dyes, adhesion promoters, flame retardants, heat and/or ultraviolet light stabilizers and resinous organosiloxane copolymers to enhance the physical properties of the cured elastomer. Diatomaceous earth and calcium hydroxide are two preferred additives based on their ability to reduce the degradation in physical properties, particularly tensile strength and modulus and the increase in compression set value that occur when the cured elastomer comes into contact with oil heated to 150°C. or higher. The presence of calcium hydroxide also further reduces the compression set value of the cured elastomer. The silica filler can be treated in the presence of at least a portion of the other ingredients of the present compositions by blending these ingredients together until the filler is completely treated and uniformly dispersed throughout the composition to form a homogeneous material. The ingredients that are present during treatment of the silica typically include the silica treating agents and at least a portion of the polydiorganosiloxanes referred to herein as ingredients A and B. The organohydrogensiloxane and platinum-containing catalyst are typically added after treatment of the silica has been completed. If calcium hydroxide is one of the ingredients, it is also added at this time. Irrespective of the type of mixer used, blending of the silica, filler treating agent(s) and ingredients A and B is continued while the composition is heated at temperatures from about 100 to 250°C. under reduced pressure to remove volatile materials. The resultant product is then cooled prior to being blended with the organohydrogensiloxane (Ingredient C) and/or the platinum catalyst (Ingredient D), depending upon whether it is desired to prepare a one-part or two-part curable composition of this invention. The optional additives referred to hereinbefore can be added at this time or during blending of the silica with ingredients A and B. In-situ treatment of the silica can require anywhere from 15 minutes to 2 hours, depending upon the amount of material being processed, the viscosity of the material and the shear rate to which the material is subjected during processing. Alternatively, treatment of the silica can occur before the silica is blended with other ingredients of the present compositions. Methods for treating finely divided silica fillers prior to incorporating the silica into a polyorganosiloxane composition are known in the art. To ensure adequate blending of all ingredients, the mixing equipment in which the present compositions are prepared should be capable of subjecting the composition to a high rate of shear. The advantage of using this type of a high intensity mixer to prepare silica filled polyorganosiloxane compositions is taught in U.S. Patent No. 3,690,804, which issued to Minuto on June 1, 1976. In accordance with the disclosure of this patent, the tip of the stirring device in the mixer is rotated at a speed of from 25 to about 250 feet per second, which would generate considerable shearing forces. The exemplified compositions are blended in a Henschel high intensity mixer wherein the rotor was operated at a speed of 3800 revolutions per minute, equivalent to a rotor tip speed of 157 feet per second. Dough type mixers equipped with sigma shape blades, are not as efficient as mixers wherein the mixing surfaces are of a relatively flat paddle configuration. Examples of the paddle type mixers include the Henschel mixer disclosed in the aforementioned Minuto patent and certain mixers manufactured by Neulinger A.G. The blade is preferably rotated at a speed of at least 100 revolutions per minute. Curable compositions prepared using the present method typically exhibit viscosities of about 0.5 up to about 10,000 Pa·s at 25°C. Preferred compositions are extrudable. To facilitate blending and transfer of the compositions and minimize entrapment of air during mixing a viscosity of less than about 10 Pa·s at 25°C. is preferred, particularly for extrudable compositions. Because mixtures of ingredients A and/or B with the curing agent (ingredient C) and the platinum-containing catalyst may begin to cure under the conditions encountered during storage of these composition even in the presence of a catalyst inhibitor, to ensure long term storage stability it is desirable to separate the curing agent and the catalyst until it is desired to cure the composition. This can be achieved by packaging the curing agent and curing catalyst in separate containers or by encapsulating the curing catalyst in a thermoplastic organic or silicone resin that melts or softens at the temperature to which the composition is intended to be heated during the curing process. One part compositions curable by a platinum-catalyzed hydrosilation reaction and containing as the hydrosilation catalyst a liquid platinum compound that is microencapsulated within a thermoplastic organic polymer together with methods for preparing the microencapsulated catalyst are described in U.S. Patent No. 4,766,176, which issued to Lee et al. on August 23, 1988. The present curable compositions can be formed into shaped articles by press molding, injection molding, extrusion or any of the other methods used to fabricate organosiloxane compositions. In the absence of one of the aforementioned catalyst inhibitors or an encapsulated catalyst, the compositions will cure at ambient temperature over a period of several hours or days or within several minutes when heated at temperatures of up to 250°C. Compositions containing one of these catalyst inhibitors are typically cured by heating them for several minutes at temperatures of from 50 to about 250°C. A preferred range is from 100 to 200°C. It should be apparent that compositions containing a microencapsulated catalyst must be heated to at least the melting or softening point of the encapsulating polymer to liberate the catalyst. Cured elastomeric articles prepared using the curable compositions of this invention exhibit tear strengths above about 230 pounds per inch (38 kN/m) and low values of compression, that are typicially below 25% without adversely affecting other desirable properties of the cured elastomer or the extrudability of the composition from which it is formed. This unique combination of properties make the elastomers desirable for a number of end use applications, including gaskets and fabricated articles wherein at least a portion of the article is relatively thin and subjected to large amounts of stress. Articles of this type include diaphragms and bladders. The following examples describe preferred curable compositions of this invention and the desirable properties of elastomers, particularly low values of compression set and high tear strength, prepared by curing these compositions. The example is intended to illustrate the present invention and should not be interpreted as limiting the invention as defined in the accompanying claims. Unless indicated to the contrary, all parts and percentages are by weight and all viscosities were measured at 25°C. Example 1This example demonstrates the improvement in tear strength and compression set of cured elastomers achieved by including from 1 to 3 percent, based on the total weight of vinyl-containing polydiorganosiloxanes, of a polydiorganosiloxane containing vinyl radicals on non-terminal silicon atoms when the viscosity of the polydiorganosiloxane containing vinyl radicals only on the terminal silicon atoms is less than the 20 Pa·s lower limit required by the compositions claimed in U.S. patent No. 4,753,978 to Jensen. Curable organosiloxane compositions were prepared by blending to homogeneity in a dough type mixer the entire quantity (325 parts) of a fume silica having a nominal surface area of 380 m2 per gram, 62.5 parts of diatomaceous earth, 1.9 parts of sym-tetramethyldivinyldisilazane, 65 parts of hexamethyldisilazane, 9.4 parts water and 422.5 parts of a dimethylvinylsiloxy terminated polydimethylsiloxane having a viscosity of about 10 Pa·s at 25°C. (ingredient A). This mixture was heated for one hour by circulating steam through the jacket of the mixer while volatile materials were removed under reduced pressure. Following completion of the heating cycle the resultant master batch (composition I) was blended to homogeneity with the quantities of ingredients A and B specified in the following Table 1 together with 7.2 parts of a silanol terminated polydimethylsiloxane having a viscosity of about 0.04 Pa·s at 25°C. and containing about 4 weight percent of silicon-bonded hydroxyl groups. Ingredient B was a dimethylvinylsiloxy-terminated dimethylsiloxane/methylvinylsiloxane copolymer exhibiting a viscosity of 0.3 Pa·s and containing 2 mole percent of methylvinylsiloxane units. Two-part curable compositions of this invention and compositions evaluated for comparative purposes were prepared by dividing each of the resultant mixtures (composition II) into 250 gram samples. A 250 gram sample of each composition evaluated was blended to homogeneity with one of two different organohydrogensiloxanes and ingredient D, a reaction product of hexachloroplatinic acid and sym-tetramethyldivinyldisiloxane that had been diluted with a liquid dimethylvinylsiloxy terminated polydimethylsiloxane in an amount sufficient to achieve a platinum content of 0.7 weight percent, based on the weight of both parts of the curable composition. The amount of ingredient D, the catalyst for the curing reaction of the composition, was equivalent to from 5 to 10 parts per million parts by weight of platinum, based on the weight of the complete curable composition. One of the two organohydrogensiloxanes, (C1) contained 0.8 weight percent silicon-bonded hydrogen, exhibited a viscosity of 0.016 Pa·s and corresponded to the general formula (Me3SiO1/2)12.7(Me2SiO)29.1(MeHSiO)54.6(MeSiO3/2)3.6. The second (C2), a contained 1 weight percent of silicon-bonded hydrogen atoms, exhibited a viscosity of 0.024 Pa·s and was represented by the general formula (SiO4/2)4.4Me2HSiO1/2)8. 0.5 grams of methylbutynol as a platinum catalyst inhibitor (ingredient F) was also added to each of the compositions. The amount of ingredient C1 or C2 added was equivalent to a molar ratio of silicon-bonded hydrogen atoms to vinyl radicals in the total curable composition of 1.25. The compositions were cured in the form of sheets having a thickness of 1.9 mm. by confining the compositions in a chase that was then placed in hydraulic press. The compositions were heated for 5 minutes at a temperature of 150°C. Test samples were then cut from each of the sheets to determine the physical properties of the cured materials. The American Society of Testing Procedures (ASTM) method used to measure the various properties evaluated included ASTM-412 for tensile strength and elongation, ASTM-D625, Die B for tear strength, ASTM-D2240, Shore A scale for durometer hardness values and ASTM D395 for compression set values. Table 1 summarizes the parts by weight of ingredients A and B added to composition I and the amounts of ingredient C1 and C2 added to composition II. The physical properties of the cured compositions are summarized in Table 2. Sample No. Ingredient A (parts) B (parts) C1 (grams) C2 (grams) 1196.36.3 (1%)1.980 2183.618.8 (3%)2.150 3171.331.3 (5%)2.320 4158.843.8 (7%)2.480 5202.601.900 6196.3 6.3 (1%)01.59 7 183.8 18.8 (3%) 0 1.72 8171.331.3 (5%)01.85 9158.843.8 (7%)01.99 10202.6001.51 Sample No. Tear Strength kN/m Hardness (Shore A) Compression Set % Tensile Strength MPa 140.45326.86.2 246.35622.25.4 342.36128.55.4 417.56634.17.3 534.15232.88.1 614.75222.75.9 736.55723.15.4 817.56025.75.1 920.36429.47.0 1021.25329.28.3 The data in Table 2 demonstrate that by using the curable compositions of this invention one is able to substantially improve the tear strength and/or reduce the compression set of cured elastomers relative to prior art materials prepared using extrudable organosiloxane compositions without adversely affecting other desirable properties such as tensile strength, hardness and elongation. While the tear strength exhibited by comparative sample 3 was higher than the value for sample 1, sample 1 exhibited the lower compression set value. Example 2This example demonstrates the lower compression set values achieved using a silica treating agent of this invention. Curable organosiloxane compositions were prepared using the types and amounts of ingredients and the procedure described in the preceding Example 1. In this instance, the comparative examples replaced the 0.31 parts of sym-tetramethyldivinyl-disilazane (T1) used as the silica treating agent with 0.92 parts of a hydroxyl terminated dimethylsiloxane/methylvinylsiloxane copolymer containing about 10 weight percent vinyl radicals and about 16 weight percent hydroxyl radicals (T2). The concentration of vinyl radicals contributed to the composition by each of these silica treating agents was equal. The amounts of ingredients A and B added to the masterbatch and the amounts of organohydrogensiloxanes C1 or C2 added to prepare the curable compositions are summarized in Table 3 and the compression set values of the cured elastomers are summarized in Table 4. Sample No. Ingredient A PartsB PartsC1 Grams C2 Grams 11a196.36.31.980 11b196.36.301.59 12a183.818.82.150 12b183.818.801.72 13a171.331.32.310 13b171.331.301.82 Sample Treating Agent Compression Set Value (%) 11aT126.8 11aT262.0 11bT122.7 11bT263.2 12aT122.2 12aT269.1 12bT123.1 12bT272.4 13aT128.5 13aT249.9 13bT125.7 13bT263.2 In every instance, the sample prepared using the polyorganosiloxane as the filler treating agent exhibited a higher compression set value than the sample containing the disilazane-treated filler.	A curable organosiloxane composition comprising the product obtained by mixing to homogeneity: (A) from 96 to 99.5 weight percent, based on the total weight of (A) and (B), of a first diorganoalkenylsiloxy terminated polydiorganosiloxane exhibiting a viscosity of 5 to 20 Pa·s at 25°C. and containing essentially no alkenyl radicals bonded to non-terminal silicon atoms; (B) from 0.5 to 4 weight percent, based on the combined weights of (A) and (B), of a second diorganoalkenylsiloxy terminated polydiorganosiloxane that is miscible with said first polydiorganosiloxane and exhibits a viscosity of from 0.1 to 20 Pa·s at 25°C., where from 1 to 5 mole percent of the non-terminal repeating units of said second diorganoalkenylsiloxy-terminated polydiorganosiloxane contain an alkenyl radical; (C) an amount sufficient to cure said composition of an organohydrogensiloxane that is miscible with (A) and (B) and contains an average of more than two silicon-bonded hydrogen atoms per molecule, (D) a hydrosilation catalyst comprising a metal from the platinum group of the periodic table or a compound of said metal, the amount of said catalyst being sufficient to promote curing of said composition at a temperature of from ambient to 250°C., and (E) from 10 to 60 weight percent, based on the weight of said composition, of a reinforcing silica filler that is treated with at least one organosilicon compound, a portion of which is sym-tetramethyldivinyldisilazane, where the organic radicals bonded to the silicon atoms of (A), (B) and (C) are monovalent hydrocarbon or halogenated hydrocarbon radicals, wherein the ingredients (A), (B), and (C) are miscible with each other and wherein the molar ratio of silicon-bonded hydrogen atoms to ethylenically unsaturated hydrocarbon radicals in the composition is 0.8 to 3.	DOW CORNING; DOW CORNING CORPORATION	GRAY THOMAS EDWARD; JENSEN JARY DAVID; GRAY, THOMAS EDWARD; JENSEN, JARY DAVID
EP-0489392-B1	489,392	EP	B1	EN	19,970,122	1,992	20,100,220	new	C12Q1	C12N1	C12M1, C12N1, C12Q1	C12Q 1/04B	Culture medium supplement for fastidious organisms	The present invention is a fastidious organism supplement which comprises growth factors and components to neutralize the toxicity of a polyanionic anticoagulant. The supplement is useful to isolate, grow, recover and/or enhance detection of fastidious organisms in culture media.	1. Field of the InventionThis invention relates to a fastidious organism supplement, and more particularly to a neutralizing supplement, and to a method for making the supplement. 2. Description of Related ArtA polyanionic anticoagulant is an essential ingredient in all blood culture media. Sodium polyanetholesulfonate (SPS) and sodium amylosulfate (SAS) are examples of polyanionic anticoagulants that may be added to blood culture media. SPS, in particular, is routinely added to commercial blood culture media. SPS has many beneficial effects when used in culture media, such as the inhibition of enzymes, proteins and processes that inactivate the growth of microorganisms. Such enzymes, proteins and processes include phagocytosis, complement, lysozymes and aminoglycoside antibodies. However, SPS is toxic to many strains of organisms, including Neisseria meningitidis, Neisseria gonorrhoeae, Peptostreptococcusanaerobius, Streptobacillus moniliformis, Gardnerella vaginalis, and Mycoplasma sp. A discussion about SPS and the variables influencing the speed and recovery rate of microorganisms is incorporated by reference, C.L. Strand and J.A. Shulman, Bloodstream Infections, 21-44 (1988). Numerous attempts have been made to neutralize the toxic effect of polyanionic anticoagulants in different media, especially in blood culture media, and to enhance the isolation, growth, recovery and/or detection of fastidious organisms. The neutralization of SPS by hemoglobin has been reported by S.C. Edberg, et al. in Inactivation of the Polyanionic Detergent Sodium Polyanetholesulfonate by Hemoglobin. J. Clin. Microbiol. 18:1047-1050 (1983). It was reported that hemoglobin can inactivate SPS but since hemoglobin is one of the major constituents inside blood culture bottles, and since by lysis its concentration can change over time, it is extremely difficult to predict whether the amount of free hemoglobin will be enough to inhibit a particular isolate of Neisseria in an individual blood culture bottle. The neutralization of SPS by gelatin (typically 1.0 to 1.2% w/v) has been reported by M. Weinstein, et. al. in Controlled Evaluation of Modified Radiometric Blood Culture Medium Supplemented with Gelatin for Detection of Bacteriemia and Fungemia. J. Clin. Microbiol. 25:1373-1375 (1987). The presence of gelatin in SPS-containing blood culture medium was shown to significantly inhibit the recovery of a variety of fastidious organisms, including staphylococci and members of the Enterbacteriaceae family. U.S. Patent No. 4,217,411 to Le Frock, et al. discloses enrichment for enhancing the detection and growth of the etiological agents of bacteriemia comprising Fildes peptic digest of blood and certain other compounds. The enrichment comprises Fildes peptic digest, Vitamin B12, NAD, L-Glutamine, Co-enzyme A, Pyruvate, Catalase, Glutamate, Vitamin K1, Co-Carboxylase and Cysteine hydrochloride. The enrichment supports growth of a number of organisms, but does not contain a neutralizing effect for polyanionic anticoagulants. The addition of gelatin to blood culture media to prevent inhibition of various organisms caused by SPS has been suggested by Reimer, et al., in Controlled Evaluation of Trypticase Soy Broth with and without Gelatin and Yeast Extract in the Detection of Bacteriemia and Fungemia. Diagn. Microbiol. Infect. Dis. 8:19-24 (1987). However, the addition of gelatin without sufficient growth factors was found not to enhance the growth of fastidious organisms. It was concluded that blood culture media could not be used for non-blood samples by Abdou, et al., in Unsuitability of Blood Culture Media Containing Sodium Polyanetholesulfonate for the Detection of Fastidious Microorganisms in CSF and Other Blood-Free Body Fluids. Zbl. Bakt. Hyg., I. Abt. Orig. A 254, 109-117 (1983). It was found that SPS containing media could not be used for culturing cerebral spinal fluid and other blood-free body fluids and that media without anticoagulants could not be used to culture blood. Fastidious organisms in clinical microbiology, are difficult to isolate or cultivate on ordinary media because of their need for special nutritional factors. In particular, factor V and factor X are nutritional factors which stimulate the growth of a number of fastidious bacteria including Haemophilus influenzae, Haemophilus parainfluenzae and Gardnerella vaginalis. Since factors X and V cannot be made by fastidious organisms in a culture media, they need to be supplied nutritionally to a culture media for proper growth of the fastidious organisms. Factor X is haemin (hemin), a complex organic molecule which is present in hemoglobin in red blood cells. Several species of Haemophilus are examples of bacteria which require factor X or haemin for growth. Factor V is nicotinamide adenine dinucleotide, or NAD, a large complex organic molecule which is required for the growth of several fastidious bacteria, including some species of Haemophilus. NAD is present in whole blood and serum, but its level in these fluids is variable and not stable when in aqueous solution. Therefore, blood and blood products cannot be relied upon to serve as good sources of factor V. Most blood culture media do not contain adequate levels of these growth factors. This is due to the fact that most blood culture media are sterilized in manufacturing by autoclaving, and since some growth factors, such as factor V, are heat labile, factor V becomes inactivated. There are a number of available supplements for use in microbiological culture media which are intended to enhance the isolation of fastidious organisms. None of these supplements, however, provides growth factors and neutralizes the toxic effects of polyanionic anticoagulants. Available supplements for stimulating the growth and recovery of nutritionally fastidious microorganisms include Fildes Enrichment (sold by Becton Dickinson Microbiology Systems, Cockeysville, Maryland), ISOVITALEX® Enrichment (trademark of Becton, Dickinson and Company) sold by Becton Dickinson Microbiology Systems, Cockeysville, Maryland, BACTO® Supplements (trademark of Difco) sold by Difco Laboratories, Detroit, MI and Hemoglobin (sold by Becton Dickinson Microbiology Systems, Cockeysville, Maryland). Fildes Enrichment is a peptic digest of defibrinated sheep blood containing factor X, and possibly factor V. It is not able to neutralize the toxic effects of polyanionic anticoagulants in culture media. ISOVITALEX Enrichment, contains factor V, but does not contain factor X and is not able to neutralize the toxic effects of polyanionic anticoagulants in culture media. The BACTO Supplements include BACTO Supplements A, B, C and VX. BACTO Supplement A is a desiccated yeast concentrate which contains crystal violet, a dye which inhibits growth of many bacteria and is not acceptable as a blood culture medium supplement. BACTO Supplement A preserves the thermolabile and thermostable growth accessory factors, including glutamine, factor V, cocoarboxylase and factor X. BACTO Supplement A is unable to neutralize the toxic effects of polyanionic anticoagulants in culture media. BACTO Supplement B is a desiccated yeast concentrate which provides growth factors required to support the growth of both Haemophilus and Neisseria species. BACTO Supplement B preserves the thermolabile and thermostable growth accessory factors of fresh yeast, and contains factor V and factor X. BACTO Supplement B is unable to neutralize the toxic effects of polyanionic anticoagulants in culture media. BACTO Supplement C is a desiccated yeast concentrate which provides growth factors required to support the cultivation of Haemophilus influenzae and Neisseria gonorrhoeae. BACTO Supplement C contains the thermolabile and thermostable growth accessory factors of fresh yeast, including factor V, factor X and cocoarboxylase. BACTO Supplement C is unable to neutralize the toxic effects of polyanionic anticoagulants in culture media. BACTO Supplement VX is a lyophilized concentrate of growth factors used as an enrichment for the cultivation of Neisseria gonorrhoeae, Haemophilusinfluenzae and other fastidious organisms. BACTO Supplement VX contains factor V, but it does not contain factor X and is unable to neutralize the toxic effects of polyanionic anticoagulants in culture media. Hemoglobin provides factor X, is able to neutralize the toxic effects of polyanionic anticoagulants in culture media, but it does not contain factor V. The following table summarizes the characteristics of available supplements in regard to providing growth factors and polyanionic anticoagulant neutralization, in culture media. GROWTH FACTORSPOLYANIONIC ANTICOAGULANT NEUTRALIZATIONFACTOR XFACTOR VISOVITALEX-+- FILDES Enrichment+var.- BACTO Supplement XV-+- BACTO Supplement B++- BACTO Supplement C++- Hemoglobin+-+ var.=variable results The available supplements are not able to provide a combination of growth factors and polyanionic anticoagulant neutralization. Available supplements are for use in plated media or liquid media which normally do not contain polyanionic anticoagulants. Therefore, the available supplements do not contain properties that neutralize the toxic effects of polyanionic anticoagulants. The available supplements discussed in Table 1, will not allow the growth of fastidious organisms and in particular both Neisseria and Haemophilus species in blood culture medium when cultured from body fluids such as normally sterile body fluids other than blood. Such body fluids (i.e. cerebrospinal fluid, joint fluid, peritoneal fluid) are typically tested using solid, plated media, or nutrient broths other than blood culture media. Plated media cannot accommodate large sample sizes (maximum of about 0.2 ml) and cannot be used with automated blood culturing systems such as the BACTEC® system (trademark of Becton, Dickinson and Company) sold by Becton Dickinson Diagnostic Instrument Systems, Towson, Maryland. Blood culture media, however, may accommodate large sample sizes and can be used with automated blood culturing systems such as the BACTEC system. Freshly drawn whole blood generally suffices to neutralize the toxic effects of anticoagulants and provide necessary growth factors, but there are many problems and disadvantages in its use. Banked blood (such as outdated blood units, or commercially available sheep blood) sometimes does not contain sufficient amounts of necessary growth factors and therefore cannot be relied upon to support the growth of fastidious organisms, in particular, Haemophilus and Gardnerella strains. Thus, a special need exists for a fastidious organism supplement which neutralizes the toxic effect of polyanionic anticoagulants and provides necessary growth factors which are often absent or limiting in culture media, and to stimulate the isolation, growth, recovery and/or enhanced detection of fastidious organisms. SUMMARY OF THE INVENTIONThe present invention is a fastidious organism supplement (FOS) composition comprising: (a) NAD or a functional substitute thereof; (b) hemin or a functional substitute thereof; (c) an albumin or a functional substitute thereof; (d) a polycationic compound being a water soluble cationic polymer or oligomer; and (e) an acid and its salt or buffer. FOS may be used in microbiological cultures, without inhibiting the growth of fastidious organisms. A preferred supplement of the invention comprises: (a) NAD; (b) hemin; (c) bovine serum albumin; (d) water-soluble polycationic polymer; and (e) citric acid. A further aspect of the invention includes a method for making a fastidious organism supplement as defined above comprises: (a) freeze drying NAD, hemin and bovine serum albumin in a first vial; (b) mixing an aqueous reconstituting solution of water-soluble polycationic polymer or oligomer and citric acid in a second vial; and (c) adding said aqueous reconstituting solution to said freeze dried solution in said first vial. FOS is useful in stimulating recovery of nutritionally fastidious microorganisms from body fluids such as normally sterile body fluids which have been added to blood culture media. Primary applications include samples of pediatric blood, cerebrospinal fluid and synovial fluid which are tested using blood culture media. FOS solves the problem of using polyanionic anticoagulants in culture media without inhibiting the growth of organisms which are sensitive to polyanionic anticoagulants. FOS also solves the problem of providing growth factors which are often absent or limiting in culture media. An advantage of FOS is that it may be used in culture media methods for only neutralizing the toxic effects of a polyanionic anticoagulant, for only providing growth factors or a combination of both. A further advantage is that FOS can be used in automated blood culturing systems such as the BACTEC system. A further advantage of FOS is that it stimulates the growth, recovery, isolation and/or enhanced detection of both Haemophilus and Neisseria species in a culture media which may contain polyanionic anticoagulants. Another advantage of FOS is that it may be used in many types of culture media such as plated media and preferably in blood culture media. DETAILED DESCRIPTIONNicotinamide adenine dinucleotide (NAD) is a complex organic molecule and is useful for the growth of a number of fastidious organisms. The functional substitute for NAD includes, but is not limited to, β-nicotinamide adenine dinucleotide (β-NADH) (reduced form of NAD), β-nicotinamide adenine dinucleotide phosphate (reduced β-NADP or oxidized β-NADPH form of NADP), and in general any form of the related chemical which serves as a functional substitute for NAD, including all salt forms of these compounds. A desirable compound which serves as a functional substitute for NAD is β-NADH and the preferred compound is NAD. Hemin is a compound present in red blood cells and is useful for the growth of a number of fastidious organisms. The functional substitute for hemin includes, but is not limited to, hemoglobin, myoglobin, protoporphyrin, hematin, heme, protoheme and in general any related compounds which serve as a functional substitute for hemin. A desirable compound which serves as a functional substitute for hemin is hemoglobin and the preferred compound is hemin. An albumin has the capability to interact with and neutralize the toxicity of a polyanionic anticoagulant. The functional substitute for albumin includes, but is not limited to, bovine serum albumin, serum albumin, gelatin, globulins, soluble proteins, digests of proteins, free amino acids, arginine, histidine, lysine, choline salt, guanidine salt, water soluble cationic chemicals and protamine sulfate. A desirable albumin is serum albumin and the preferred is bovine serum albumin. Polycationic compounds also interact with and neutralize the toxicity of polyanionic anticoagulants. Since polycationic compounds are positively charged, polyanionic anticoagulants which are anionic molecules (negatively charged), will bind to polycationic compounds. The polycationic compound comprises water soluble polycationic polymers or oligomers. A desirable polycationic compound is GAFQUAT® 755N polymer (trademark of GAF, Wayne, NJ) sold by Serva Biochemicals, Inc. of Montvale, New Jersey. GAFQUAT 755N polymer is a vinylpyrrolidone (1-ethenyl-2-pyrrolidinone; CAS registry no.: 00053633-54-8). An acid and its salt or buffer allow the pH of certain components in a composition to be adjusted to produce optimum clarity and stability. An acid and its salt or buffer include, but is not limited to nonvolatile pH adjusting chemicals. Such chemicals include, but are not limited to, dicarboxylic acids and tricarboxylic acids. Dicarboxylic acids include, but are not limited to, malic acid, tartaric acid, mandelic acid, succinic acid, and fumaric acid. Tricarboxylic acid includes, but is not limited to, citric acid. A desirable acid is a tricarboxylic acid and the preferred acid is citric acid. The desired pH of the FOS composition is from 1.5 to 4.0, while the preferred pH is from to 2.0 3.5 and the most preferred pH is 2.5. FOS preferably may be used to stimulate the isolation of fastidious organisms such as, but not limited to, Neisseria meningitidis, Neisseria gonorrhoeae, Peptostreptococcus anaerobius, Streptobacillus moniliformis, Gardnerella vaginalis, Mycoplasma sp., Haemophilus influenzae, Haemophilus parainfluenzae and other strains of Haemophilus, Neisseria and Gardnerella. The isolation of the fastidious organisms includes their growth, recovery and/or enhanced detection in culture media. In an even more preferred embodiment of the invention, FOS comprises: (a) NAD; (b) hemin; (c) bovine serum albumin; (d) a vinylpyrrolidone polymer, such as GAFQUAT 755N; and (e) citric acid. FOS may be packaged in several configurations, wherein, all components are preferably sterile in their packaging and use. An illustration of four alternative packaging configurations are as follows: 1. All components of FOS are freeze dried and sterile water is used to reconstitute the components. 2. NAD or a compound which is the functional substitute for NAD is freeze dried along with any combination of the other components from none to all. Any component not freeze dried is in the aqueous solution and serves as the reconstituting fluid. 3. All components of FOS in solution are stored frozen or refrigerated. 4. All components of FOS are in aqueous solution. The above configurations are examples and are not the only possible ways in which FOS can be packaged. A preferable determinant of the FOS packaging configuration is to have NAD or a compound which is the functional substitute for NAD dried, frozen or refrigerated. FOS may be stored at refrigerator temperatures, from 2 to 6° C, wherein under those conditions, the FOS is stable for several weeks. FOS preferably may be used in a method which stimulates the isolation of fastidious organisms, in a culture media which lacks certain growth factors and/or which contains a polyanionic anticoagulant. Polyanionic anticoagulants include, but are not limited to, SPS and SAS. FOS is preferably used in blood culture media when used to culture body fluids, such as normally sterile body fluids, other than blood. Such body fluids (i.e. cerebral spinal fluid, joint fluid, peritoneal fluid) are typically tested using solid, plated media, or nutrient broths other than blood culture media. FOS is preferably used in automated blood culturing systems such as the BACTEC system. FOS is desirably used in a method for providing growth factors in culture media. FOS is preferably used in a method for neutralizing the toxic effects of a polyanionic anticoagulant in culture media. FOS is most preferably used in a method for neutralizing a polyanionic anticoagulant and for providing growth factors in culture media. FOS, as preferably used in accordance with this disclosure, may contain conventional additives and ingredients. Conventional additives include, but are not limited to, yeast extract, brain-heart infusion, trypticase soy digest and water. The examples are not limited to any specific embodiment of the inventio, but are only exemplary. EXAMPLE 1METHOD OF MAKING FOS AND THE EFFECT OF ADDING FOS TO A BLOOD CULTURE MEDIUMFOS was made and used as follows: 1. Vial number one comprised 20 ml of freeze dried components comprising NAD, hemin and bovine serum albumin and vial number two comprised 10 ml of reconstituting fluid, comprsing, GAFQUAT 755, citric acid and water. 2. The reconstituting fluid was transferred from vial number two to vial number one. 3. Components in vial number one were mixed so as to allow the freeze dried components to go into solution in the added fluid so as to form reconstituted FOS. The initial nominal concentration and concentration range of each ingredient in the reconstituted FOS are shown in Table 2. ComponentNominal ConcentrationConcentration RangeNAD0.10% (w/v)0.01% - 1.0% Hemin0.0015%0.00015% - 0.015% Bovine serum albumin7.5%0.15% - 22.5% GAFQUAT 755N polymer 1.65%0.30% - 75.0% Citric acid0.42% 0.05% - 5.0% 4. 2 ml of the FOS was then added to 30 ml of a blood culture medium. The final nominal concentration of each FOS ingredient in the blood culture medium is shown in Table 3. ComponentNominal ConcentrationConcentration RangeNAD0.0065% (w/v)0.0006% - 0.06% Hemin0.0001%0.00001% - 0.001% Bovine serum albumin0.50%0.01% - 1.5% GAFQUAT 755N polymer0.11%0.020% - 5.0% Citric acid0.03%0.003% - 0.3% EXAMPLE 2COMPARATIVE ANALYSIS OF AVAILABLE FASTIDIOUS ORGANISM SUPPLEMENTS TO THE FASTIDIOUS ORGANISM SUPPLEMENT OF THE PRESENT INVENTIONTesting was conducted to determine if the available fastidious organism supplements as compred to FOS, would allow the growth of Haemophilus influenzae, Neisseria gonorrhoeae and Neisseria meningitidis in a blood culture medium. The following amounts of fastidious organism supplements were used in solution in each BACTEC vial: (v/v) ISOVITALEC1% FILDES Enrichment5% BACTO Supplement XV1% BACTO Supplement B1% BACTO Supplement C1% Hemoglobin2% Whole Blood10-15% FOS6.25% Two strains of each organism were inoculated into the BACTEC NR 6A medium. Inoculum size was between 5 and 75 c.f.u. total per vial. The vials were incubated at 35 to 37°C and tested on a BACTEC 660 for positive growth values. If they were not instrument positive after seven days subcultures ware performed. Each condition was tested in duplicate and the results achieved were recorded as follows in Table 5. Time to Detection in Days ADDITION N. gc #1 N. gc # 2 N. men # 1 N. men # 2 H. flu # 1 H. flu # 2 NoneNGNG2.92/NDNDNG Whole Blood1.01.81.01.81.81.0 FILDESNGNGNGNG1.00.8 Hemoglobin1.81.81.01.8NDND ISOVITALEXNGNG1.91.8/NG5.02.0 BACTO Sup. XVNGNG1.81.8/ND4.02.0 BACTO Sup. BNGNG2.0/NG1.8NDND BACTO Sup. CNGNGNG1.81.80.8 FOS1.82.01.01.01.00.8 NG = No growth on subculture ND = No detection by instrument but subculture positive The above results show that FOS performed equally to whole blood in its ability to allow the growth of fastidious organisms in blood culture media. However, the available supplements were not able to allow the growth of both Haemophilus and Neisseria species.	A fastidious organism supplement comprising: (a) NAD or a functional substitute thereof; (b) hemin or a functional substitute thereof; (c) an albumin or a functional substitute thereof; (d) a polycationic compound being a water soluble cationic polymer or oligomer; and (e) an acid and its salt or buffer. The supplement of claim 1 wherein the functional substitute of NAD is selected from β-NAD, β-NADP and β-NADPH. The supplement of claim 1 wherein the functional substitute of hemin is selected from hemoglobin, myoglobin, protoporphyrin, hematin, heme and protoheme. The supplement of claim 1 wherein albumin or a functional substitute thereof is selected from serum albumin, bovine serum albumin, gelatin, globulins, soluble proteins, digests of proteins, free amino acids, arginine, histidine, lysine, water soluble cationic chemicals, choline, quanidine salts and protamine sulfate. The supplement of claim 1 wherein said acid is a dicarboxylic or tricarboxylic acid. The supplement of claim 1 having a pH of from 1.5 to 4.0. The supplement of claim 1 comprising: (a) NAD; (b) hemin; (c) bovine serum albumin; (d) water-soluble polycationic polymer; and (e) citric acid. The supplement of claim 7 wherein the components have the following concentrations in percent weight per volume: (a) 0.10 NAD; (b) 0.0015 hemin; (c) 7.5 bovine serum albumin; (d) 1.65 water-soluble polycationic polymer; and (e) 0.42 citric acid. A method for making a fastidious organism supplement according to any of claims 1-8 comprising: (a) freeze drying NAD, hemin and bovine serum albumin in a first vial; (b) mixing an aqueous reconstituting solution of water-soluble polycationic polymer or oligomer and citric acid in a second vial; and (c) adding said aqueous reconstituting solution to said freeze dried solution in said first vial.	BECTON DICKINSON CO; BECTON DICKINSON AND COMPANY	GOLDENBAUM PAUL E; GRAZIOSI ANN M; GOLDENBAUM, PAUL E.; GRAZIOSI, ANN M.
EP-0489393-B1	489,393	EP	B1	EN	19,960,228	1,992	20,100,220	new	G01N33	C07B59	G01N33, G21H5	G01N 33/534	Method and apparatus for labelling materials, especially monoclonal antibodies, with radioisotopes and simultaneously purifying the materials from unincorporated isotopes	Materials are labelled with a radioisotope by passing them through a column (10) packed with (a) beads (30) coated with an oxidizing reagent for coupling the radioisotopes to the materials, (b) an anion resin (36), and (c) a material (34) for trapping elemental isotope, and flowing a mixture of the radioisotope and a solution of the material to be labelled through the column.	1. Field of the InventionThe present invention relates to the preparation and use of molecules carrying attached thereon radiolabeled species. 2. Description of the Prior ArtThe use of radiolabeled therapeutic and diagnostic agents has recently received renewed interest. The development of monoclonal antibodies of high avidity and specificity has encouraged the development of new agents for diagnostic and therapeutic treatment of cancer. These radiolabeled monoclonal antibodies, ligands, unsaturated fatty acids and other compounds are finding clinical applications both in vitro (for example in radioimmunoassay systems) and in vivo (for example in diagnostic imaging,radiotherapy and other novel techniques such as radioimmunoguided surgery). Bifunctional chelates are being utilized to radiolabel biomolecules, e. g., antibodies and other agents with Y⁹⁰, In¹¹¹, Re¹⁸⁶, Ga⁶⁷ etc., for diagnostic and therapeutic purpose, however, I¹²⁵, I¹³¹ and I¹²³ remain the radioisotopes of choice for use with the method and apparatus of this invention. Several remote or semiautomatic radiolabelling, specifically radioiodination, systems have been described (see for example, Ferens JM, Krohn KA, Beaumier PL et al., High-level iodination of monoclonal antibody fragments for radiotherapy. J Nucl Med 1984;25:367-70; or James SFW., Fairweather DSL, Bradwell AR., A shielded sterile apparatus for iodinating proteins, Med Lab Sci 1983;40:67-8; or Henville A. Jenkin G., A simple and cheap remotely operated system for the iodination of proteins, Anal Biochem 1973;52:336-41). These systems are dependent on gel filtration columns to separate bound from free isotope and in line pumps to propel reagents from one vessel to another. Such systems are prone to leakage, difficult to shield, and require decontamination after use. Other shieldable, disposable and relatively cheap systems are reported (see for example, Weadock KS, Anderson LL, Kassis AI, A simple remote system for the high-level radioiodination of monoclonal antibodies; J Nuc Med All Sci 1989;33:37-41, or James Watson SF, Fairweather DS, Bradwell AR, A shielded, sterile apparatus for iodinating proteins, Med Lab Sci 1983;40:67-68.) but these systems are complex to use requiring manipulation of valves and positioning of needles. These systems are inherently less reliable for iodinating since the result will depend on the mechanics of vial coating and the timing of the iodination and purification reactions. These systems are also more difficult to shield than the present invention because there are multiple vials to shield (apparatus is spread out) and a lead wall is also required. Another technique is the 'single vial technique' described in U.S. patent No. 4,775,638. This technique, although simple looking, requires manipulations of reagents with a syringe, and the timing of incubations. The mechanics of vial coating with the iodination reagent, manipulation of reagents and timing of the reaction, contribute to reduced consistency of results. Also, it would be difficult to safely shield the user from the radiation field emanating from the syringe utilized in this method, especially when preparing therapeutic doses of I¹³¹ labeled agents. A similar technique to the 'single vial technique' described above is the Iodo-Bead™ method of Pierce Chemical. This method is essentially identical to the 'single vial technique' except that instead of coating the reaction vial with oxidant, one or more Iodo-Beads™ are added to the reaction vial. The same concerns for reagent manipulation, timing of incubation and shielding apply to this technique. In addition, the Iodo-Bead™ has a polystyrene base which will absorb oxidized iodine from the reaction mixture and thus reduce the percent incorporation of iodine into the agent of interest. Radioiodinated monoclonal antibodies and other radiolabelled compounds may soon serve as standard diagnostic and therapeutic tools in clinical oncology. When preparing these agents, the integrity of the agent must be maintained while minimizing personnel exposure to radioactivity, including direct exposure to radiation and internal exposure to the thyroid. Thyroid uptake of radioiodine can easily result if elemental radioiodine generated in the labeling process is not contained. The ability to prepare these agents in a consistent manner, including specific activity, yield and purity will be useful in evaluating potential therapies. Simplification of the radiolabeling process will allow widespread use of the new therapies as they become available. Summary of the InventionMany of the disadvantages of the prior art methods and apparatus are alleviated by this invention. According to the invention, a method of labelling materials with a radioisotope comprises the steps of providing a sealed column having an inlet end and an outlet end, the column being packed with sequential stages of (a) beads coated with an oxidizing reagent for coupling the radioisotopes to the biomolecule, (b) an anion resin, and (c) a material for trapping elemental radioisotope, and flowing a mixture of the radioisotope and a solution of the material to be labelled through the column, and collecting the purified product at the effluent side of the device. The radiolabeling reaction (incorporation of radiolabel into the functional material) and the purification reaction (removal of unincorporated radiolabel from the radiolabeled material) occur as the reaction mixture flows through the column. In addition, all unincorporated radiolabel is contained and trapped within the column, thus, reducing the quantity of radioactive waste generated and eliminating the need to handle this waste. In a preferred embodiment of the invention, the mixture is flowed through a device, typically a column, as described This method is particularly suited for labeling monoclonal and polyclonal antibodies for use in radioimmunoguided surgery, radiotherapy and diagnostic imaging. Consistent radiolabeled antibody yields and purity are obtained when utilizing this method without releasing volatile radioiodine. Higher yields of radiolabeled antibody are obtained when using the device compared to other methods. The apparatus used in the method is easily shielded and can be operated remotely if a pump such as a peristaltic pump is utilized to flow the reaction mixture through the column. Radiolabeling by this method is rapid and easy and does not generate radioactive waste except for that contained within the device itself. The invention also includes an apparatus for labelling materials with a radioisotope comprising a sealed column having an inlet and an outlet, the column being packed with, in the order named, (a) beads coated with an oxidizing reagent for coupling the radioisotope to the material, (b) an anion resin, and (c) a material for trapping elemental radioisotope, whereby when a radioisotope and a buffer solution of the material are passed through the column, the radioisotope becomes reactively coupled to the material. In a preferred embodiment of the invention, the beads of (a) are coated with an iodination reagent. Further the material for trapping elemental radioisotope is chloromethylated styrene resin. Additional material for trapping elemental isotope may be placed at the inlet end of the column. Finally, filters may be placed at the inlet ends and outlet ends of the column between beads (a) and (b). This particular apparatus has many advantages over similar devices of the prior art. For one, the higher surface area of the glass beads coated with an oxidizing agent enhances the reaction kinetics of the operation. The apparatus permits a more efficient conversion of the radiolabel to labelled materials. Virtually all the radioactivity is contained in one vessel and requires no valves or connectors. After use, the ends of the apparatus can be sealed and its entire contents remain self-contained for safe disposal. Exposure of the operator's hands to the radioactivity is not significant. The approaches of the prior art require significant hand manipulation of syringes or bottles thus making the possibility of radiation exposure to the hand a real concern. Finally, the apparatus of the invention permits higher specific activity of the labelled materials. Brief Description of the DrawingsThe invention may be more fully understood from the following detailed description thereof taken in connection with the accompanying drawings which form a part of this application and in which: Figure 1 is a cross-sectional view of a column for labelling materials with a radioisotope constructed in accordance with a preferred embodiment of this invention; Figure 2 is a system in which the apparatus of Fig. 1 may be used for labelling materials with radioisotopes; Figure 3 is a graph depicting the results of radiolabelling of Mab 17-1A; and Figure 4 is a graph depicting the results of radiolabelling human antibody utilizing the apparatus of this invention. Description of the Preferred EmbodimentThe apparatus of this invention may be best seen in Figure 1 in which a column 10 is depicted. The column has an inlet end 12 provided with an end cap 14 from which is connected a stainless steel inlet tubing 16 thence through silicone tubing 18 to a Luer adaptor with IV sites 20. The column also has an outlet end 22 which is provided with an end caps 14 which is connected through stainless steel tubing 16 thence silicone tubing 18 to a Luer adaptor 20. The interior of the column is packed with glass beads 30 coated with a mild oxidizing agent as will be described. Positioned upstream from the glass beads 30 is a chloromethylated styrene resin 32, a polyethylene frit filter 35 and an end plug 14. Positioned downstream from the glass beads is another filter 35 and an anion resin 36, chloromethylated styrene resin 34, a third filter 35, and an end plug 14. The apparatus of this invention may be used in a flow system depicted in Figure 2 in which the apparatus 10 receives a reaction mixture, as will be described, from the supply source 40, which is coupled by silicone tubing 42 through a peristaltic pump 44, through the device 10, and a filter 46, thence to a collection vial 48. The apparatus contains a bed of glass beads 30 which have been uniformly coated with an oxidizing agent for coupling the radioisotope to a material. While many radioisotopes as will be described may be used, the invention will be described for simplicity in the context of the iodination of an antibody. For the iodination of antibody, the preferred oxidant is Iodogen. Iodogen is a mild oxidizing agent (formula 1,3,4,6-Tetrachloro-3, 6-diphenyl glycoluril) which is insoluble in water. The use of this mild oxidant for coupling limits the chemical damage done to functional agents in the iodination process. A thin layer of iodogen (available from Pierce Chemical) is coated onto the beads using the chloroform solvent evaporation technique recommended by Pierce. This Iodogen coating does not wash off the beads when they are utilized as intended in the present invention, which is to serve as a mild oxidizing agent for the oxidation of iodide ion, and also by virtue of the large surface area of the glass beads, to expose the reaction mixture to a large oxidizing surface with which to react and thus dramatically increase the kinetics of the reaction involving the oxidation of iodide ion. In the preferred embodiment, the iodogen coated glass beads 30 are ∼100 µm (microns) in diameter as utilized in the device for iodinating mono or polyclonal antibodies or their fragments. The size of the glass beads used in the device determines the total iodogen surface area to which the functional agent is exposed during the coupling reaction. The total exposed iodogen surface area in turn determines the rate of reaction (kinetics) of the coupling reaction. In the preferred embodiment, a glass bead size has been chosen which provides a sufficiently rapid reaction rate that, the reaction mixture can be rapidly flowed through the device at 1ml per minute, and the flow rate can be increase or decreased ten fold, 0.1ml per minute to 10ml per minute, without effecting the yield (% coupling) from the device. In this way the consistency of results from the device is enhanced. In some instances the optimum glass bead diameter may be larger or smaller than 100 µm (microns) depending on the geometry of the device which in no way is restricted by this description, or by the physical or chemical properties of the functional agent of interest in the reaction mixture. Iodogen has been found to adhere well to glass beads, however, any material may be substituted for glass provided that the iodinating agent used adheres to the material and does not wash through into the radioiodinated product and that the material does not react with oxidized iodine, thus removing iodine from the reaction mixture. The geometry of the beads need not be spherical, and non-porous as well as very highly porous materials can be used to enhance the available surface area, however, the surface area of the carrier of the iodination reagent (oxidant) must be well known in order that the appropriate quantity of oxidant can be deposited thereon. The chemical agent coated onto the glass beads is not restricted to iodogen but can be any mild oxidizer which can be made to be insoluble in water by any method, either before or after the coating process. Other mild oxidizers which may be used include chloramine T, Lactoperoxidase and iodine monochloride, for example. The quantity of iodogen coated glass beads 30 utilized in the device will depend on the desired yield or iodine incorporation, geometry of the device and chemical and physical properties of the reacting functional agent as stated above. In the preferred embodiment, the apparatus contains an anion resin 36 through which the reaction mixture passes after passing through the iodogen coated glass beads. The anion resin 36 removes and traps I⁻, IO⁻, IO3 -, IO4 -, or other negatively charged iodine species thus effecting a purification of the radioiodinated functional agent. The preferred anion resin is Biorad Labs AG1X8 which has a high affinity for these iodine species. Other materials or methods such as gel filtration media, organic or inorganic ion exchangers, other methods for size exclusion chromatography, etc., which are well known in the art may be utilized in the device to effect a purification of the reaction product. The apparatus contains a bed of chloromethylated polystyrene resin 34 through which the reaction product passes after passing through the iodogen coated glass beads 30 and the anion resin 36. This chloromethylated polystyrene resin 34 absorbs and traps I₂, ICl, I⁺ or any other oxidized iodide species which may remain in the reaction product, thus effecting an additional purification step. There is enough resin present in this resin bed to absorb and trap any oxidized iodide present as an impurity in the reaction product as well as any amount of oxidized iodide that might be generated if all the iodide present on the anion resin previously described were oxidized. In this way, all radioiodine species are contained and trapped within the device. Other materials such as TEDA (Triethylenediamine), charcoal, any styrene based resins, or other materials well known in the art to absorb and trap oxidized iodide may be utilized in the device as a substitute for any chloromethylated styrene resins utilized in the preferred embodiment of this invention. The chloromethylated styrene resin bed described above has an additional function when the device is used to radioiodinate functional agents, which is to trap volatile radioiodine species that may be generated within the device at some time after the device has been used for the intended purpose. There is an additional, identical chloromethylated styrene resin bed 32 on the inlet side of the device, adjacent to the iodogen coated glass bead bed 30. In this way, there is a chloromethylated styrene resin bed at each end of the column which will absorb and trap any volatile oxidized radioiodine species which may be generated at some time after the use of the column. This renders the column free from radioactivity release to the environment. Best Mode for Carrying out the Invention The radiolabeling procedure is performed by passing the reaction mixture through the device and collecting the eluant using the system of Figure 2. The apparatus is composed of a cylindrical column, 60 mm (2.75 inches) long by 9.5 mm (0.375 inches) in diameter, containing the oxidant adjacent to an anion resin 36 with a chloromethyl styrene plug 14 at each end. The column can be glass or plastic. The column contains three polyethylene frit filters 35 having a pore size opening of ∼70 µm (microns). These frit filters 35 are placed within the glass column 10, one at each end and one separating the glass beads 30 from the anion resin 36. The frit filter 35 on the inlet side ensures the even application of the reaction mixture onto the device. The filter 35 between the glass beads 30 and the ion exchanger 36 eliminates mixing of these two components which could potentially generate oxidized iodine in used devices. The filter 35 on the outlet side prevents resin particles from entering the purified product. Frit filters 35 can be constructed of any inert material. The pore size of the frit filters 35 must be smaller than the resin particle size. The column has a means for introduction of the reaction mixture and elution of the purified product under sterile or semi-sterile conditions. In the preferred embodiment, the envelope of the column is a glass cylinder sealed at each end by a silicone rubber plug 14 which is penetrated by stainless steel tubing 16. Silicone rubber inlet and outlet lines 18 are connected to the stainless steel tubings 16. The ends of the silicon tubings are fitted with Luer adapters 20 with IV sites (Medex Corp.). In this way the device is sealed but accessible by piercing the IV sites on the inlet and outlet side of the device with a needle. To utilize the apparatus in a sterile condition, the device can be opened by removing the Luer adapters with IV sites and sterilized by the ethylene oxide technique. When the Luer adapters are reassembled using aseptic technique, the device becomes a sealed sterile unit. The radiolabeling reaction is initiated by flowing the mixture (from container 40) of monoclonal antibody and radiolabel through the apparatus. In the preferred embodiment, the reaction mixture is pumped onto the device with a peristaltic pump 44 (Figure 2) by piercing the IV site on the inlet side of the device with a needle connected to the outlet side of the pump tubing. The purified product is collected from the outlet side of the apparatus in the collection vial 48. A syringe or other method could be used to introduce the reaction mixture to the device. The reaction mixture is added in a buffered solution, preferably phosphate buffered saline at pH 7-7.5. For other proteins and molecules the optimum buffer parameters may be different but can be determined experimentally. The radioiodine can be ¹²⁵I, ¹²³I or ¹³¹I available commercially as NaI in NaOH, preferably at a pH of 8-10. The radioiodine should be premixed with the monoclonal antibody and buffer solution before introduction to the device. When iodinating monocolonal antibodies, the reaction mixture is introduced to the device at a flow rate ∼1 ml per minute. The flow rate can range from ∼0.1 ml to 10 ml per minute at room temperature without adversely effecting the yield and purity of the product. When iodinating other proteins or compounds the optimum flow rate may be different but can be determined by experiment. After the reaction mixture has been pumped onto the apparatus, the pump 44 is allowed to continue pumping until no more reaction product is eluting from the apparatus. In this way, the device is pumped dry or semi-dry. The apparatus is then rinsed by pumping 1 ml of the same buffer used to dilute the reaction mixture through the apparatus. The rinse, which contains ∼20% of the product can be collected together with the first elution of product. In the preferred embodiment, this method is used to iodinate monoclonal and polyclonal antibodies, however, the device can be used to radioiodinate any iodinatable species including any protein, any organic compound or biomolecule containing an activated phenyl group, i.e., a phenyl group with an electron donating group attached (examples of which include, -OH, -NH₂, -NHR, -NR₂), any organic compound or biomolecule containing heterocylic rings, i.e., certain histidyl moeities, any organic compound or biomolecule substituted with trimethylsilyl or tri n-butyl tin functional groups, tri n-butyl tin substituted phenyl groups not containing electron donating groups, any biomolecule containing tyrosine. Other species which can be radioiodinated via this method include steroids, fatty acids, peptides, proteins, hormones, enzymes, toxins, amino acids, and carbohydrates. Although, in the preferred embodiment the method is used to iodinate antibodies, the method can be adapted to include its use in radiolabeling antibody with other isotopes such as ⁹⁰Y, ¹¹¹In, ¹⁸⁶Re, ⁶⁷Ga and other radiometals. The present invention is partly based on the discovery of a method to improve the reaction kinetics of the iodination reaction, this kinetic effect was not utilized in the prior art. The improved reaction kinetics result when a mild oxidizing agent is made available on a very large surface area within the small volume of the device to react with a monoclonal antibody/radioiodine mixture. The large oxidizing surface presented to the reaction mixture increases the probability for molecular collisions which result in radioiodination of the antibody. The increased rate of iodination embodied by the present invention allows the assemblage of oxidation and purification components into a small, flow through design for the iodination of functional agents which is also very easily shielded when radioiodines are used. Example 1Radioiodination of a monoclonal antibody to colorectal cancer #17-1a (Centocor Corp.) was obtained as a 10 mg/ml solution in saline. ¹²⁵I was obtained from E. I. du Pont de Nemours and Company, Billerica, Massachusetts, Catalog No. NEZ033L as a high specific activity, reductant free solution of NaOH at a pH 8-10, at 4 mCi/ml, 17.4 Ci/mg. Radioiodination was accomplished utilizing a modification of the iodogen (1,3,4,6 tetrachloro-3, 6-diphenylglycoluril) method, Fraker, P.J. and Speck, J.C. Biochem. Biophys. Res. Commun. 80: 849-857 (1978), utilizing the iodogen as a thin coating on glass beads, in a flow through design of Fig. 1. Labeling was performed by passing 4.0ml of the antibody/radiolabel mixture through a device at a flow rate of 1ml per minute and collecting the eluant. A mixture containing 30 mg of F(ab')2 fragment of monoclonal antibody 17-1A (Centocor Corp.) and 1.43 mCi of ¹²⁵I as sodium iodide was diluted to a total volume of 4.0 ml with pH 7.4 phosphate buffered saline and pumped through the device at a flow rate of 1.2 ml/min. The eluant was collected and assayed by capintec ion chamber. A second solution composed of 4.0 ml of pH 7.4 phosphate buffered saline was then pumped through the apparatus of Fig. 1 and the eluant collected and assayed by capintec ion chamber. A sample of the product collected from the first eluant collection was analyzed for purity by instant TLC . The purity was 95% and the yield based on a combination of the two elutions was 89.9%. The degree of incorporation of I¹²⁵ into the 17-1a monoclonal antibody was found to be a function of the antibody concentration in the reaction mixture. In the antibody concentration range examined, (0.125-7.5 mg/ml) the incorporation yield varied from ∼50-90% and the product purity was ∼95% as determined by instant TLC . This data is shown in Figure 3. The radiochemical purity was determined by thin layer chromatography. A sample of the iodinated antibody was developed on a silica gel impregnated fiberglass instant TLC plate (Gelman Sciences). The developing solution is Normal Saline and the developed plate is read on an Auto Changer 3000 radiochromatogram scanner (Bioscan Inc., Washington, D.C.). The percent purity is calculated as the area under the peak of the radiation profile of the antibody divided by the area of the radiation profile of the TLC plate in its entirety. Example 2Generic human IgG was obtained from Cooper Biomedical (Malvern, PA) as a lyophilized powder which was reconstituted in 50 mm PBS solution at pH 7-7.5. A reaction mixture was prepared as is described in Example 1 but this time including the generic human IgG and passed through the apparatus of Figures 1 and 2. More specifically, a mixture containing 50 mg of generic human IgG and 917 uCi of ¹²⁵I as sodium iodide was diluted to a total volume of 4.0 ml with pH 7.2 phosphate buffered saline. This solution was pumped through a apparatus prepared as stated above at a flow rate of 1.2 ml/min, and the eluant collected and assayed with a capintec ion chamber. A second solution composed of 4.0 ml of pH 7.2 phosphate buffered saline was then pumped through the apparatus and the eluant collected and assayed by capintec ion chamber. A sample of the product was collected from the first eluant collection vial 48 and analyzed for purity by Instant TLC . The purity was 99% and the yield based on a combination of the two eluations was 86.8%. The results of this experiment are shown in Figure 4.	A method of labelling materials with a radioisotope comprising the steps of: providing a sealed column having an inlet end and an outlet end, the column being packed with sequential stages of (a) beads coated with an oxidizing reagent for coupling the radioisotopes to the materials, (b) an anion resin, and (c) a material for trapping elemental radioisotope, flowing a mixture of the radioisotope and a solution of the material to be labelled through the column. A method of claim 1 wherein the material is a monoclonal antibody. A method of claim 1 wherein the radioisotope is ¹²³I, ¹²⁵I, or ¹³¹I. A method of claim 1 wherein the radioisotope is ¹¹¹In or ⁶⁷Ga, ⁹⁰Y, ¹⁸⁶Re, ⁸⁹Y, or ¹¹¹Ag.. A method of claim 1 wherein the beads of stage (a) are coated with an iodination reagent. A method of claim 1 wherein the material for trapping elemental radioisotope is chloromethylated styrene resin. A method of claim 1 wherein the column is provided with an additional stage (c) at the inlet end. A method of claim 7 wherein the radioisotope is ¹²³I, ¹²⁵I, or ¹³¹I. A method of claim 7 wherein the beads of stage (a) are coated with an iodination reagent. A method of claim 7 wherein the column is provided with a filter at the inlet and outlet ends and between stages (a) and (b). A method of claim 10 wherein the beads of stage (a) are coated with an iodination reagent. Apparatus for labelling materials with a radioisotope comprising: a sealed column having an inlet and an outlet, the column being packed with, in the order named, (a) beads coated with an oxidizing reagent for coupling the radioisotope to the material, (b) an anion resin, and (c) a material for trapping elemental radioisotope, whereby when a radioisotope and a buffer solution of the material are passed through the column, the radioisotope becoming reactively coupled to the material. The apparatus of claim 12 wherein the beads of packing (a) are coated with an iodination reagent. The apparatus of claim 12 or 13 wherein the material for trapping elemental radioisotope is chloromethylated styrene resin. The apparatus of claim 12 wherein the column is also packed with an additional material for trapping elemental isotope at the inlet end. The apparatus of claim 15 wherein the column is provided with a filter at the inlet and outlet ends and between packings (a) and (b).	DU PONT; E.I. DU PONT DE NEMOURS AND COMPANY	TAYLOR WILLIAM R; TAYLOR, WILLIAM R.
EP-0489394-B1	489,394	EP	B1	EN	19,970,716	1,992	20,100,220	new	G06F11	G06F11	G01R31, H03M1, G06F3	G01R 31/3167, G01R 31/3185S1	Semiconductor integrated circuit	A semiconductor integrated circuit having a test circuit built therein is disclosed which comprises an A/D converter to be connected to an peripheral circuit, a digital circuit connected to the A/D converter, a digital signal switching device for connecting the output of the A/D converter and that of the digital circuit selectively and a boundary scan output circuit connected to the output of the digital signal switching device connects the A/D converter to the boundary scan output circuit in a normal mode and the signal fetched in the boundary scan output circuit are outputted therefrom in test mode. Semiconductor integrated circuits having an analog circuit built therein and an analog integrated circuit in which a test circuit is built-in are also disclosed.	The present invention relates to a semiconductor integrated circuit incorporating a test circuit for mass production test (referred to as a board test hereinafter) of printed circuit boards mounting semiconductor and other devices thereon. The quantity of functions incorporated into a board has been dramatically increased owing to the recent advancement of semiconductor technology. It is accordingly most important for a semiconductor integrated circuit mounted onto the board to be designed suitable for the board test in order to secure the quality of the mass-produced board. One representative technique therefor is the boundary scan employed as IEEE standard 1149.1-1990 IEEE Standard Test Access Port and Boundary-Scan Architecture (refer to Simplification of Board Test by Boundary Scan by Peter Hansen, et al. in Nikkei Electronics dated January 8, 1990, no. 490, pp. 301-7). Hereinbelow, one example of a semiconductor integrated circuit incorporating the aforementioned boundary scan test circuit will be depicted with reference to Fig. 4. Fig. 4 is a block diagram of a board mounting a conventional semiconductor integrated circuit. In Fig. 4, reference numerals denote respectively: 401 a board, 402, 403 integrated circuits A, B mounted on the board 401, 404 a digital signal input terminal of the integrated circuit A402, 405 a digital signal output terminal of the integrated circuit A402, 406 a digital signal input terminal of the integrated circuit B403 which terminal is connected to the digital signal output terminal 405, 407 a digital signal output terminal of the integrated circuit B403, 408 a digital signal input terminal of the board 401 which terminal is connected to the digital signal input terminal 404 of the integrated circuit A402, 409 a digital signal output terminal of the board 401 and connected to the digital signal output terminal 407 of the integrated circuit B403, 410 a test switching terminal connected in common to the integrated circuits A402 and B403, 411 a test signal input terminal of the board 401, 412 a test signal output terminal of the board 401, 413 a boundary scan input circuit, 414 a boundary scan output circuit, 415 a test signal output terminal of the integrated circuit A402, and 416 a test signal input terminal of the integrated circuit B403. The operation of the board mounting the conventional semiconductor integrated circuits in the structure as above will be discussed now hereinbelow. When the test switching terminal 410 is set for the normal operation mode, the boundary scan input circuit 413 of the integrated circuit A402 operates as a normal digital signal input circuit, taking a signal through the digital signal input terminal 408 into the integrated circuit A402. On the other hand, the boundary scan output circuit 414 of the integrated circuit A402 works as a normal digital signal output circuit, with outputting a signal through the digital signal output terminal 405 to the digital signal input terminal 406 of the integrated circuit B403. The integrated circuit B403 operates in the same manner as the integrated circuit A402. Therefore, the signal input through the digital signal input terminal 408 is, on the whole of the board, processed in the integrated circuits A402 and B403 and is outputted to the digital signal output terminal 409. If the mass producing quality of the board 401, that is, whether all the input/output terminals of the integrated circuits A402 and B403 are perfectly soldered is to be confirmed in this state, a signal output to the digital signal output terminal 409, when a complicated test data is input through the digital signal input terminal 408, should be compared with an expected value. According to this method, however, it is necessary to know the input/output response of the integrated circuits A402 and B403 during the normal operation beforehand, and moreover, it is difficult to specify which of the terminals is improperly connected in the case where the expected value is not obtained. The boundary scan test circuit has been devised to solve the aforementioned disadvantages. When the test switching terminal 410 is set for the test mode, the boundary scan input circuit 413 and the boundary scan output circuit 414 operate as shift registers connected in series. In other words, the signal input through the test signal input terminal 411 is, after making a round of the input/output circuit of the integrated circuit A402, outputted to the test signal output terminal 415 of the integrated circuit A402. The signal at the test signal output terminal 415 is input to the test signal input terminal 416 of the integrated circuit B403 and output to the test signal output terminal 412 of the board 401 after making a trip of the input/output circuit of the integrated circuit B403. The board 401 will be checked in a manner as described below. (1) After the test switching terminal 410 is set to the test mode, a signal to set a desired data in the digital signal output terminals 405 and 407 of the integrated circuits A402 and B403 is input through the test signal input terminal 411. The value of the digital signal output terminal 409 is first checked. (2) Then, the test switching terminal 410 is set to the normal operation mode and the signal from the digital signal input terminal 408 is taken inside through the digital signal input terminal 404 of the integrated circuit A402. The resulting signal from the digital signal output terminal 405 is taken into the integrated circuit B403 through the test signal input terminal 406. (3) The test switching terminal 410 is switched to the test mode again. The data taken into the integrated circuits A402 and B403 in the above (2) is taken outside through the test signal input terminal 412 in series and the value is checked. In the above-described procedure, it is possible to inspect the board 401 without knowing the function of the normal operation of the integrated circuits A402 and B403. Now, the integrated circuits A402 and B403 will be described more in detail with reference to Fig. 5. Fig. 5 is a block diagram indicating the internal structure of the conventional semiconductor integrated circuit, in which reference numerals respectively designate: 501 an integrated circuit, 502 to 504 digital signal input terminals (DI), 505 to 507 digital signal output terminals (DO), 508 a test switching terminal (TS), 509 a test signal input terminal (TI), 510 a test signal output terminal (TO), 511 to 513 boundary scan input circuits (CI), and 515 to 517 boundary scan output circuits (CO). Each of the boundary scan input and output circuits 511 to 513 and 515 to 517 has a digital signal input terminal D, a clock input terminal CK, a digital signal output terminal Q, a test switching terminal TS, a test signal input terminal TI, and a test signal output terminal TO. A digital circuit 514 performs the original function of the integrated circuit 501. The semiconductor integrated circuit of the above structure operates in a manner as follows. When the test switching terminal 508 is set to the normal mode, the boundary scan input circuits 511 to 513 and the boundary scan output circuits 515 to 517 serve as flip-flops, so that an input through D is output to Q and TO. Therefore, the integrated circuit 501 functions normally. Meanwhile, when the test switching terminal 508 is set for the test mode, the boundary scan input circuits 511 to 513 work as flip-flops to input a signal from TI and output the same to TO, while the boundary scan output circuits 515 to 517 work as flip-flops to have a TI input and Q and TO outputs. The TO output of the boundary scan input circuit 513 is connected to the TI input of the boundary scan output circuit 517. Accordingly, the digital signal input through the test signal input terminal 509 of the integrated circuit 501 is, passing through the six flip-flops, outputted to the test signal output terminal 510. The operation depicted with reference to Fig. 4 is thus realized. The internal structure of the boundary scan input circuits (CI) 511 to 513 and boundary scan output circuits (CO) 515 to 517 will be described by way of example with reference to Figs. 6 and 7. Fig. 6 is a circuit diagram inside the boundary scan input circuit within the conventional semiconductor integrated circuit shown in Fig. 5, in which reference numerals denote respectively: 601 a digital signal input terminal (D), 602 a clock input terminal (CK), 603 a digital signal output terminal (Q), 604 a test switching terminal (TS), 605 a test signal input terminal (TI), 606 a test signal output terminal (TO), 607 and 608 flip-flops, and 609 a digital signal switching device. The boundary scan input circuit in the above structure operates as described hereinbelow. With the test switching terminal 604 set to the normal mode, the digital signal switching device 609 is connected to the side of the digital signal input terminal 601. A data input terminal of the flip-flop 608 is connected to the output terminal of the digital signal switching device 609. Therefore, when a clock is fed to the clock input terminal 602, the data at the digital signal input terminal 601 is outputted to the digital signal output terminal 603 and the test signal output terminal 606. If the test switching terminal 604 is switched to the test mode, the digital signal switching device 609 is connected to the side of the test signal input terminal 605, so that the data at the digital signal input terminal 601 is outputted to the digital signal output terminal 603 and the data at the test signal input terminal 605 is outputted to the test signal output terminal 606. Fig. 7 illustrates an example of a circuit diagram inside the boundary scan output circuit of the conventional semiconductor integrated circuit of Fig. 5. In Fig. 7, reference numerals indicate respectively: 701 a digital signal input terminal (D), 702 a clock input terminal (CK), 703 a digital signal output terminal (Q), 704 a test switching terminal (TS), 705 a test signal input terminal (TI), 706 a test signal output terminal (TO), 707 and 708 flip-flops, and 709 a digital signal switching device. The operation of the above boundary scan output circuit will be explained below. When the test switching terminal 704 is set to the normal mode, the digital signal switching device 709 is connected to the side of the digital signal input terminal 701. Since the data inputs at the flip-flops 708 and 707 are both connected to an output of the digital signal switching device 709, the data at the digital signal input terminal 701 is outputted to the digital signal output terminal 703 and the test signal output terminal 706 when a clock is added to the clock input terminal 702. If the test switching terminal 704 is in the test mode, the digital signal switching device 709 is connected to the side of the test signal input terminal 705, and the data at the test signal input terminal 705 is outputted to the digital signal output terminal 703 and the test signal output terminal 706. The operation discussed with reference to Fig. 5 is realized by the above-described boundary scan input/output circuits. In the foregoing prior art, all the semiconductor integrated circuits on the board are supposed to be constituted of digital circuits. However, particularly in the case of processing video signals, there may be often mounted both analog circuits and digital circuits on the same board and the boundary scan method cannot meet the board test. From an article in Proceedings of the Custom Integrated Circuit Conference, May 1989, pages 22.4.1-22.4.4, IEEE, New York, US; P.P. Fasang: Boundary scan and its application to analog-digital ASIC testing in a board/system environment , a testing principle is known in which an integrated circuit contains boundary scan cells placed next to the signal pins. During normal application or mission function, a signal travels from the mission input through the boundary scan cell into the application circuit. The response from the application circuit travels out to the mission output pin through a second boundary scan cell. When the integrated circuit is mounted on a printed circuit board and the pins are not physically accessible, test data can be applied to the application circuit in a serial manner via the test data input pin. Likewise, the response from the application circuit can be captured into the boundary scan cell on the output board and serially shifted out via the test data output pin. In this article, also analog-digital testing is possible, but in order to manage the testing problem, the analog circuit parts must be separated from the digital circuit parts, and demultiplexers are used to observe the digitized analog input signals via the output boundary scan cells during testing, and multiplexers are used to control the digital circuit with digital test patterns applied during testing via the input boundary scan cells. It is an object of the present invention to provide a semiconductor integrated circuit having a test circuit built therein to facilitate the board testing of mass produced printing circuit boards each having both analog and digital circuits thereon, or analog circuits only. According to the invention, a semiconductor integrated circuit is structured as defined either in claim 1 or in claim 3. A preferable embodiment is defined in dependent claim 2. These and other features of the present invention will become clear from the following description taken in conjunction with the preferred embodiments thereof with reference to the accompanying drawings throughout which like parts are designated by like reference numerals, and in which: Fig. 1 is a block diagram of a board mounting a semiconductor integrated circuit according to a first embodiment of the present invention; Fig. 2 is a block diagram of a board mounting a semiconductor integrated circuit according to a second embodiment of the present invention; Fig. 3 is a block diagram of a board mounting a semiconductor integrated circuit according to a third embodiment of the present invention; Fig. 4 is a block diagram of a board mounting a conventional semiconductor integrated circuit; Fig. 5 is a block diagram inside the conventional semiconductor integrated circuit; Fig. 6 is a circuit diagram of a boundary scan input circuit within the conventional semiconductor integrated circuit of Fig. 5; and Fig. 7 is a circuit diagram of a boundary scan output circuit within the conventional semiconductor integrated circuit of Fig. 5. A semiconductor integrated circuit according to the present invention will be discussed with reference to the accompanying drawings. Fig. 1 is a block diagram of a board mounting a semiconductor integrated circuit according to a first embodiment of the present invention. As shown in Fig. 1 there are arranged an integrated circuit 102 according to the first preferred embodiment and an analog peripheral circuit 103 on a board 101. The integrated circuit 102 is comprised of an A/D converter 104 connected to the analog peripheral circuit 103 via an A/D convension input terminal 105 and reference voltage input terminals 106 and 107, a digital circuit 108 connected to outputs of the A/D converter 104, a digital signal switching device 109 consisted of an array of switching means for selecting either of outputs 110 and 111 of the A/D converter 104 and the digital circuit 108 and a boundary scan output circuit 113 connected to outputs of the digital signal switching circuit 109. The board 101 has a control terminal 112 for controlling the digital signal switching device 109 in accordance with control signals applied therethrough, a test signal input terminal 114 for inputting test signals to the boundary scan output circuit 113 in the test mode and a test signal output terminal 115 for outputting a signal resulted in response to a test signal input from the test signal input terminal 114. The operation of the board mounting the integrated circuit of the above-described structure will be depicted hereinbelow. What is different from the conventional example is that the A/D converter 104 is built in the integrated circuit 102, and the operation of the A/D converter 104 is achieved when being connected to the analog peripheral circuit 103 through the terminals 106 to 107. If the A/D converter 104 is improperly connected to the analog peripheral circuit 103 or the integrated circuit 102, this is detected from a shift of an output data of the A/D converter 104. For inspection of the connection, first, the digital signal switching device 109 is switched by the signal switching control terminal 112 to be connected to the output 110 of the A/D converter 104. At this time, the boundary scan output circuit 113 is held in the normal mode to take the outputs of the A/D converter 104 thereinto. Then, after the boundary scan output circuit 113 is set to the test mode, the output data of the A/D converter 104 is taken out from the test signal output terminal 115 in series. The taken-out data is compared with an expected value. Although an error is generated to the expected value because of the analog processing, the error is judged acceptable so long as it is within a preset allowance. According to the present embodiment, it is easily detected whether or not the analog circuit in the periphery of the A/D converter built in the digital integrated circuit is properly mounted with use of the boundary scan circuit. Fig. 2 is a block diagram of a board mounting a semiconductor integrated circuit according to a second embodiment of the present invention. In the drawing, reference numerals respectively denote: 201 a board, 202 an integrated circuit of the instant embodiment, 203 an analog peripheral circuit of the integrated circuit 202, 204 an analog circuit built in the integrated circuit 202, 205 an analog signal switching device, 206 to 207 analog signal input terminals to the integrated circuit 202, and 208 a test switching control terminal to control the analog signal switching device 205. Reference numerals 105 to 115 have the same functions as those indicated by the same references in Fig. 1. The operation of the board mounting the integrated circuit as above will be explained hereinbelow. The difference of the board of Fig. 2 from that of Fig. 1 is that both the analog circuit 204 and the A/D converter 104 are built in the integrated circuit 202. When the test switching terminal 208 is set in the normal mode, the A/D conversion signal input terminal 105 is connected to the output of the analog circuit 204, thereby performing the normal function. Meanwhile, since the test switching terminal 208 assumes two test modes, the A/D conversion signal input terminal 105 is connected either to the analog signal input terminal 206 or to the analog signal input terminal 207. Therefore, if the output of the A/D converter 104 is checked according to the same procedure as above in Fig. 1, it becomes possible to detect whether the analog signal input terminals 206, 207 or reference voltage input terminals 106, 107 are properly connected to the analog peripheral circuit 203, or whether the analog peripheral circuit 203 connected to these terminals works properly. According to the second embodiment, it is possible to detect the connecting state of the analog signal input terminals or the analog peripheral circuit even when the terminals or the circuit are directly connected to the A/D converter. Further in Fig. 3, there is shown a block diagram of a board mounting a semiconductor integrated circuit according to a third embodiment of the present invention. In Fig. 3, reference numerals denote respectively: 301 a board, 302 an analog peripheral circuit, 303 an analog integrated circuit, 304 a digital integrated circuit, 305 and 306 analog signal input terminals, 307 an A/D converter, 308 an analog signal switching device, 311 a boundary scan output circuit, 312 an analog circuit, 313 a test signal output terminal for the analog integrated circuit 303, 314 a test signal input terminal for the digital integrated circuit 304, 315 a test signal output terminal for the digital integrated circuit 304, and 316 a test signal output terminal of the board 301. The operation of the above-described board will be explained below. The board of the instant embodiment is different in that the analog integrated circuit 303 is incorporated into the boundary scan circuit. Therefore, there are provided inside the analog integrated circuit 303 the A/D converter 307, analog signal switching device 308 and boundary scan output circuits 311 for test purpose, besides the analog circuit 312. The state of the analog signal input terminals 305, 306 each of which is a connecting terminal to the analog peripheral circuit 302 is sequentially taken into the A/D converter 307 by a test switching control terminal 310 and taken out from the test signal output terminal 313 after being parallel-series converted in the boundary scan output circuits 311. Accordingly, it is detected whether or not the analog signal input terminals 305, 306 are connected well to the analog peripheral circuit 302, or the analog peripheral circuit 302 connected to these terminals is driven properly. Therefore, the third embodiment makes the board test possible even when the analog integrated circuit is built in the boundary scan circuit. As is described hereinabove, the following advantages are achieved by the present invention: (1) In a semiconductor integrated circuit comprising a digital circuit and an A/D converter, by providing digital signal switching devices to which are input outputs from the A/D converter and the digital circuit and, boundary scan output circuits connected to outputs of the digital signal switching devices, it becomes possible to inspect the connection of the semiconductor integrated circuit with an analog peripheral circuit for the A/D converter which circuit is mounted outside the semiconductor integrated circuit or the state of the analog peripheral circuit itself. (2) In a semiconductor integrated circuit comprising an analog circuit, an A/D converter and a digital circuit, by providing an analog signal switching device to which are input outputs from the analog signal input terminals and analog circuit, the A/D converter connected to an output of the analog signal switching device, the digital circuit connected to outputs of the A/D converter, digital signal switching devices to which are input outputs from the A/D converter and digital circuit, and a boundary scan output circuits connected to outputs of the digital signal switching devices, it becomes possible to inspect the connection of the semiconductor integrated circuit with an analog peripheral circuit mounted outside the semiconductor integrated circuit, or the state of the analog peripheral circuit itself. (3) In a semiconductor integrated circuit consisting of an analog circuit alone, by providing an analog signal switching device connected to outputs of analog signal input terminals, an A/D converter connected to an output of the analog signal switching device, and boundary scan output circuits connected to outputs of the A/D converter, it becomes possible, similar to the other digital semiconductor integrated circuits, to inspect the connection of the semiconductor integrated circuit with a peripheral circuit of terminals or the state of the peripheral circuit itself according to a simple inspecting program.	A semiconductor integrated circuit (102; 202) comprising an A/D converter (104) to be connected to an analog peripheral circuit (103; 203); a digital circuit (108) connected to the output side of said A/D converter (104); a digital signal switching device (109) connected to both the output side of said A/D converter (104) and the output side of said digital circuit (108) for switching its output from the output side (110) of said A/D converter (104) to the output side (111) of the digital circuit (108), or vice versa, in accordance with a switching control signal (112); and a boundary scan output circuit (113) connected to the output of said digital signal switching device (109) which is operable in a normal mode in which outputs of said digital signal switching device (109) are fetched thereinto and in a test mode in which the fetched outputs are outputted (115) therefrom sequentially in response to a test signal (114) applied thereto. A semiconductor integrated circuit according to claim 1, characterized by an analog circuit (204) connected between the analog peripheral circuit (203) and the A/D converter (104), and an analog signal switching device (205) for switching between the outputs of said analog peripheral circuit (203) and the outputs of said analog circuit (204) in accordance with a switching control signal (208). A semiconductor integrated circuit (301) comprising an analog circuit (312) to be connected, via analog signal input terminals (305, 306), to an analog peripheral circuit (302); an analog signal switching device (308) for switching the outputs of said analog peripheral circuit and the output of said analog circuit (312) in accordance with a test switching control signal (310); an A/D converter (307) connected to the output side of said analog signal switching device (308); and a boundary scan output circuit (311) connected to the output side of said A/D converter (307), said analog signal switching device (308) connecting the output (309) of said analog circuit (312) to said A/D converter (307) in a normal mode and switching the outputs (305, 306) of said analog peripheral circuit (302) sequentially to said A/D converter (307) in a test mode in accordance with said test switching control signal (310).	MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.	IMAI KIYOSHI; TAGUCHI SEIICHI; TAKADA TAKU; TSUJI TOSHIAKI; IMAI, KIYOSHI; TAGUCHI, SEIICHI; TAKADA, TAKU; TSUJI, TOSHIAKI; IMAI, KIYOSHI, 803, LIONSMANSION NIJOJO HIGASHI
EP-0489395-B1	489,395	EP	B1	EN	19,950,927	1,992	20,100,220	new	D06P1	D06P3	D06P1, D06P3	D06P 3/82V3, D06P 3/82V2, D06P 1/651B4	Dyed mixed knit fabric and method for its manufacture	A dyed union knit fabric comprised of at least a polyurethane elastic fiber containing a chlorine-induced degradation inhibitor in a proportion of 0.5-4.5 weight% relative to the weight of the fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, which has been dyed with mixed dyes of acid dyes, dispersion dyes, metal-complex dyes, reactive dyes and direct dyes, and markedly improved in resistance to chlorine-induced change in shade by allowing to contain at least one compound having a reaction amount of chlorine of 50 milliequivalent per gram or more, specifically one member of mono- and/or polyhydroxybenzene derivatives in a proportion of 0.1-20% relative to the weight of the fiber; and a method for manufacturing same. According to the present invention, excellent resistance to chlorine-induced change in shade as well as chlorine-induced degradation can be afforded to the dyed union knit fabric.	FIELD OF THE INVENTIONThe present invention relates to a method of dyeing a union knit fabric made with a polyurethane elastic fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, and to a union knit fabric obtained by said method. The present invention specifically relates to a method of dyeing a knit fabric comprised of a polyurethane elastic fiber having improved resistance to chlorine-induced degradation in various chlorinated aqueous environments, which does not impair the improved resistance imparted to the fabric, and to a dyed union knit fabric which retains superior resistance to chlorinated aqueous environments which said method provides. BACKGROUND OF THE INVENTIONPolyurethane elastic fibers obtained from 4,4'-diphenylmethane diisocyanate, polyhydroxy polymer with a relatively low degree of polymerization, multifunctional active hydrogen compounds, and so on exhibit high rubber elasticity, superior mechanical properties in tensile stress and recoverability, and excellent thermal property. For this reason, they have been given much attention and used as functional materials for clothes such as foundation garments, socks and sportswears. The dyeing of a knitted fabric containing polyamides is disclosed in JP-A-57 143 358 and JP-A-61 113 864. However, it has been known that exposure of goods made with elastic fibers which have been formed mainly from long chain synthetic elastic segmented polyurethanes to chlorinated aqueous environments with chlorine bleaching agents can cause considerable lowering of the physical properties of the segmented polyurethane. It has been also known that swimwear made with polyurethane fibers and polyamide fibers is subject to lowered physical properties of the fibers upon long-term exposure to the water in swimming pools containing 0.5-3 ppm (parts per million) active chlorine. In fact, many attempts have been made so far to impart proof or resistance to chlorine-induced degradation. For example, U.S. Patent No. 4340527 teaches zinc oxide, and Japanese Patent Publication No. 35283/1986 (corresponding with DE-A-33 34 070) teaches magnesium oxide and alminium oxide as additives which prevent chlorine-induced degradation. Nevertheless, improvements are still needed since the above-mentioned polyurethane elastic fiber containing a chlorine-induced degradation inhibitor, which is used to manufacture union knit fabric loses most of the resistance to chlorine after dyeing, etc., because the degradation inhibitor once contained in the fiber elutes out during dyeing, finishing and processing stages, particularly during the dyeing process which the goods made of the union knit fabric undergo, due to a low pH of dye liquor despite the resistance to chlorine which the raw fiber possesses. The present invention provides resistance to the chlorinated water to the dyed textile goods made with at least a polyurethane elastic fiber, and a method for manufacturing them, thereby resolving the problems of the prior art as described above. That is, the present invention relates to a dyed union knit fabric manufactured by dyeing a union knit fabric comprised of at least a polyurethane elastic fiber containing one or more chlorine-induced degradation inhibitors selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide and hydrotalcite compounds in a proportion of 0.5-5.0 weight% based on the weight of the fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, wherein the polyurethane elastic fiber contains said inhibitors in a proportion of 0.5-4.5 weight% based on the weight of the fiber and the polyamide fiber and/or the cation dyeable polyester fiber exhausts or shows a dye uptake of not less than 0.01% owf of at least one member selected from the group consisting of acid dyes, metal-complex dyes fluorescent dyes, disperse dyes, reactive dyes, direct dyes, and cation dyes. Also, the present invention relates to a method for manufacturing the above dyed union knit fabric, wherein the pH of dye bath is maintained at not less than 4.5 throughout the dyeing process from the beginning to the end thereof when dyeing a union knit fabric comprised of at least a polyurethane elastic fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, the polyurethane elastic fiber containing one or more members of the group consisting of magnesium oxide, zinc oxide, alminium oxide, magnesium hydroxide, zinc hydroxide, alminium hydroxide and hydrotalcite compounds in a proportion of 0.5-5.0 weight% based on the weight of the fiber, with at least one member dye of the group consisting of acid dyes, metal-complex dyes, fluorescent dyes, disperse dyes, reactive dyes, direct dyes and cation dyes. The polyurethane elastic fiber used in the present invention is an elastic fiber obtained by spinning a polymer composition containing a polyurethane to be mentioned below as a main component. As the polyurethane in the present invention, usable are polymers obtained by reacting a polymer diol having a number average molecular weight of not less than 600, preferably 1000-5000 and a melting point of not more than 60°C, an isocyanate based on an organic diisocyanate, and a multifunctional active hydrogen compound having a molecular weight of not more than 400. Examples of the polymer diol include polyether glycols such as polytetramethylene ether glycol and polyethylene propylene ether glycol; polyester glycols obtained by reacting at least one member of glycols such as ethylene glycol, 1,6-hexane diol, 1,4-butane diol and neopentyl glycol with at least one member of dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid and isophthalic acid; polycaprolactone glycol; polyhexamethylene dicarbonate glycol; and mixtures and copolymers of two or more of them. Examples of the organic diisocyanate include 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and mixtures of two or more of them. A small amount of triisocyanate may be co-used. Examples of the multifunctional active hydrogen compounds include ethylenediamine, 1,2-propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, hydrazine, 1,4-diaminopiperazine, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, water, and mixtures of two or more of them. A small amount of a terminator such as monoamine or monoalcohol may be added to the above-mentioned compounds, if desired. Of those, preferred is diamine solely or one based on diamine. The way of forming an elastic fiber by spinning a composition based on polyurethane is not subject to particular limitation, but dry spinning of a composition based on polyurethane, which is dissolved in a solvent is preferable. As the solvent, there may be exemplified, but not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea and hexamethylphosphoramide. The components other than polyurethane to be contained in the composition based on polyurethane include chlorine-induced degradation inhibitors such as metal oxides and metal hydroxides (e.g. magnesium oxide, zinc oxide, alminium oxide, magnesium hydroxide, zinc hydroxide, alminium hydroxide, hydrotalcite compounds) which may be used solely or in combination, with preference given to magnesium oxide and zinc oxide. The way of adding an inhibitor into the polyurethane solution is not particularly limited, but preferably performed by adding same in finely divided particles having an average diameter of 0.05-3 µm. The chlorine-induced degradation inhibitor such as metal oxide, etc. is added in a proportion of 0.5-5.0 weight%, preferably 1.0-3.0 weight% based on the polyurethane. The proportion of the residual magnesium oxide, etc. relative to the polyurethane after dyeing is 0.5-4.5 weight%, preferably 1.0-4.5 weight%, more preferably 2.0-4.0 weight%. The polyurethane elastic fiber in accordance with the present invention is of 20-100 denier, preferably 40-80 denier. The elastic fiber is used in the state of covering yarn or bare yarn. The polyamide fiber to be knitted with the polyurethane elastic fiber of the present invention is not particularly limited and exemplified by nylon 6 and nylon 6,6. Similarly, the cation dyeable polyester fiber is not particularly limited and can be a fiber obtained from polyesters prepared by copolymerization of an ester-forming compound having a sulfo group such as 5-sulfoisophthalic acid with a conventional polyester, or copolymerization along with another ester-forming compound, wherein the sulfo group preferably forms a metal salt such as sodium salt. This cation dyeable polyester fiber can dye in sufficiently deep shade with cation dyes at a temperature of not more than 100°C. The union knit fabric is subject to no particular limitation and may be a weft-knitted fabric, a warp-knitted fabric, a tricot fabric or a raschel fabric. Its stitch may be half stitch, back half stitch, double atlas stitch, double dembhigh stitch, or the like with no particular limitation. From the standpoint of handling touch, the surface of the fabric is preferably made with a polyamide fiber and/or a cation dyeable polyester fiber. The knit fabric is subjected to scouring, relaxing and drying under the usual conditions, in which heat setting temperature is between 150°C and 190°C, preferably between 160°C and 180°C. Dyeing is done in a dye bath for 20-120 minutes, preferably for 40-60 minutes. The dyeing machine is one usually employed, such as wince dyeing machine and liquor flow dyeing machine. The dyestuff to be used is one normally employed by dye makers for dyeing polyamide fibers or for dyeing cation dyeable polyester fibers, such as acid dyes, metal-complex dyes, fluorescent dyes, disperse dyes, cation dyes, and so on. The polyamide fiber and/or the cation dyeable polyester fiber of the present invention exhaust(s) and/or show(s) a dye uptake of not less than 0.01% owf, preferably 0.05% owf, more preferably 0.1% owf relative to the union knit fabric of at least one of the above dyes. In the present invention, it is essential that pH of dye liquor be maintained at 4.5 or above, preferably at 5 from the initiation to the termination of dyeing, and for this to be achieved, for example, an organic acid ester is added to the dye liquor. In the organic acid ester are formate, acetate, butyrate, lactate and orthoformate. An alkali agent such as soda ash may be used along with the organic acid ester. The organic acid ester is used in a proportion of 0.1-10 weight%, preferably 1-5 weight% based on the weight of the fabric. The preferable organic acid ester is orthoformate. The orthoformate is exemplified by trimethyl orthoformate and triethyl orthoformate, with preference given to trimethyl orthoformate. The orthoformate is used in a proportion of 0.01-10 weight%, preferably 0.5-5 weight% based on the weight of the fabric. Where it is used in a proportion of less than 0.01 weight%, sufficient dyeing is unattainable, while used in more than 10 weight%, the chlorine-induced degradation inhibitor elutes out in a large amount, resulting in marked lowering of product properties. An alkali agent such as soda ash may be used along with the orthoformate. An ester of formic acid and an alkylene glycol having an alkylene of 2 to 5 carbon atoms may be used for maintaining the pH of die liquor not less than 4.5. In such ester are monoesters and diesters of formic acid and ethylene glycol, and mixtures thereof; and monoesters and diesters of formic acid and propylene glycol, and mixtures thereof, with preference given to monoesters and diesters of formic acid and ethylene glycol, and mixtures thereof. The ester of formic acid and an alkylene glycol having an alkylene of 2 to 5 carbon atoms may be used in a proportion of 0.01-3.0 weight%, preferably 0.1-1.0 weight% based on the weight of the fabric. Where it is used in a proportion of less than 0.01 weight%, sufficient dyeing is unattainable, while used in more than 3.0 weight%, the chlorine-induced degradation inhibitor elutes out in a large amount, resulting in marked lowering of product properties. An alkali agent such as soda ash may be used along with the ester of formic acid and an alkylene glycol having an alkylene of 2 to 5 carbon atoms. The present invention aims at imparting resistance to chlorine-induced degradation to a polyurethane elastic fiber while imparting resistance to change in shade to a dyed union knit fabric made with said elastic fiber. It has been known that products dyed with mixed dyes of acid dyes, dispersion dyes, metal-complex dyes, reactive dyes and direct dyes are susceptible to shade change in chlorinated environments. In particular, a long-term exposure of a union knit fabric made with a polyurethane elastic fiber and a polyamide synthetic fiber, and dyed with acid dyes, dispersion dyes, metal-complex dyes or reactive dyes to the chlorinated water containing 0.5-3 ppm active chlorine such as the water in swimming pools results in decoloring, yellowing and saddening of the shade of the fabric particularly when the fabric has been dyed in fluorescent or brilliant shades. In view of the above situation, the present inventors have conducted intensive studies based on a new idea and as a result, achieved the present invention which remarkably resolves various problems as described. That is, the present invention provides a union knit fabric comprised of at least a polyurethane elastic fiber, and a polyamide fiber and/or a polyester fiber, which has been dyed with mixed dyes of acid dyes, dispersion dyes, metal-complex dyes, reactive dyes and direct dyes, and markedly improved in resistance to chlorine-induced change in shade in various chlorinated environments without impairing the original color of the fabric by allowing to contain at least one compound having a reaction amount of chlorine of 50 milliequivalent per gram or more, specifically one member of mono- and/or polyhydroxybenzene derivatives of the following formula 1, 2 or 3 in a proportion of 0.1-20% relative to the weight of the fiber via immersion in a hot bath, and a method for manufacturing it. In addition to the resistance to chlorine-induced degradation, resistance to chlorine-induced change in shade can be increased by blending said compounds during dyeing and/or before and after the dyeing. (OH)x― Z⁵―(B⁵)y (III) wherein Z¹ is an aromatic group; Z², Z³, Z⁴ and Z⁵ are independently aromatic groups the same as or different from Z¹; A is a bivalent group such as alkylene, sulfonyl, sulfide and azo; B¹ is a monovalent group such as alkyl, alkoxy, nitro, sulfone and amino, or hydrogen atom; B², B³, B⁴ and B⁵ are independently monovalent groups the same as or different from B¹, or hydrogen atom; R¹ and R² are the same or different and each is a group selected from the group consisting of alkyl and aryl; and k, l, m, n, s, t, u, v, x and y are positive integers satisfying the following formulas Q-1 to Q-5. 0 ≦ k ≦ 4 1 ≦ k+1 ≦ 5 0 ≦ m ≦ 4 1 ≦ m+n ≦ 5 0 ≦ s ≦ 4 1 ≦ s+t ≦ 5 0 ≦ u ≦ 4 1 ≦ u+v ≦ 5 1 ≦ x ≦ 4 1 ≦ x+y ≦ 6 Each symbol in formulas (I) to (III) represents the following. As regards Z¹, Z², Z³, Z⁴ and Z⁵, the aromatic group means phenylene group such as 1,4-phenylene, 1,3-phenylene and 1,2-phenylene, naphthylene group such as 1,4-naphthylene, 1,5-nephthylene and 1,6-naphthylene. As regards A, the alkylene group has 1 to 20, preferably 1 to 10 carbon atoms, which is exemplified by methylene, ethylene, propylene, trimethylene, vinylene, ethynylene and propenylene. As regards B, the alkyl group has 1 to 10, preferably 1 to 5 carbon atoms, which is exemplified by methyl, ethyl, propyl, isopropyl, butyl and t-butyl. As regards B, the alkoxy group has 1 to 10, preferably 1 to 5 carbon atoms, which is exemplified by methoxy, ethoxy, propoxy, isopropoxy and butoxy. As regards R¹ and R², the alkyl group has 1 to 10, preferably 1 to 5 carbon atoms, which is exemplified by methyl, ethyl, propyl, isopropyl, butyl and t-butyl. As regards R¹ and R², the aryl group is exemplified by phenyl, tolyl, xylyl, biphenyl and naphthyl. The compounds of formula (I) may be exemplified by diphenylmethane derivatives into which a hydroxyl group has been introduced, such as 4,4'-methylenebisphenol, 4,4'-(1-methylethylidene)bisphenol, 4,4'-ethylidenebisphenol, 4,4'-(1-α-methylbenzylidene)bisphenol, 4,4'-cyclohexylidenebisphenol, 4,4'-[1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene]bisphenol, 4,4'-[(4-hydroxyphenyl)methylene]bis(methylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4',4''-ethylidinetrisphenol, 4,4',4''-methylidinetrisphenol, 2,2'-methylenebis(4-methylphenol), 4,4'-(1-methylethylidene)bis(2,6-dimethylphenol), phenolphthalein, 1,4-phenylene-4,4'-bisphenol, 1,4-bis(4-hydroxyphenyl)cyclohexane, bis(3,5-dihydroxyphenyl)methane, 2,2'-bis(4-hydroxynaphthyl)methane, 2,2'-bis(5-hydroxynaphthyl)methane, 2,2'-bis(6-hydroxynaphthyl)methane, 2,2'-bis(7-hydroxynaphthyl)methane, 2,2'-bis(8-hydroxynaphthyl)methane, 2,2'-bis-(4,7-dihydroxynaphthyl)methane, 2,2'-bis(3,6-dihydroxynaphthyl)methane, and polymers obtained by using them as monomers; diphenylsulfone derivatives into which a hydroxyl group has been introduced, such as bis(4-hydroxyphenyl)sulfone and bis(3,5-dihydroxyphenyl)sulfone, and polymers obtained by using them as monomers; diphenylsulfid derivatives into which a hydroxyl group has been introduced, such as 4,4'-dihydroxydiphenylsulfid and bis(3,5-dihydroxyphenyl)sulfid, and polymers obtained by using them as monomers; diphenylether derivatives into which a hydroxyl group has been introduced, such as 4,4'-dihydroxydiphenyl ether and bis(3,5-dihydroxyphenyl) ether, and polymers obtained by using them as monomers; and azobenzene derivatives into which a hydroxyl group has been introduced, such as 4,4'-dihydroxyazobenzene and bis(3,5-dihydroxy)azobenzene, and polymers obtained by using them as monomers. Examples of the compounds of formula (II) include biphenyl derivatives into which a hydroxyl group has been introduced, such as 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,3'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,5-dihydroxybiphenyl, 2,4-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 3,5,4'-trihydroxybiphenyl, 2,4,4'-trihydroxybiphenyl, 2,6,4'-trihydroxybiphenyl, 3,3',5,5'-tetrahydroxybiphenyl, and polymers obtained by using them as monomers; and binaphthyl derivatives into which a hydroxyl group has been introduced, such as 2,2'-bis(4-hydroxynaphthyl), 2,2'-bis(5-hydroxynaphthyl), 2,2'-bis(6-hydroxynaphthyl), 3,3'-bis(6-hydroxynaphthyl), 2,2'-bis(8-hydroxynaphthyl), 1,1'-bis(3-hydroxynaphthyl), 1,1'-bis(4-hydroxynaphthyl), 1,1'-bis(5-hydroxynaphthyl), 1,1'-bis(6-hydroxynaphthyl), 1,1'-bis(7-hydroxynaphthyl), 1,1'-bis(8-hydroxynaphthyl), and polymers obtained by using them as monomers. Examples of the compounds of formula (III) include 3-hydroxybenzoic acid and/or its methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters using the 3-hydroxybenzoic acid as an acid component, and polymers obtained by using them as monomers; 4-hydroxybenzoic acid and/or its methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters using the 4-hydroxybenzoic acid as an acid component, and polymers obtained by using them as monomers; 3,5-dihydroxybenzoic acid and/or its methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters using the 3,5-hydroxybenzoic acid as an acid component, and polymers obtained by using them as monomers, 2,4-dihydroxybenzoic acid and/or its methyl, ethyl, isopropyl, t-butyl, amyl and stearyl esters using the 2,4-hydroxybenzoic acid as an acid component, and polymers obtained by using them as monomers; hydroxyacetophenones such as 3-hydroxyacetophenone, 4-dihydroxyacetophenone, 3,5-dihydroxyacetophenone and 2,4-dihydroxyacetophenone, and polymers obtained by using them as monomers; hydroxybenzyl ketones such as 3-hydroxybenzyl ethyl ketone, 4-hydroxybenzyl ethyl ketone, 3-hydroxybenzyl isopropyl ketone, 4-hydroxybenzyl isopropyl ketone, 3-hydroxybenzyl butyl ketone, 4-hydroxybenzyl butyl ketone, 3-hydroxybenzyl amyl ketone, 4-hydroxybenzyl amyl ketone, 4-hydroxybenzyl stearyl ketone and 3-hydroxybenzyl stearyl ketone, and polymers obtained by using them as monomers; and alkylphenols such as isopropylphenol, butylphenol and amylphenol, and polymers obtained by using them as monomers. Of the polymers obtained by using mono- and/or polyhydroxybenzene derivatives of formula 1, 2 or 3 as monomers, a polymer wherein aromatic ring is directly bound with aromatic ring, which can be produced by oxidative coupling of the monomers, is preferable. Such a polymer can be produced by a well-known method such as an oxidative coupling of phenol compounds by horse-radish peroxidase. A formalin condensate obtained from the phenol compounds described above, such as the conventional novolak resin may be used. A method for determining the amount of chlorine reacting with the compounds to be added for the improved resistance to chlorine-induced shade change is as follows. Determination of reaction amount of chlorineThe determination method for the reaction amount of chlorine (hereinafter referred to as C) is described in the following, wherein % means weight%. (1) Reagent and its preparationi) Sodium hypochlorite solution Sodium hypochlorite (guaranteed reagent, 30 g) (Nakarai Tesque) is diluted with pure water to give a 1 ℓ solution. ii) Diluted aqueous solution of acetic acid (10%) Acetic acid (5 g) is diluted with pure water to make the total amount 50 g. iii) Starch indicator (5%) Soluble starch (1 g, Nakarai Tesque) is dissolved in pure water to make the total amount 20 g. iv) Acetic acid A guaranteed reagent (Nakarai Tesque) is used as it is. v) Aqueous solution of potassium iodide (20%) Potassium iodide (guaranteed reagent, 100 g) (Nakarai Tesque) is dissolved in pure water to make the total amount 500 g. vi) N/10 Sodium thiosulfate normal solution A normal solution (Nakarai Tesque) is used as it is. (Potency of the normal solution : f) vii) Solvent A suitable solvent is selected according to the properties of the substance to be determined for the reaction amount of chlorine (hereinafter referred to as sample). In the present invention, chloroform, methaol, ethanol, isopropyl alcohol, methyl isopropyl ketone (all of which are guaranteed reagents produced by Nakarai Tesque) and pure water are used as they are and/or in mixture. (2) Preparation of sample solutionA given amount of a sample (S gram, preferably about 0.1 g) is precisely weighed with a chemical balance, and dissolved in a solvent which is selected in (1)-vii) in a 100 ml-volumetric flask to make the total amount 100 ml. (3) Instruments to be used (the figure in parentheses refer to instrument number)i) 25 ml buret (1) ii) pipet 25 ml (1), 10 ml (2), 5 ml (1), 2 ml (1) iii) measuring pipet 10 ml (1) iv) Erlenmeyer's flask with a plug 100 ml (determination number + 2 for blank test) v) magnetic stirrer, stirring rod (same as the number of Erlenmeyer's flask) vi) clock (1) (4) Determination procedure for reaction amount of chlorinei) N/10 sodium thiosulfate is charged in a 25 ml buret. ii) With the use of a 25 ml pipet, a sodium hypochlorite solution is dispensed in the 100 ml Erlenmeyer's flasks to be used for the determination, each of which being equipped with a stirring rod. Two flasks are prepared for the blank test. iii) The sample solution is dispensed in the Erlenmeyer's flasks of ii) with a 10 ml pipet. The solvent is dispensed by 10 ml in the flasks for the blank test. iv) A 10%-diluted aqueous solution of acetic acid is added to each Erlenmeyer's flask by 1 ml, with a 10 ml measuring pipet while stirring. The time clocking is initiated from the moment when the diluted aqueous solution of acetic acid is added, which moment is taken as minute 0. v) After a given time, one Erlenmeyer's flask is taken, and 5 ml of an aqueous solution of 20% potassium iodide and then 2 ml of acetic acid are added. The reaction time is normally set for 5, 10, 20, 30 and 40 minutes. vi) A sodium thiosulfate normal solution is dropwise added thereto under stirring until the solution in the flask loses most of its color. Several drops of an starch indicator are added, and the dropwise addition is continued until the purple color completely disappears. The point at which the purple color disappears is taken as titration end point. The same procedure is repeated at each predetermined time period to measure the titre. (titre : V ml) vii) As the blank test, titration is conducted immediately after the addition of the diluted acetic acid and at each time period predetermined for the titration of the sample in vi). These two titres are averaged to give the titre of the blank (Vo ml). (5) Calculation of reaction amount of chlorine (C)i) The correlation of x and y is calculated from the following equation (1) by the least square method, wherein x is reaction time and y is Vo-V of each reaction period: y = a + bx (correlation function : r) The correlation coefficient of the straight line is preferably 0.98 or above for the determination precision. ii) The value C is calculated from the following equation (2) using an extrapolation value, namely a, which is the value of the straight line obtained when the reaction time (x) is 0: C = a × f ÷ S [unit of C:milliequivalent per gram, f:potency of N/10 sodium thiosulfate normal solution, S:amount of sample (g)] As the compounds whose reaction amount of chlorine is 50 milliequivalent per gram or more, there may be mentioned those exemplified as the compounds of formula 1, 2 and 3 as shown above, with preference given to 4,4'-biphenol, Bisphenol A and 4,4'-dihydroxydiphenyl sulfone. Note that of the compounds having the reaction amount of chlorine of 50 milliequivalent per gram or more as measured by the above method, hydroxybenzophenone derivatives, catechols, pyrogallols and gallates are not preferable, since they themselves have colors. As the polyhydroxybenzene derivatives in the present invention, those having a hydroxyl group at the ortho- and/or para-position(s) which develop color by reacting with basic additives contained in polyamide fiber and/or polyester fiber, and polyurethane elastic fiber to form a quinone structure, such as hydroquinone, catechol and pyrogallol are not preferable from the standpoint of hue of the dyed fabric, and polyhydroxybenzene derivatives which do not take a quinone structure when oxidized, such as phenol, resorcin and phloroglucin are preferable. The proportion of the chlorine-induced shade change inhibitor to be contained in the knit fabric is in the range of 0.1 to 20 weight%, preferably 0.5-10 weight%. Where it is contained in a proportion below said range, the effect is seldom observable, while contained beyond said range, handling touch becomes undesirable. The use of an anionic phenol compound which does not take a quinone structure by reacting with an alkali, as a dye fixing agent during dye fixing of the fabric benefits the object of the invention. The dye fixing agent to be used in the present invention is an anionic phenol compound which does not take a quinone structure by reaction with an alkali. Examples of the phenol compound include phenolsulfonic acid-formaldehyde resin, sulfone compounds of novolak type resin, methane sulfonic acid of novolak type resin, benzylated phenolsulfonic acid, thiophenol compounds, dihydroxydiphenyl sulfone compounds, ligand compounds thereof and metal chelate compounds thereof. The anionic phenol compound is used in a proportion of 1-20% owf (on the weight of fiber), preferably 3-10% owf based on the polyamide fiber. Where it is contained in a proportion of 1% or below, durable dye fixation cannot be obtained, while contained in a proportion of 20% owf or above, handling touch becomes firm and undesirable despite sufficient fixation effect. The anionic phenol compound is applied on the fabric by immersing the dyed knit fabric in a solution of an anionic phenol compound, padding a solution of an anionic phenol compound on the knit fabric, or spraying same on the knit fabric, of which the immersion is most desirable since it permits efficient application of the dye fixing agent on the knit fabric by the least number of steps including dye finishing, and it results in homogeneous application of the agent. The dye fixation temperature is in the range of 40°C to 100°C, preferably 60°C to 90°C. Resin treatment agents, softners, antistatic agents, water repellents, etc. may be added in the solution to be used for immersion, padding or spraying according to the present invention. Orthoformate is co-used in the dye fixation mentioned above. Unless the dye method of the present invention is employed, prevention of chlorine-induced degradation in the dyed final product becomes ineffective due to the reduced amount of the degradation inhibitor which was once contained in the fiber during spinning. The present invention is hereinbelow described in detail by illustrating working examples and comparative examples in which % means weight% unless otherwise specified. Example 1-4, Comparative Example 1-3A prepolymer was prepared by reacting polytetramethylene ether glycol having a hydroxyl group on the both termini which has a number average molecular weight of 2000 with 4,4'-diphenylmethane diisocyanate in a molar ratio of 1:2. The prepolymer thus prepared was then subjected to chain extension with 1,2-propylenediamine to give a polyurethane solution of 30% polymer concentration (solvent : dimethylformamide) and 2000 poises viscosity at 30°C. To this solution were added magnesium oxide having an average particle diameter of 0.1-2.0 µm dispersed in dimethylformamide by attriter, in a proportion of 3% based on the polyurethane, then antioxidant, ultraviolet absorber and gas yellowing-preventive, and the mixture was stirred to give a spinning dope. After defoaming, the spinning dope was extruded into a spinning chimney in a heated air flow (180°C) from a five-hole spinneret (hole diameter : 0.2 mm). The yarns were twisted at 10000 rpm, and wound at a rate of 500 m/min. while applying 6% winding oil to the yarns, thereby obtaining five-filament, 40 denier polyurethane elastic fiber (A). For comparison, polyurethane elastic fiber (A2) was obtained in the same manner as for (A) with no addition of magnesium oxide. Besides, 12-filament, 50 denier fiber (B1) was prepared from nylon 6. Using the tricot knitting machine (28 gauge, Karlmeyer), the gray state goods were prepared. The draft of fibers (A) and (A2) was 100%, knit-in length was 70 cm/480 course for fibers (A) and (A2), and 160 cm/480 course for fiber (B1) (55 looming course), and the stitch was half stitch. Each of the knit fabrics obtained from fibers (A) and (B1), or (A2) and (B1) in the gray state was subjected to scouring, relaxing, drying and heat setting, followed by dyeing. Dyeing was done using Kayacyl Blue BR, 5.0% owf (acid dye) at 40-95°C for 45 minutes. The knit fabric was rinsed with warm water at 50°C for 10 minutes, and successively dye fixed, after which it was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 180°C for 30 seconds and heat-set. The chlorine-induced degradation of each knit fabric thus obtained was tested, in which the fabric was 40% warpwise drawn and immersed in chlorinated water (pH 7.5, 30°C, 30 ppm) for 6 hours, and stress before and after the immersion was measured to determine the degradation (brittleness), the results of which are summarized in Table 1. In Table 1, A to F under dye liquor formulation refer to the aforementioned dye liquor supplemented with the following agents. A :NC Acid W (Nikka Kagaku) 2 g/ℓ B :Sand Acid V (Sand) 2 g/ℓ Soda ash 0.3 g/ℓ C :Sand Acid VA (Sand) 2 g/ℓ Soda ash 0.3 g/ℓ D :Sand Acid VSK (Sand) 2 g/ℓ Soda ash 0.3 g/ℓ E :Acetic acid 0.4 g/ℓ Ammonium sulfate 2 g/ℓ Anionic leveling agent 1.2 g/ℓ F :Acetic acid 1.0 g/ℓ Ammonium sulfate 2 g/ℓ Anionic leveling agent 1.2 g/ℓ Example 5-7, Comparative Example 4-8The following test was performed using the same fiber and the knit fabric as used in Examples 1-4. The fabric was dyed with Kayacyl Blue BR, 5% owf (acid dye) at from 40°C to 95°C for 45 minutes and at 95°C for 30 minutes (liquor ratio : 13:1), then rinsed with warm water at 50°C for 10 minutes, followed by dye fixing. Thereafter, the fabric was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 180°C for 30 seconds and heat-set. For textile printing, the fabric was dyed with fluorescent dyes under the same conditions as above, and subjected to printing, steaming at 100°C for 40 minutes, and rinsing with water, alkali soaping, rinsing with warm water and rinsing with water, which steps were repeated in cycles. Upon dye fixation, the fabric was dehydrated, spread, dried at 160°C for 30 seconds and heat-set. (Example 7) The chlorine-induced degradation of each knit fabric thus obtained was tested, in which the fabric was 40% warpwise drawn and immersed in chlorinated water (pH 7.5, 30°C, 30 ppm) for 6 hours, and stress before and after the immersion was measured to determine the degradation (brittleness), the results of which are summarized in Table 2. In Table 2, A to F under dye liquor formulation refer to the aforementioned dye liquor supplemented with the following orthoformate and/or other agents. G and H refer to printing with a color paste supplemented with the following orthoformate or acetic acid. In Comparative Example 5, dyeing was insufficient, namely, dye exhaustion was 0.01% owf or below. A :Trimethyl orthoformate 1 g/ℓ B :Trimethyl orthoformate 1 g/ℓ Soda ash 0.1 g/ℓ C :Acetic acid 0.4 g/ℓ Ammonium sulfate 2 g/ℓ Anionic leveling agent 1.2 g/ℓ D :Trimethyl orthoformate 0.005 g/ℓ E :Trimethyl orthoformate 10 g/ℓ F :Trimethyl orthoformate 1 g/ℓ G :Trimethyl orthoformate 1 g/ℓ (printing) H :Acetic acid 0.4 g/ℓ Example 8-10, Comparative Example 9-13The following test was performed using the fiber and the knit fabric as obtained in Examples 1-4 and Comparative Example 1-3. The fabric was dyed with Kayacyl Blue BR, 5% owf (acid dye) at from 40°C to 95°C for 45 minutes and at 95°C for 30 minutes (liquor ratio : 13:1), then rinsed with warm water at 50°C for 10 minutes, followed by dye fixing. Thereafter, the fabric was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 180°C for 30 seconds and heat-set. For textile printing, the fabric was dyed with fluorescent dyes under the same conditions as above, and subjected to printing, steaming at 100°C for 40 minutes, and rinsing with water, alkali soaping, rinsing with warm water and rinsing with water, which steps were repeated in cycles. Upon dye fixation, the fabric was dehydrated, spread, dried at 160°C for 30 seconds and heat-set. (Example 10) The chlorine-induced degradation of each knit fabric thus obtained was tested, in which the fabric was 40% warpwise drawn and immersed in chlorinated water (pH 7.5, 30°C, 30 ppm) for 6 hours, and stress before and after the immersion was measured to determine the degradation (brittleness), the results of which are summarized in Table 3. In Table 3, A to F under dye liquor formulation refer to the aforementioned dye liquor supplemented with the following ester of formic acid and alkylene glycol having an alkylene of 2 to 5 carbon atoms and/or other agents. G and H refer to printing with a color paste supplemented with the following ester of formic acid and alkylene glycol having an alkylene of 2 to 5 carbon atoms or acetic acid. In Comparative Example 10, dyeing was insufficient, namely, dye exhaustion was 0.01% owf or below. A :Ethylene glycol monoformate 1 g/ℓ B :Ethylene glycol monoformate 1 g/ℓ Soda ash 0.1 g/ℓ C :Acetic acid 0.4 g/ℓ Ammonium sulfate 2 g/ℓ Anionic leveling agent 1.2 g/ℓ D :Ethylene glycol monoformate 0.005 g/ℓ E :Ethylene glycol monoformate 10 g/ℓ F :Ethylene glycol monoformate 1 g/ℓ G :Ethylene glycol monoformate 1 g/ℓ (Example 10) H :Acetic acid 0.4 g/ℓ Example 11-13, Comparative Example 14-19The following test was performed using the fiber and the knit fabric as obtained in Example 1-4 and Comparative Example 1-3. The fabric was dyed with Kayacyl Blue BR, 5.0% owf (acid dye), using trimethyl orthoformate 1 g/ℓ and soda ash 0.1 g/ℓ at from 40°C to 95°C for 45 minutes and at 95°C for 30 minutes (liquor ratio : 13:1), then rinsed with warm water at 50°C for 10 minutes, followed by dye fixing. The dye fixing was performed with a formalin condensate of dihydroxydiphenylsulfone and aromatic sulfonic acid (Nylon Super-N, Nissei Kasei) as a dye fixing agent in a proportion of 5% owf (liquor ratio : 15:1), at from 40°C to 70°C for 10 minutes and at 70°C for 20 minutes. Thereafter, the knit fabric thus obtained was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 160°C for 30 seconds and heat-set. In Comparative Example 18, the fixation treatment was conducted as described above except the use of tannic acid as a dye fixing agent. Example 13 and Comparative Example 19 underwent textile printing which was conducted as in the following. After dyeing with fluorescent dyes under the same conditions as above, the fabric was subjected to printing, steaming at 100°C for 40 minutes, and rinsing with water, alkali soaping, rinsing with warm water and rinsing with water, which steps were repeated in cycles. The dye fixation was carried out using 5% owf (liquor ratio : 15:1) formaldehyde condensate of sulfonated dihydroxydiphenylsulfone (FK 707, Fuji Kagaku) as a dye fixing agent at from 40°C to 70°C for 10 minutes and at 70°C for 20 minutes, after which the fabric was dehydrated, spread, dried at 160°C for 30 seconds and heat-set. The chlorine-induced degradation of each knit fabric thus obtained was tested, in which the fabric was 40% warpwise drawn and immersed in chlorinated water (pH 7.5, 30°C, 30 ppm) for 6 hours, and stress before and after the immersion was measured to determine the degradation (brittleness), the results of which are summarized in Table 4. In Table 4, A to G under dye fixation refer to the above-mentioned dye fixation liquor supplemented with the following orthoformate or acetic acid. H and I refer to agents used during dye fixation for textile printing. In Comparative Example 15, dyeing was insufficient, namely, dye exhaustion was 0.01% owf or below. A :Trimethyl orthoformate 0.5 g/ℓ B :Trimethyl orthoformate 1 g/ℓ C :Trimethyl orthoformate 10 g/ℓ D :Trimethyl orthoformate 0.005 g/ℓ E :Acetic acid 0.4 g/ℓ F :Trimethyl orthoformate 0.5 g/ℓ G :Trimethyl orthoformate 0.5 g/ℓ H :Trimethyl orthoformate 0.5 g/ℓ I :Acetic acid 0.4 g/ℓ Example 14-21, Comparative Example 20-23In addition to the fibers as obtained in Example 1-4 and Comparative Example 1-3, 10-filament, 50 denier atmospheric cation dyeable polyester fiber (B2) which was produced by melt spinning was used as a polyester fiber to give a knit fabric. Each gray state fabric comprised of fibers (A) and (B1) was subjected to scouring, relaxing, drying, heat setting and dyeing. The fabric was dyed in a dye bath containing trimethyl orthoformate (0.5 g/ℓ) and Kayacyl Blue BR, 5% owf (acid dye) at a liquor ratio of 13:1 at from 40°C to 95°C for 30 minutes and at 95°C for 30 minutes, after which it was rinsed with warm water at 50°C for 10 minutes, followed by immersion of the dyed fabric in a dispersion of a chlorine-induced shade change inhibitor (Bisphenol A, 5% owf) at from 40°C to 80°C for 50 minutes. Dye fixation was performed with an anionic polyphenol except tannic acid and trimethyl orthoformate as companion fixing agents. The dyed fabric thus obtained was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 160°C and heat-set. Example 14The chlorinated water-induced shade change of the dyed fabric obtained as above was tested by immersing 1 part of the knit fabric in 400 parts of chlorinated water (available chlorine 100 ppm, pH 7.0) at 40°C for 30 minutes in a manner such that the chlorinated water stream vertically hits the fabric surface. The hue of the finished union knit fabric and that after the chlorinated water treatment were measured, based on which color fastness to chlorine (degree of shade change) was estimated. The results are summarized in Table 5. Example 15A gray state fabric comprised of fibers (A) and (B2) was subjected to scouring, relaxing, drying, heat setting and dyeing. The fabric was dyed in dye bath containing trimethyl orthoformate (1.0 g/ℓ) and Diacryl Brilliant Blue AC-E, 1% owf (cation dye) at a liquor ratio of 18:1 at from 40°C to 100°C for 45 minutes and at 100°C for 30 minutes, after which it was rinsed with warm water at 50°C for 10 minutes, followed by immersion of the dyed fabric in a dispersion of a chlorine-induced shade change inhibitor (Bisphenol A, 5% owf) at from 40°C to 80°C for 50 minutes. The dyed union knit fabric obtained as above was subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 16A dyed union knit fabric was prepared in the same manner as in Example 14 except that 4,4'-biphenol, 5% owf, was used as a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 17A dyed union knit fabric was prepared in the same manner as in Example 14 except that 4,4'-dihydroxybenzo sulfone, 5% owf, was used as a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 18A dyed union knit fabric was prepared in the same manner as in Example 14 except that 3,5-dihydroxybenzyl ethyl ketone, 5% owf, was used as a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 19A dyed union knit fabric was prepared in the same manner as in Example 14 except that Bisphenol A polymer (average molecular weight 1000), 5% owf, produced by reacting Bisphenol A as a monomer with horseradish peroxidase as a catalyst, was used as a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 20A dyed union knit fabric was prepared in the same manner as in Example 14 except that 4,4'-biphenol, 2% owf, was used as a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Example 21A dyed union knit fabric was prepared in the same manner as in Example 14 except that 4,4'-biphenol, 10% owf, was used a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Comparative Example 20A dyed union knit fabric was prepared in the same manner as in Example 14 without using a chlorine-induced shade change inhibitor, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Comparative Example 21A dyed union knit fabric was prepared in the same manner as in Example 15 except that a chlorine-induced shade change inhibitor was not used, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Comparative Example 22A dyed union knit fabric was prepared in the same manner as in Example 15 except that a union knit fabric comprised of fibers (A) and (B2) was used, no chlorine-induced shade change inhibitor as described above was used, and tannic acid and tartar emetic were used as chlorine-induced shade change inhibitors and dye fixing agents, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Comparative Example 23A dyed union knit fabric was prepared in the same manner as in Example 14 except that no chlorine-induced shade change inhibitor as described above was used and tannic acid and tartar emetic were used as chlorine-induced shade change inhibitors and dye fixing agents, and subjected to the chlorinated water treatment. The results are summarized in Table 5. Note that in all of the above-mentioned examples, not less than 80 weight% of MgO contained in the fiber (A) remained in the fiber (A) of the dyed knit fabric which underwent all treatment procedure. Example 22-28, Comparative Example 24-27The fiber and the fabric as used in Example 14-21 were used except that magnesium oxide in the fiber (A) mentioned in Example 1-4 was replaced with zinc oxide. This fiber is referred to as A3. The fabric comprised of fibers (A3) and (B2) was dyed in a dye bath (liquor ratio : 18:1) containing trimethyl orthoformate (0.5 g/ℓ) and Diacryl Brilliant Blue AC-E (cation dye), 1% owf, at from 40°C to 100°C for 45 minutes and at 100°C for 30 minutes, after which it was rinsed with warm water at 50°C for 10 minutes, followed by application of a chlorine-induced shade change inhibitor, Bisphenol A, 5% owf, which showed 79.5 milliequivalent per gram reaction amount of chlorine as determined by the method described above, at from 40°C to 80°C for 50 minutes. The knit fabric thus obtained was centrifugally dehydrated, squeezed with mangle, dried in pin tenter at 160°C and heat-set. The chlorinated water-induced shade change of the dyed fabric obtained as above was tested by immersing 1 part of the knit fabric in 400 parts of chlorinated water (available chlorine 100 ppm, pH 7.0) at 40°C for 30 minutes in a manner such that the chlorinated water stream vertically hits the fabric surface. The hue of the finished union knit fabric and that after the chlorinated water treatment were measured, based on which color fastness to chlorine (degree of shade change) was determined. The results are summarized in Table 6. The examples and comparative examples were conducted using different chlorine-induced shade change inhibitors in the same manner as in the aforementioned examples and comparative examples. The results are shown in Table 6. Note that in Example 22-28, not less than 90 weight% of zinc oxide contained in the fiber (A3) remained in the fiber (A3) of the dyed knit fabric which underwent all treatment procedure.	A dyed union knit fabric manufactured by dyeing a union knit fabric comprised of at least a polyurethane elastic fiber containing one or more chlorine-induced degradation inhibitors selected from the group consisting of magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide and hydrotalcite compounds in a proportion of 0.5-5.0 weight% based on the weight of the fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, wherein the polyurethane elastic fiber contains said inhibitors in a proportion of 0.5-4.5 weight% based on the weight of the fiber and the polyamide fiber and/or the cation dyeable polyester fiber exhausts or shows a dye uptake of not less than 0.01% owf of at least one member selected from the group consisting of acid dyes, metal-complex dyes fluorescent dyes, disperse dyes, reactive dyes, direct dyes, and cation dyes. A dyed union knit fabric according to claim 1, wherein the fabric contains at least one compound of the following formulas (I), (II) and (III) (OH)x―Z⁵―(B⁵)y (III) wherein Z¹ is an aromatic group; Z², Z³, Z⁴ and Z⁵ are independently aromatic groups the same as or different from Z¹; A is a bivalent group such as alkylene, sulfonyl, sulfide and azo; B¹ is a monovalent group such as alkyl, alkoxy, nitro, sulfone and amino, or hydrogen atom; B², B³, B⁴ and B⁵ are independently monovalent groups the same as or different from B¹, or hydrogen atom; R¹ and R² are the same or different and each is a group selected from the group consisting of alkyl and aryl; and k, l, m, n, s, t, u, v, x and y are positive integers satisfying the following formulas Q-1 to Q-5. 0 ≦ k ≦ 4 1 ≦ k+1 ≦ 5 0 ≦ m ≦ 4 1 ≦ m+n ≦ 5 0 ≦ s ≦ 4 1 ≦ s+t ≦ 5 0 ≦ u ≦ 4 1 ≦ u+v ≦ 5 1 ≦ x ≦ 4 1 ≦ x+y ≦ 6 having a reaction amount of chlorine of not less than 50 milliequivalent per gram as determined by the method described in the specification in a proportion of 0.1-20% relative to the weight of the fabric. A method for manufacturing a dyed union knit fabric of claim 1, wherein the pH of dye bath is maintained at not less than 4.5 throughout the dyeing process from the beginning to the end thereof when dyeing a union knit fabric comprised of at least a polyurethane elastic fiber, and a polyamide fiber and/or a cation dyeable polyester fiber, the polyurethane elastic fiber containing one or more members of the group consisting of magnesium oxide, zinc oxide, alminium oxide, magnesium hydroxide, zinc hydroxide, alminium hydroxide and hydrotalcite compounds in a proportion of 0.5-5.0 weight% based on the weight of the fiber, with at least one member dye of the group consisting of acid dyes, metal-complex dyes, fluorescent dyes, disperse dyes, reactive dyes, direct dyes and cation dyes. A method for manufacturing the dyed union knit fabric according to Claim 3, which comprises the use of orthoformate for dyeing. A method for manufacturing the dyed union knit fabric according to Claim 3, which comprises the use of an ester of alkylene glycol having an alkylene of 2 to 5 carbon atoms and formic acid for dyeing. A method for manufacturing the dyed union knit fabric according to Claim 3, 4 or 5, which comprises the use of an anionic phenol which does not take a quinone structure by reacting with an alkali, and orthoformate for dye fixing.	TOYO BOSEKI; TOYO BOSEKI KABUSHIKI KAISHA	ARIMATSU YOSHIKAZU C O TOYO BO; CHIBA SHUJI C O TOYO BOSEKI KA; IDO YOSHINORI C O TOYO BOSEKI; SHIMIZU TAKEHIKO C O TOYO BOSE; SUZUKI HAJIME C O TOYO BOSEKI; ARIMATSU, YOSHIKAZU, C/O TOYO BOSEKI KABUSHIKI K.; CHIBA, SHUJI, C/O TOYO BOSEKI KABUSHIKI KAISHA; IDO, YOSHINORI, C/O TOYO BOSEKI KABUSHIKI KASIHA; SHIMIZU, TAKEHIKO, C/O TOYO BOSEKI KABUSHIKI K.; SUZUKI, HAJIME, C/O TOYO BOSEKI KABUSHIKI KAISHA
EP-0489399-B1	489,399	EP	B1	EN	19,960,918	1,992	20,100,220	new	G01D5	G01D5	G01D5, G01J1, G02B3	G01D 5/36C	Displacement detector	Disclosed is a displacement detector including light generation source for generating a light, a scale to be irradiated by the generated light and displaceable relative to the irradiated light, first detection device having a photo-sensing element for detecting a light transmitted through the scale for detecting displacement information of the scale, a mark having a focusing function formed integrally with the scale, and second detection device having a photo-sensing element for sensing the light focused by the mark for detecting a reference position of the scale.	Displacement DetectorThe present invention relates to a displacement detector. Especially, the present invention relates to a technique to determine a reference point which is an origin point in a displacement detector such as an encoder which detects displacement of an optical scale. A rotary encoder for measuring a rotation angle or a rotation speed of a disk-shaped optical scale, which is an example of a displacement detector, is disclosed in the US-A-5 026 985, US-A-4 263 506 and US-A-4 477 189. The JP-A-63 081 212 discloses a rotary encoder which uses a cylindrical optical scale having a slit-like grating formed on a side thereof to measure a rotation angle thereof at a relatively high resolution with a simple construction. By the rotary grating being cylindrical, no alignment of two gratings (a rotary grating and a fixed grating) which has been required in the prior art is necessary, and a cancellation effect for a detection error due to the eccentricity of a rotating shaft is attained. Thus, the high precision and the simplicity in mounting are attained. Such advantage is achieved by providing a focusing optical system in the scale (in a hollow area) and projecting, by the focusing optical system, an image of the grating in a first region on the side of the scale to the grating in a second region on the opposite side of the scale to the first region with respect to the rotating shaft of the scale. On the other hand, an improved encoder which uses a similar slit grating or a cylindrical optical scale having a convexo-concave grating with a regular sloped surface such as a V-shaped groove formed on a transparent cylindrical member was suggested by the patentee. It utilizes a principle of Talbot interference which is a Talbot effect of the grating instead of the focusing optical system. According to such encoder, in addition to the effect of the prior art described above, it can further improve the simplification of the overall configuration, the volume reduction and the inertia reduction. When the above encoder is used in various systems, it is desirable to determine a reference position or an origin point of the rotation. By obtaining an origin point signal, an encoder capable of detecting an absolute position is provided. Configurations to obtain the origin point signal are shown in the above patents. The EP-A-0 439 804as prior art under Art 54(3) EPC shows to direct a light beam through two different portions of a diffraction grating of a rotary scale to be then detected by first detection means. Further, a light-condensing portion is provided separately from the grating. Light condensed by the light condensing portion is detected by second detection means to detect a reference position of the scale. Furthermore, the DE-A-3 542 154 shows a displacement detector which employs a reference mark, consisting of two cylindrical lenses. Zero impulse detectors detect the reference mark delivering correction zero impulses, thereby providing a high precision and a simple construction. It is an object of the present invention to provide a displacement detector by which a reference position signal can be produced with a high precision and a simple construction. According to the invention this object is achieved by the features of claim 1. Advantageous further developments are set out in the dependent claims. According to the invention the light beam from the light-generation means is split by a splitting means and the split light beams pass through the first portion of the cylindrical rotary scale. These split light beams are received by the second detection means after they have passed through the light-condensing mark portion to obtain a reference position signal with high precision while a simple construction of the displacement detector is guaranteed. According to the invention it is not necessary to provide a light-divider within the cylindrical rotary scale. According to the present invention the number of parts are reduced, the assembly is facilitated and the size of the detector is reduced. The present invention will be apparent from the following description of the preferred embodiments of the present invention. Fig. 1 shows a top view of an embodiment not according to the present invention, Fig. 2 shows a side view of the embodiment, Fig. 3 shows a detail of an optical system for detecting a reference position, Fig. 4 illustrates an operation of the detection of a reference position signal, Fig. 5 illustrates an operation of the detection of the reference position signal, Fig. 6 shows an ideal waveform of an output signal of the encoder of the embodiment, Fig. 7 shows an actual waveform of the output signal of the encoder of the embodiment, Fig. 8 shows an output waveform from a photo-detector, Fig. 9 shows an output waveform of the produced reference position signal, Fig. 10 shows an optical scale in the embodiment, Fig. 11 shows a modification of the embodiment not according to the present invention which uses a zone plate, Fig. 12 shows an enlarged view of the zone plate in Fig. 11, Fig. 13 shows a side view of another embodiment not according to the present invention, Fig. 14 shows a detail of an optical system for detecting a reference position in Fig. 13, Fig. 15 shows top view and side view of an embodiment of the present invention, Fig. 16 shows a perspective view of an optical system for detecting a reference position in Fig. 15, Figs. 17A and 17B show variations of a scale, and Fig. 18 shows a configuration of a drive system using the encoder. An embodiment not according to the present invention is now explained in detail with reference to the drawings. Fig. 1 shows a top view of an embodiment of the rotation detector not according to the present invention and Fig. 2 shows a side view thereof. In Fig. 1, numeral 1 denotes a semiconductor laser generating a coherent light beam having a wavelengths λ (= 780 nm). Numeral 2 denotes a collimator lens system converting a divergent light beam emitted from the semiconductor laser 1 into a substantially parallel light beam. Light irradiation means comprises the semiconductor laser 1 and the collimator lens system 2. Numeral 3 denotes a rotary optical scale having a cylindrical grating, which is rotated in either of directions shown by arrows. The scale 3 is coupled to a rotating drive shaft 5 of a motor at a center of a bottom 7 and used as an optical scale for detecting a rotation angle of the drive shaft 5 or the like. Fig. 10 shows a perspective view of the scale 3. The scale 3 is made of a light transmitting optical material. At least the grating region of the scale 3 has light transmittancy. A number of V-shaped grooves are arranged at a constant pitch over the entire circumference on an inner side of the cylindrical scale 3 to form the grating region. Return to Fig. 1, numeral 40 denotes a half-mirror (beam splitter) which is positioned in the cylindrical scale 3 and obliquely fixed thereto and splits a portion of an incident light to reflect it downward. Photo-detectors 4a, 4b and 4c which are photo-sensing means for detecting the rotate information of the scale are positioned at a position opposite to the light irradiation means with respect to the scale 3. Output signals of the respective photo-detectors are supplied to a signal processing circuit 6 comprising a rotation pulse count circuit, a rotation direction discrimination circuit, a signal interpolation circuit and a reference position signal generation circuit. In Fig. 2 showing a side view, a light beam split downward by the half mirror 40 is directed to a reference position detecting mark 41. The mark 41 is formed on a bottom surface of the bottom 7 of the scale at one point in one revolution to form a convex area having a focusing function like a cylindrical lens extending transversely to the circumferential direction. The convex area has the merit of being formed in the same process as that of the V-shaped grooves in the grating region of the scale 3. Numeral 45 denotes a photo-detector for detecting the light transmitted through the mark 41 to obtain a reference position signal. The photo-detector output signal is supplied to the signal processing circuit 6 producing the reference position signal. The original point of the rotation is derived from the reference position signal. The count value of the count circuit is reset by the reference position signal, thereby to determine the rotation angle from the original point or the absolute value of amount of rotation. Enlarged views shown in the bottom of Fig. 1 show a detail of the grating region of the scale 3. The V-shaped grooves and the plane areas are alternately arranged to form the grating. The V-shaped grooves with a number of n are arranged on the inner side of the cylinder at a constant pitch p (rod) along the circumference (n x p = 2π rod). The V-shaped groove has a width of 1/2·P (rod). Each of the two planes consisting of the V-shaped groove has a width of 1/4·P (rod). Each inclined plane is inclined at an angle  with respect to a line connecting the bottom and the center of the V-shaped groove, the angle being not less than a critical angle ( = 45 degrees in the present embodiment). A distance d (an inner diameter of the scale) along the optical axis between the grating in a first region 31 of the scale 3 and the grating in a second region 32 is selected so as to satisfy: d = N·P2/λ (N = 3) P = πd/n (n: total number of slits) where P is a grating pitch and λ is a wavelength. By setting the diameter d of the scale 3, as above the image of the grating in the first region 31 on the side of the scale 3 can be directly projected onto the grating in the second region 32, without focusing optical system in the hollow of the scale 3. The projected grating image is so called as a Fourier image, which is produced by a self-focusing of the image due to a light diffraction phenomenon. In the present embodiment since the scale 3 is cylindrical, the Fourier image tends to be curved and its contrast is reduced to some degree. However, there is no practical problem if the light irradiation means (1 and 2) and the scale 3 are constructed so as to satisfy: (N - 1/4)P2/λ < d < (N + 1/4)P2/λ (N: natural number) P = πd/n (n: total number of slits) In the present embodiment not according to the invention, the material of the scale 3 is plastic and the scale 3 is produced by an injection molding method or a compression molding method to facilitate mass production. Accordingly, it provide low cost manufacturing method as compared with the conventional photolithography process. In the encoder of the present embodiment not according to the invention, as an external environmental temperature changes, the diameter d of the scale, the grating pitch P and the wavelength λ of the semiconductor laser change slightly. So, there is some possibility that relative positional shift between the focusing position of the Fourier image and the grating plane may happen to cause the reduction of the S/N ratio of the detection signal. For example, as the temperature rises, the diameter d of the scale increases, the pitch P of the grating increases accordingly, and further, the wavelength λ shifts to the long wavelength side. The position L of the Fourier image changes by a factor of P2/λ as derived from the equation L = N·P2/λ. Therefore, the material of the scale and the characteristic of the semiconductor laser are selected so that the change (Δd) of the diameter d of the scale and the displacement (ΔL) of the Fourier image by the temperature change are as close as possible, whereby the relative positional shift between the position of the grating plane and the focusing position of the Fourier image can be reduced and the S/N ratio of the detection signal does not deteriorate even if the external temperature changes. In the semiconductor laser having the wavelength of 780 nm used in the present embodiment, the wavelength variation is approximately 10 nm for the temperature change of 50°C. The material of the scale is preferably one having a large thermal expansion coefficient. In the present embodiment, the material of the scale 3 is plastic (acrylic resin having n = 1.49). Since a thermal expansion coefficient of the plastic material is larger than that of glass or the like, the plastic material has an advantage of the reduction of the S/N ratio of the output signal by the temperature change being smaller. Therefore, it is very suitable for the material of the scale of the encoder of the present embodiment because of both said advantage and the advantage of its low cost. The light source which may be used in the present invention is not limited to the semiconductor laser. For example, the semiconductor laser 1 in Fig. 1 or Fig. 2 may be replaced by a point light source LED. Further cost reduction is attained by using the LED which is less expensive than the semiconductor laser. A principle of measurement of the rotation information in the present embodiment not according to the invention is now explained with reference to Fig. 1. The light beam from the semiconductor laser 1 is converted to a convergent light beam by adjusting the position of the collimator lens system 2. The convergent light beam is incident on the first region 31 of the scale 3. The convergent light beam is used because the side plane of the scale 3 has a refractive power corresponding to a concave lens due to a difference between the curvature of the outer side plane and that of the inner side plane. The light having entered the scale is substantially parallel by the concave lens action. As shown in the enlarged left view of Fig. 1, the light beam which reaches the grating 30a in the first grating region passes through the plane 30a and enters the cylinder. The light beam which reaches the grating plane 30b-1 is totally reflected toward the plane 30b-2 because the inclination angle is larger than the critical angle. It is also totally reflected at the plane 30b-2. Thus, the light beam which reaches the plane 30b-1 does not enter the rotating member, but it is returned to the substantially incident direction. Similarly, the light beam which reaches the plane 30b-2 is also returned after the repetition of the total reflection. Accordingly, the light beams which reach the two inclined planes 30b-1 and 30b-2 of the V-shaped groove in the first region 31 do not go into the cylinder but they are reflected, and only the light beam which reaches the plane 30a goes into the cylinder. Thus, in the first region 31, the diffraction grating with V-shaped groove has the same function as that of a transmission type amplitude grating. The light beam is diffracted at the grating in the first region 31, and diffracted light beams of 0-order ±1-order, ±2-order and so on are generated by the grating. By the interference of two or three light beams of 0-order and ±1-order, the Fourier image of the grating in the first region 31 is focused in the scale 3. The Fourier image is repeatedly focused behind the grating plane at positions corresponding to integer multiples of a distance L. In the present embodiment, the wavelength λ of the light source, the grating pitch P and the position of the collimator lens 2 are selected so that the third (N=3) Fourier image is focused on the grating plane in the second region 32. The brightness pitch of the Fourier image is equal to the grating pitch P in the first region 31 and the second region 32. The light beam is split into two directions S and T by the half-mirror 40 which is arranged to go into the cylinder (Fig. 2). The light beam having passed through the half-mirror 40 to go straight in the direction S is incident on plane 30a in the second region 32, and it passes through the plane 30a to reach the photo-detector 4c since the incidence of the light beam is substantially normal, as shown in the enlarged right view of Fig. 1. The light beams which reach the two inclined planes 30b-1 and 30b-2 of the V-shaped plane are greatly deflected in different directions due to the incident angles of approximately 45 degrees and reach the photo-detectors 4a and 4b, respectively. In the second region 32, the light beam is divided in the three directions by the three planes of different inclination directions, that is, the two inclined planes each inclined in different direction to the incident light beam and the plane between V-shaped grooves, and the divided light beams reach the photo-detectors 4a, 4b and 4c arranged at the positions corresponding to those planes, respectively. Thus, in the second region 32, the V-shaped grating functions as a light beam splitter. If the scale 3 is rotated, an amount of light detected by the photo-detectors 4a, 4b and 4c will change. The balance of the amount of light incident on each photo-detector changes in accordance with the relative displacement of the positions of the grating and the Fourier image. As a result, when the scale 3 is rotated counterclockwise, the amount of light changes as shown in Fig. 6 as the grating is rotated. In Fig. 6, an abscissa represents a rotation angle of the cylindrical grating and an ordinate represents a detected amount of light. Signals a, b and c correspond to the photo-detectors 4a, 4b and 4c, respectively. When the scale 3 is rotated clockwise, the signal a corresponds to the photo-detectors 4b, the signal b to the detector 4a, and the signal c to the detector 4c. The direction of rotation can be determined by this difference. Fig. 6 shows a theoretical amount of light change, when the contrast of the Fourier image is very high and close to an ideal one. Since the actual contrast of the Fourier image is lower, each amount of light changes substantially sinusoidally as shown in Fig. 7. The rotation information such as rotation angle, rotation speed or rotation acceleration is derived from those signals. A method for detecting the reference position or the origin point by using the light beam split in the direction T by the half-mirror 40, is now explained in detail with reference to Fig. 3. Fig. 3 shows a detail of the detection optical system for detecting the reference position, which is viewed in the direction A-B of Fig. 2. The plane 8 at the bottom 7 of the scale on which the light beam is incident, is planar, and the mark 41 for generating the reference position signal is formed at a point on a circumference of a rear surface of the plane 8. The mark 41 comprises a cylindrical lens having a one-dimension focusing action. Said cylindrical plane slenderly extends transversely (normal to the plane of the drawing) to the circumference of the scale. The photo-detector 45 for producing the reference position signal is provided below the mark 41. The entire area except the portion where the mark 41 is formed, is of a light diffusion plane 9 in order to enhance a sensitivity for detecting the reference position, although it is not necessarily the light diffusion plane. Figs. 4 and 5 illustrate the detection of the reference position signal. In Fig. 5, the cylindrical lens mark 41 is shifted from the photo-sensing plane 42 of the photo-detector 45. In this case, the light transmitted through the plane 8 is diffused by the diffusion plane 9 so that only a small portion of the light is directed to the photo-sensing plane 42. In Fig. 4, on the other hand, the scale has been displaced from the position of Fig. 4 so that the optical axis of the cylindrical lens of the mark 41 aligns to the photo-sensing plane 42. In this case, the light beam applied to the mark 41 is focused by the cylindrical lens so that a maximum amount of light is directed to the photo-sensing plane 42. Fig. 8 shows the change in the amount of light in the photo-sensing plane 42 by the rotation of the slit. Normally, only a small portion of the light reaches the photo-sensing plane 42, and an output of the amount of light is of low level L0. During a short period in which the reference slit passes, the amount of light on the photo-sensing plane 42 is maximum. Fig. 9 shows the reference position signal produced by a circuit (not shown) based on the amount of light. Thus, the absolute reference position signal is produced at a predetermined one point in one revolution (360 degrees). When a plurality of marks 41 are provided along the circumference, the plurality of reference position signals are produced in one revolution. In a modification of the mark 41, a zone plate may be used to attain an equivalent function to that of the above embodiment. Fig. 11 shows such a modification not according to the invention in which the same numerals designate the same parts. A one-dimensional Fresnel lens which corresponds to the cylindrical lens in the above embodiment is formed at a portion on the lower plane 9 of the bottom of the scale to form a zone plate 44 having a focusing function in only the direction of movement of the scale. Fig. 12 shows an enlarged view of the zone plate. In the present modification, it is an amplitude type zone plate among the conventional Fresnel zone plate. A light shielding area is formed by a totally reflection plane as shown in Fig. 12. In the Fresnel zone plate, the light shielding areas and the light transmitting areas are alternately arranged at an interval RN: RN = λP2 (2N- 1) N = 1, 2, 3, .... where λ is a light wavelength and P is a principal focal distance of the Fresnel zone plate corresponding to a distance from the zone plate 44 to the photo-sensing plane 42 in Fig. 11. Another embodiment not according to the present invention is now explained. Fig. 13 shows a configuration thereof, and the same numerals as those shown in Fig. 2 designate the same parts. It differs from the previous embodiment in that the reference position which is the original point is detected by using the light beam split in the direction T by the half-mirror 40. The photo-detector 45 for detecting the reference position is arranged in parallel to the photo-detector 4 for reading the scale. Fig. 14 shows a detail of the reference position detecting optical system in the vicinity of the mark in the present embodiment. The plane 8 of the bottom 7 of the scale on which the light beam is incident is planar and a mark 43 for detecting the reference position is provided at one point on a circumference on the plane 8. The mark 43 comprises a cylindrical lens having a one-dimension focusing function as the mark in the previous embodiment does, and the cylindrical plane slenderly extends in the direction (normal to the plane of the drawing) transverse to the circumferential direction. A notch is formed in the lower plane 9 of the bottom 7 of the scale to form a reflection plane 44 having an inclination of 45 degrees. Since the reflection plane 44 is set at more than a critical angle, it totally reflects the light beam directed from the above in the orthogonal direction to direct it toward the outer side of the cylinder. The reflection plane 44 need not be mirror-finished and is integral with the cylinder grating. Therefore, it is easily manufactured. The light beam reflected at the reflection plane 44 is further focused by the cylinder outer surface to the photo-detector 42. The plane except the mark 43 is the light diffusion plane as it is in the previous embodiment in order to enhance the detection sensitivity. In Fig. 14, the optical axis of the cylindrical lens of the mark 43 aligns to the photo-sensing plane 42 of the photo-detector 45. In this case, the light beam incident on the cylindrical lens is focused by the lens, so that a maximum amount of light is incident on the photo-sensing plane 42. In the present embodiment not according to the invention, the reference position signal similar to that of Fig. 6 or Fig. 7 is produced. Further, in the present embodiment, the photo-detector for detecting the reference position signal can be positioned in the vicinity of other photo-detector to further reduce the volume of the detection system. An embodiment of the present invention is now explained. Fig. 15 shows a top view and a side view of the present embodiment. The same numerals to those shown in the embodiment of Figs. 1 and 2 designate the same parts. The features of the present embodiment over the previous embodiments are the following three points. (1) In the previous embodiments, the light beam is split by the half-mirror 40 located in the cylindrical scale and the split light beam is directed to the mark which is the reference position, while in the present embodiment, a diffraction grating plate 50 having a beam splitting function is arranged between the lens 2 and the cylindrical scale 3 to split the light beam into three beams (0-order, ±1-order). The direction of arrangement of the grating of the diffraction grating plate 50 is orthogonal to the direction of arrangement of the grating of the scale 3. One of the split light beams (+1-order) in directed to the mark 3d. The 0-order light is irradiated to the grating of the scale 3 and the rotation information is measured by using the Fourier image as it is in the previous embodiment. The -1-order light is an unnecessary light. (2) The mark (41, 43) is arranged on the bottom of the cylindrical scale in the previous embodiments, while in the present embodiment, a mark 3d is arranged on the outside plane of the cylindrical scale separately from the grating. (3) The detecting element 4d for detecting the reference position is arranged on a substrate in parallel with the detecting elements 4a, 4b and 4c for reading the scale to form a single photo-detecting unit 4. The operation to detect the reference position in the present embodiment is explained below. The mark 3d used to detect the reference position is provided at one point on the circumference on the outside plane 3b (on which the light beam is incident) of the scale 3. The mark 3d comprises a cylindrical lens having a one-dimension focusing function as it does in the previous embodiment, and the cylindrical plane slenderly extends in the direction (in the plane of the drawing) transverse to the circumferential direction of the scale. The cylindrical plane is positioned such that only the +1-order deffracted light having passed through the cylindrical scale 3 is directed thereto. The plane except the mark 3d is the light diffusion plane as it is in the previous embodiments. The cylindrical lens may be replaced by the zone plate as it is in the previous embodiment. The pitch of the deffraction grating plate 50 is selected to meet the above condition. When the +1-order light of the split light beams is irradiated to the cylindrical plane, it is focused on the detecting element 4d. In Fig. 15, the optical axis of the cylindrical lens of the mark 3d aligns to the detecting element 4d. In this case, the light beam incident on the cylindrical lens is focused by the lens, so that a maximum amount of light is incident on the photo-sensing element 4d. In this manner, the reference position is detected. While the mark 3d is provided on the outside plane 3b of the scale 3, it may be provided on the conical plane 3c to attain the same effect. In this present embodiment, the same reference position signal as that in Fig. 6 or Fig. 7 is produced. Like in the previous embodiments, the photo-detector for detecting the reference position signal may be arranged closely to other photo-detectors to enhance the volume reduction of the detection system. In the embodiments described above, the reference position is detected by using the encoder having the grating formed thereon by forming grooves having inclined surfaces at the constant pitch on the light transmitting cylindrical scale. Alternatively, a rotary encoder having a disk-shaped rotary scale as shwon in Fig. 17A or a linear encoder having a planar linear scale as shown in Fig. 17B may be used to detect the reference position. The scale having the grating and the mark which has the focusing function on the same plane can be formed by the injection molding process. Thus, it is advantageous in the manufacturing cost of the scale. The grating of the scale is not limited to the grooves but it may be of brightness slit type. In the above embodiments, the mark comprises the cylindrical lens having the focusing function or the zone plate, although other members having an equivalent function may be used. While one-dimensional focusing function has been described above, two-dimensional focusing function may be utilized to attain the same function. Fig. 18 shows an example of a system utilizing said encoder. It shows a configuration of a drive system having a rotary encoder. An encoder 111 described above is connected to a rotation output portion of drive means 110 including a motor, an actuator and a drive source such as an internal combustion engine, to detect the rotation status such as a rotation angle or a rotation speed as well as the reference position of rotation. The detection output of the encoder 111 is fed back to control means 112, which sends a drive signal to the drive means 110 so as to attain the condition set by setting means 113. By constructing such a feedback system, the rotation condition set by the setting means 113 is attained. Such a drive system is applicable to various machine tools, manufacturing tools, measuring instruments, robots, cameras, audio/video equipments, information equipments as well as any apparatus having the drive means.	A displacement detector, comprising light-generation means (1) for generating a light; a cylindrical or disk-shaped rotary or planar linear scale (3) having a grating formed on a side plane thereof, wherein the light is irradiated to a first portion (31) on the side plane and directed to a second portion (32) different from said first portion (31); first detection means (4a, 4b, 4c) for detecting said light irradiated through said grating in said second portion (32) to detect displacement information of said scale (3); a light-condensing mark portion (3d) provided on said scale (3) separately from said grating; second detection means (4d) for detecting the light condensed by said light-condensing portion (3d) to detect a reference position of said scale (3); and a splitting means (50) for splitting said light beam from said light-generation means (1) to direct the split light beam to said light-condensing portion (3d) through said first portion (31). A displacement detector according to claim 1, characterized in that said splitting means (50) comprises a diffraction grating. A displacement detector according to claim 1, characterized in that said light-condensing mark portion (3d) comprises a lens. A displacement detector according to claim 1, characterized in that said light-condensing mark portion (3d) comprises a zone plate. A displacement detector according to claim 1, characterized in that said light-condensing mark portion (3d) is provided on the side plane of said scale (3). A displacement detector according to claim 1, characterized in that said scale (3) comprises a light-transmissive grating having a concave-convex surface inclined to an incident light, with said grating being arranged at a constant pitch. A displacement detector according to claim 1, characterized in that said light-generation means (1) comprises a semiconductor laser. A displacement detector according to claim 1, characterized in that said light-generation means (1) comprises an LED.	CANON KK; CANON KABUSHIKI KAISHA	IGAKI MASAHIKO; IGAKI, MASAHIKO,; IGAKI, MASAHIKO, C/O CANON KABUSHIKI KAISHA
EP-0489401-B1	489,401	EP	B1	EN	19,950,301	1,992	20,100,220	new	A23F5	A23F5	A23F5	A23F 5/48H, A23F 5/26B, A23F 5/18	Process for the preparation of soluble coffee	The invention relates to a process for preparing soluble coffee with an infusion quality similar to that of roast bean coffee, with which instant-typical off-flavour characters are no longer detectable. Ground roast coffee of a particle size of at most approximately 1.8 mm is treated in a percolator with saturated steam in order to separate essential aroma constituents and the separated aroma constituents obtained as condensate. The remaining roast coffee is subjected at high pressure with extraction water to a primary extraction with the aid of at least 2 percolators, the portion evaporated through pressure-relief is condensed and obtained as further aroma condensate, and the non-evaporated portion placed in interim storage as primary extract. The remaining roast coffee is then subjected at high pressure and increased temperature to a secondary extraction in at least 2 percolators, the portion of the extract evaporated through pressure-relief is separated and discarded, and the non-evaporated portion obtained as secondary portion and optionally divided into a first portion and a second portion. The remaining roast coffee is optionally subjected to a tertiary extraction at high pressure and increased temperatures in at least 2 percolators, the portion evaporated through pressure-relief is discarded and the non-evaporated portion obtained as tertiary extract. The second portion of the secondary extract and the tertiary extract, optionally after being combined, are optionally extracted with liquid or supercritical CO₂ at a high pressure, the extracted portion is discarded and the remaining extract is recovered. The various extracts are condensed in multi-stage evaporators, combined and mixed with the two aroma condensates, and the finally obtained extract with a solids concentration of approximately 35 to 55 % is freeze- or spray-dried in the usual way.	The invention relates to a process for preparing soluble coffee with an infusion quality similar to that of roast bean coffee, with which instant-typical off-flavour characters are no longer detectable. The preparation of soluble coffee is described in numerous patents. The aim of the majority of processes quoted is to prepare soluble coffee products with an aroma quality of bean coffee. Bolt (US-A-3 700 463) describes a coffee-extraction process with which the pressure, the temperature and the extraction time in the fresh-extraction stage or in the first extraction column are kept within a narrowly defined range in order to obtain a coffee extract with great similarity to a roast-coffee infusion, richness, acidity and aroma characters. For this a good-quality extract is obtained in the counter-flow process in 4 to 12 extraction columns at a temperature of 71 to 127 °C, a pressure of 0.35 to 2.5 bar and with a cycle time of 5 to 45 minutes in the fresh-extraction column. The low pressure is realized only in the fresh-extraction column, in the other extraction columns, which already contain partly extracted coffee, higher pressures (Example 1: 10.5 bar) can be realised. This is a one-stage process, with which an extract of relatively low yield is obtained. The length/diameter ratio of the extraction column is ca. 10:1. Relatively coarsely ground roast coffee is used for the extraction. Steam stripping of the ground, fresh roast coffee is also not described. Admittedly, the temperature, the pressure and the cycle time are described as critical, but only in the fresh-extraction column, not during the whole extraction process. A multi-stage extraction process is described by Matsuda, Ajinomoto General Foods (EP-A-0 097 466). The secondary extract, which is obtained in the autoclave extraction stage is split into two extraction portions: the first extract drawing from the secondary extract contains a relatively low concentration of solids and a flavour quality comparable with that of the primary extract, the second extract drawing from the secondary extract produces a higher solids concentration but a lower flavour quality. The primary extraction takes place in the temperature range of approximately 100 to 145 °C, the secondary extraction at approximately 160 to 190 °C. By splitting the secondary extract, it is intended to improve the taste while maintaining the economic yield. With this process relatively coarsely ground roast coffee is used (see Example 1). Information on the geometry of the percolators is lacking and likewise no information on pressure and cycle time during the extraction is given. According to a further known process for increasing the solubility of already partly extracted ground roast coffee (US-A-4 798 730, Scoville, GF), the ground and already partly extracted roast coffee is extracted in a one-stage process with water at a temperature of approximately 193 to 232 °C. In order to obtain a high yield of approximately 55 to 68 wt-%, relative to the originally used roast coffee, the residence time of the extract in the extractor is kept considerably lower than that of the ground roast coffee. The relationship between the residence time of the ground roast coffee and that of the extract is described as critical. The residence time of the ground, already partly extracted roast coffee is 30 to 120 minutes in the extractor, while that of the extract is only 7 to 45 minutes. The draw-off factor is at least 6, preferably 8 to 10. Partly extracted ground roast coffee is extracted with water at a temperature of 193 to 232 °C in an extraction column, the length/diameter ratio of which can be 2:1 to 20:1. The weight ratio between extract and originally used roast coffee (draw-off factor) is at least six. The residence time of the partly extracted roast coffee of 30 to 120 minutes is considerably longer than the residence time of the extract of 7 to 45 minutes in the extraction vessel. Thanks to these extraction conditions a hydrolysis of the partly extracted roast coffee is achieved and at least 50 % of the mannan fraction extracted from the roast coffee. Overall, an extraction of 55 to 68 wt-%, relative to the originally used roast coffee, is achieved. No information on grinding fineness of the roast coffee is given. For this process, pressure is obviously not critical. It is merely stated that, under the prevailing process conditions, the pressure is to be set so that the water does not evaporate. Vogel (US-A-4 707 368) describes a process for careful aroma separation, with which, prior to the percolation process, steam stripping is carried out under vacuum conditions and at a maximum of 93 °C. A further process for the production of a coffee extract is known from EP-A-0,151,772 (Joh. Jacobs & Co. GmbH). Roasted coffee beans are broken and subjected to a first hot water extraction stage for making coffee extract. The remaining roasted coffee is then subjected to a further, secondary hot water extraction. The secondary extract obtained is treated with a weakly basic ion exchanger such that, on the one hand, the pH of the extract is increased and, on the other hand, taste-impairing substances are adsorbed. In addition to preparing soluble coffee using multi-stage extraction, further processes are known for careful aroma separation, for aromatizing soluble coffee, for reducing acids and off-flavour substances and for attaining higher yields. Thus, Pfluger et al. (CA-A-965 638) describe a process for preparing an improved coffee product, with which roast coffee is extracted semi-continuously in percolators in the counter-flow process. The drawn-off extract is divided into two portions, one portion having a higher quality and a higher solids concentration and the second portion a lower solids concentration and a poorer quality. From the second portion, some of the water is evaporated in less than 30 seconds. Subsequently, the concentrated second portion is dried together with the first portion. This process is intended to minimize the occurrence of off-flavour substances. Furthermore, a percolation process is described by Katz (CA-A-1 038 229), with which the percolators display a special geometry (conical percolators; as per Example: height 4.5 m, diameter at the lower part 91 cm and at the head of the percolator 61 cm). Finally, Katz (US-A-3 944 677) describes a percolation process, with which increasingly finely ground roast coffee is used in the direction of the extraction-agent flow. However, the information on the grinding fineness is very imprecise (see Example 1). The disadvantage common to all of these known processes is that they have not managed to prepare a soluble coffee without instant-typical aroma characters and thus to achieve roast bean coffee quality. Products of higher yield, which are desired on account of profitability, display, in addition to the instant-typical aroma characters, an off-flavour occurring during the hydrolysis process, so that the quality of the thus prepared soluble coffee is not to be equated with a roast coffee infusion. The known aromatizing processes and processes for removing these aroma faults have likewise enjoyed little success to date. Admittedly, with the low-yield products a soluble coffee of better quality is obtained, but even with these products a soluble coffee with roast bean coffee flavour was not achieved, because even with these products the instant-typical aroma characters occur. Furthermore, because of the low yield, no economically justifiable process is provided. The aim of the present invention is thus to make available a process with which a soluble coffee is provided in an economically acceptable yield, with which the original aroma of the starting roast coffee is retained and off-flavour characters arising from the hydrolysis process are no longer present, so that the soluble coffee has a roast bean coffee quality. This aim is achieved by a process with multi-stage extraction of ground roast coffee including the steaming of the coffee before the extraction, followed by condensation of the distillate, a first extraction with water in at least two percolators at a temperature of up to more than 100°C, a second extraction with water in at least two percolators at a higher temperature than in the first extraction, the combining of the condensate from the steaming step with the concentrated extracts from the first and second extraction stages and the drying of the combined mixture, characterized in that a) ground roast coffee of a particle size of at most 1.8 mm, which has been moistened to a water content of 4 to 70 wt-%, relative to the ground dry roast coffee, is treated in a percolator with a length/diameter ratio of 3.2:1 to 0.9:1 with saturated steam at a pressure of 0.1 to 1 bar and a temperature of 30 to 100°C for 2 to 40 minutes, the steam loaded with coffee constituents is condensed at a temperature of 0 to 15°C to a condensate quantity of 3 to 20 wt-%, relative to the quantity of dry roast coffee used, and the condensate is obtained as aroma a , b) the coffee remaining from stage a), freed from aroma a , is subjected with extraction water to a primary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee, at a temperature of 20 to 150°C and a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.2:1 to 0.9:1 for 2 to 40 minutes per percolator and for an overall time of 10 to 200 minutes, followed by pressure-relief to 0.001 to 1 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is condensed at a temperature of 0 to 15°C and the condensate is obtained as aroma b and the non-evaporated portion as primary extract, c) the coffee remaining from stage b), freed from aroma b and from primary extract, is subjected with extraction water to a secondary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee at a higher temperature than in stage b) within a range of 100 to 215°C and at a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.2:1 to 0.9:1 for 2 to 40 minute per percolator and for an overall time of 10 to 200 minutes, followed by pressure-relief to 0.01 to 2 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is discarded, the non-evaporated portion is obtained as secondary extract, d) the primary extract is concentrated in a multi-stage evaporator to a solids concentration of 25 to 40%, and parallel to this, the secondary extract is concentrated in a multi-stage evaporator to a solids concentration of 40 to 60%, the concentrated extract solutions are combined and mixed with aromas a and b and the obtained extract, which has a solids concentration of 35 to 55%, is freeze- or spray-dried in the usual way. In a preferred embodiment the coffee remaining from stage c), freed from the discarded evaporated portion and from the secondary extract, is subjected with extraction water to a tertiary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee at a higher temperature than in stage c) within a range of 150 to 240°C and at a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.1:1 to 0.9:1 for 2 to 40 minutes per percolator and for an overall time of 8 to 160 minutes, followed by pressure-relief to 0.01 to 5 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is discarded and the non-evaporated portion is obtained as tertiary extract, which itself is extracted, in order to remove off-flavour substances, with liquid or supercritical CO₂ at a temperature of 20 to 120°C and a pressure of 60 to 400 bar and the remaining extract being concentrated in a multi-stage evaporator to a solids concentration of 40 to 60%, and being combined with aromas a and b and the concentrated extracts from the primary and secondary extractions. In another preferred embodiment the secondary extract is divided into a first portion of approximately 70% and a second portion of approximately 30%, the second portion being extracted, in order to remove off-flavour substances, with liquid or super-critical CO₂ at a temperature of 20° to 120°C and a pressure of 60 to 400 bar, the remaining extract being concentrated in a multi-stage evaporator to a solids concentration of 40 to 60% and being combined with aromas a and b and the concentrated extracts from the primary and secondary extractions. The second portion of the secondary extract and the tertiary extract are preferably combined before being extracted with CO₂. The primary, secondary and tertiary extractions are preferably carried out at a drawing-off ratio of roast coffee input to extraction quantity of 1:2 to 1:6. The cycle time in the individual extraction stages b), c) and e) is preferably 5 to 12 minutes. The pressure in the individual extraction stages b), c) and e) is, in a preferred embodiment, 35 to 60 bar. Whilst in stage a) only one percolator is usually used, in each of stages b), c) and e) at least 2 percolators, preferably 4 to 7 percolators, are used. The percolators preferably have a length/diameter ratio of 3:1 to 2:1, particularly of 2.5:1. The process is preferably carried out semi-continuously using - preferably in circular arrangement - 7 to 22 percolators in stages a) to c) and e), with, as already mentioned, only one percolator being provided for stripping stage a) and at least 2 percolators for each of the three other stages b), c) and e), which are in contact with each other within the individual stages so that the outlet of each percolator is joined to the inlet of the following percolator and the fresh extraction water being introduced into the last percolator in each case with the relatively largely extracted coffee of stages b), c) and e) and being drawn off from the first percolator in each case with slightly extracted coffee and the plant being operated with cycle times - identical for all percolators - so that in each cycle time a percolator preceding the stripping percolator of stage a) is filled with fresh, ground roast coffee and the last percolator of stage e) is emptied of completely extracted coffee, whereby stages a) to c) and e) always move on one percolator at a time towards the newly poured, fresh roast coffee. It is obvious that within the quoted temperature ranges and extraction-time ranges, operations for the individual extraction stages are such that shorter extraction times are used at higher temperatures and longer extraction times at lower temperatures. The figure shows a diagrammatic representation of an entire extraction plant with 16 percolators in total. In the following, the process according to the invention is illustrated in more detail with reference to this figure. Freshly ground roast coffee is located in the reserve vessel (1) of percolator 16. After percolator 16 has been emptied and rinsed, the roast coffee is emptied from the reserve vessel into the percolator. Immediately thereafter the ground roast coffee is moistened via process-water (2). In the following cycle saturated steam is passed through the pre-moistened roast coffee, now in percolator 1, via stripping-steam pipe (3). Steam and stripped aromas are removed with the aid of an aroma-extraction valve (4) via a pipe (5), condensed in a two-stage plate-cooler (6) and the aroma obtained collected as aroma a in a storage tank (7). The process is carried out under vacuum. In the next cycle, the stripped percolator is connected into the primary extraction stage, comprising percolators P6 to P2, and extract from percolators P6 to P3 is passed through, followed by extraction. The extract, prior to entry into percolator P2, is set to a defined temperature by means of an intermediary cooler (8). The extract is pressure-relieved via a pressure-reducing system (9) directly into a flash evaporator (10). The steam portion and the aromas are condensed in a two-stage cooler (11) and the obtained aroma is stored as aroma b in a storage tank (12). The liquid extract portion is pumped out of the flash evaporator (10) and placed in interim storage in a storage tank (13) as primary extract. The described percolator passes through the primary extraction stages P2 to P6 and is then connected into the secondary extraction stage P11 to P7. Percolator P7 remains isolated for one cycle length, while it is raised to the temperature level of percolators P8 to P11. In the next cycle, the extract from percolators P11 to P9 is passed through percolator P8, followed by extraction. The extract is pressure-relieved, analogous to the drawing of the primary extract, via a pressure-reducing system (14) directly into a further flash evaporator (15). The steam portion is condensed in a cooler (16) and stored in a container (17). This steam portion is removed from the process and discarded. The liquid extract portion is pumped out of the flash evaporator (15) and placed in interim storage in a storage tank (18) as secondary extract. Depending on the embodiment, the secondary extract is either passed without further treatment via pipe (19) to an evaporator not shown, or part of the secondary extract is drawn off via pipe (20) and subjected to a CO₂ extraction, which is explained in more detail below. Percolator P8 moves through the secondary extraction stage as far as percolator P11 and is then taken over as percolator P12 into the tertiary extraction unit P15 to P12. Here, it is firstly isolated and raised to the increased temperature level of the tertiary extraction stage. In the next cycle, the extract from percolators P15 to P14 is passed through percolator P13, followed by extraction. The process here is analogous to the previous extraction stages. The extract drawn off from percolator P13 is pressure-relieved via a pressure-reducing system (21) directly into a third flash evaporator (22), the steam portion being condensed in a cooler (23), collected in a container (24) and subsequently discarded. The liquid extract portion is pumped out of the flash evaporator (22) and placed in interim storage in a storage tank (25) as tertiary extract. The tertiary extract obtained is drawn off via the pipe (26) and, depending on the embodiment, passed alone or mixed with the second portion of the secondary extract to a CO₂ extraction column (27). The extracted portion is collected in a separator (28) and discarded, whilst the extract freed from the extracted substances is placed in interim storage in a storage tank (29). The individual extracts in interim storage are then drawn off via the pipes (19, 32 and 33) and individually passed to evaporators, which are not shown in the figure. The condensed extracts are brought together and combined with the aromas a and b drawn off via the pipes (30 and 31). The combined extract obtained is then freeze- or spray-dried in usual devices, likewise not shown. Thanks to the process according to the invention it has become possible to prepare a soluble coffee in economically acceptable yield, which displays a roast bean coffee quality and with which the typical off-flavour characters can no longer be detected. First of all it is important that the extraction time of the aroma-carrying fraction is kept very short after the steam distillation of the ground roast coffee in order to obtain the volatile aromas. The particle size of the roast coffee used approaches the grinding fineness usual with vacuum-packed coffee. Normally, percolation processes are carried out with a very large amount of fairly coarsely ground roast coffee. In addition, the number of percolators is doubled to tripled compared with usual percolation processes and their geometry is also changed to a length/diameter ratio of 3:1 to 0.9:1 (usual length/diameter ratios are in the range of 4:1 to 7:1 and even more; see US-A-4 707 368). It has surprisingly been shown that with these unusually short percolators an aroma distillate can be obtained which can be satisfactorily stored at low temperatures and contains an adequate roast coffee aroma. Furthermore, it is of essential importance that the extraction takes place under a high pressure of 5 to 100 bar, preferably 40 to 60 bar. In order to obtain the roast coffee quality with an economic degree of extraction, the extraction is carried out in 7 to 22 percolators. These percolators are each allocated to two or three extraction units, depending on the degree of profitability, the first extraction unit supplying the primary extract, the second the secondary extract and the third the tertiary extract. If a profitability of up to ca. 50 % extraction is required, relative to the roast coffee, the process can be carried out in to stages, i.e. a primary extraction and a secondary extraction suffice. If a somewhat higher profitability is to be achieved, the secondary extraction takes place at somewhat higher temperatures within the quoted temperature range, off-flavour substances occurring towards the end of the extraction. It was surprisingly found that these off-flavour substances can be surprisingly readily removed by a supercritical extraction with liquid or compressed gaseous carbonic acid from the aqueous phase. Approximately the first 70 % of the secondary extract occurring need not be subjected to this CO₂ extraction. They contain practically no off-flavour substances. Only the remaining 30 % of the secondary extract need be extracted with CO₂, if the secondary extraction is carried out at higher temperatures. With the aid of adsorbents, preferably activated carbons, molecular sieves or ion-exchanger resins, onto which the off-flavour substances located in the CO₂ phase can be adsorbed, the supercritical liquid or compressed gaseous CO₂ can be regenerated again and once more used as extraction agent for extracting off-flavour substances from the secondary extract. The surprising result, that the off-flavour substances can be removed by CO₂, suggests that they have a lipophilic nature. (Regarding the CO₂ extraction, reference is made to European Patent Application 91120763). In order to achieve a particularly high profitability (above 56.0 % extraction), a three-stage procedure, i.e. incorporating a tertiary extraction, is necessary. The entire tertiary extract is subjected to the CO₂ extraction, because the tertiary extract contains off-flavour substances. The advantage of the compressed gaseous CO₂ as extraction agent lies in regulating the selectivity of the extraction agent by varying the pressure conditions. Thus, up to 100 bar the highly volatile substances, and at 100 bar to 300 bar the less volatile substances from the secondary extract or tertiary extract, are extracted. The extraction units are connected in series within the extraction plant and can be operated under process conditions which are independent of one another, only the cycle time being the same for all extraction units. The leached-out percolator is emptied, rinsed and filled with freshly ground roast coffee. In the next cycle this percolator is stripped. After the stripping cycle, the percolator is taken over as drawing-off percolator into the primary extract unit. After drawing-off, the percolator moves cycle by cycle to the extraction water inlet of the primary extract unit. In the next cycle the percolator is taken over into the secondary extract unit and here is isolated for one cycle and brought to the new, higher temperature profile by the jacket steam heating. In the following cycle it is the drawing-off percolator of the secondary extract unit. After the secondary extract drawing, the percolator moves cycle by cycle to the extraction water inlet of the secondary extract unit. If a high profitability of over 50 % extraction is required, as already mentioned above, the tertiary stage is connected downstream as third extraction unit. With the next cycle, the percolator is connected from the secondary extract unit into the tertiary extract unit, likewise isolated here for one cycle length and raised by jacket steam heating to the temperature level, which has once again been increased. The tertiary extract drawing takes place in the following cycle. Afterwards, the percolator moves cycle by cycle to the extraction water entry of the tertiary stage. After this cycle, the percolator is disconnected from the process and emptied by pressure-relief, subsequently rinsed and then filled with freshly ground coffee. There follows the aroma stripping and then once again the extraction procedure described above. Thanks to this procedure and the fine grinding used of the roast coffee with 100 % < 1.8 mm mesh width, it is possible to regulate exactly the extraction process in the extraction units and with cycle times of 2 to 40 minutes per percolator, to carry out an extremely gentle extraction of the aroma-carrying fractions, because with the fine-grinding employed, operations can be carried out with very short residence times and low temperatures. After concentrating the individual extracts and bringing them together with the drawn-off aroma condensates, a concentrate is obtained which provides, both with the freeze-drying and with the spray-drying process, a soluble coffee powder which surprisingly is distinguishable only with difficulty from a freshly-brewed roast coffee infusion in terms of sensory perception. Instant coffee-typical characters, usually described as malty , yeasty , no longer occur, nor is a hydrolysis taste detectable. A soluble coffee prepared according to the process subject of the invention was rated by an expert panel made up of 13 very well trained test persons. They were unable to ascertain any instant-typical or other off-flavour characters. According to the view of the test persons, the soluble coffee displays a roast bean coffee quality and with regard to its aroma, compares very favourably with the aroma impression of the starting roast coffee. Market research tests have shown that many test persons cannot differentiate between the soluble coffee and roast coffee. In blind tastings, roast coffee and soluble coffee prepared according to the process subject of the invention were rated by test persons who were not aware whether it was a roast coffee or an instant coffee. Those questioned were unable to ascertain any significant difference between roast coffee and instant coffee. From the descriptions and profiles it transpired that the instant coffee lacked the typical instant flavour . The scaled appraisal gave a virtually identical rating for instant coffee and roast coffee. The extent of the similarity of the instant coffee to roast coffee was further shown in the fact that barely half of those questioned thought the tested coffee was an instant coffee. Analytical and sensory investigations by sniff analyses according to the aroma dilution method of Prof. Grosch produced the same result. The aroma values of the soluble coffee prepared according the process subject of the invention were several times higher than those of other instant coffees on the market and hardly differed from the aroma values of roast coffee. The process according to the invention is described in more detail below with reference to a detailed description of the process conditions within the individual process steps. a) Stripping Obtaining the highly volatile roast coffee aromas by stripping the finely-ground, pre-moistened roast coffee. The percolator is emptied by pressure-relief and rinsed with fresh water, the walls of the percolator being cooled to 40 °C to 80 °C. After the rinsing process, the percolator is filled with fresh finely ground roast coffee with a particle size of 100 % < 1.8 mm mesh width and the roast coffee moistened with extraction water of a temperature of 30 °C to 100 °C, preferably 75 °C to 95 °C, to a water content of 4 % to 70 %, preferably 25 to 50 %. To do this the extraction water is introduced into the percolator from below. After 30 to 180 seconds the roast coffee has completely absorbed the water. After the residence time of 30 to 180 seconds has expired, the draw-off pipe for the roast coffee aromas is cleared for the roast coffee aromas and the percolator set to the desired process pressure of 10 mbar abs to 1000 mbar abs, preferably 50 to 200 mbar. For stripping the roast coffee aromas, saturated steam of 0.1 to 1.0 bar is introduced from below into the percolator which is under process pressure; it flows through the roast coffee bed which has developed in thee percolator for a period of 2 minutes to 40 minutes, preferably 2 to 10 minutes; during this time the typical highly-volatile roast coffee aromas are removed from the roast coffee. The saturated steam with the highly-volatile roast coffee aromas is subsequently introduced via a multi-stage cooler, the condensable aromas being liquefied at a temperature of 0 to 15 °C, preferably 1 to 12 °C, until the aroma condensate accounts for 3 to 20 wt-% of the roast coffee used. The stripped aroma condensate (aroma a ) is placed in interim storage in a cooled container before being added to the concentrated extract. The non-condensable gases are removed via a vacuum pump. b) Primary extraction The primary extract is the extract which is removed from the percolator which has just been stripped and newly connected into the primary extract unit. In the primary extraction stage, the roast coffee stripped by means of saturated steam in stage a) is extracted with extraction water. The temperature pattern is so chosen that in this extraction unit only the quality-determining coffee constituents are extracted at a temperature of 20 to 150 °C, preferably 90 to 140 °C, and with a cycle time of 2 to 40 minutes, preferably 5 to 12 minutes, i.e. an overall time of 10 to 200 minutes, under a pressure of 5 to 100 bar, preferably 35 to 60 bar. The primary extract is removed from the drawing-off percolator of this extraction unit, the extraction being 25 to 30 %, preferably 28 to 32 %, with a drawing-off ratio of roast coffee input to extraction quantity of 1:2 to 1:6, preferably 1:3 to 1:5. In order to additionally obtain important aromas which are necessary to give the full roast coffee taste in the end-product, this high-quality primary extract containing no off-flavours is fed directly from the drawing-off percolator via a heat-exchanger, raised there to a temperature of 40 to 100 °C, preferably 55 to 75 °C, and pressure-relieved from the process pressure of the primary extract unit, i.e. 5 to 100 bar, preferably 35 to 60 bar, in a separator with a pressure level of 10 mbar abs to 1000 mbar abs, preferably 50 to 300 mbar abs. Lowering the pressure leads to spontaneous partial evaporation. The thus-released steam portion with the highly-volatile aromas is introduced via a two-stage cooler and condensed at a temperature of 0 to 15 °C, preferably 1 to 12 °C, to form aroma b . The quantity of aroma condensate is 3 to 20 %, preferably 4 to 11 %, relative to the amount of roast coffee used. The aroma condensate b is placed in interim storage, cooled, before being added to the concentrated extract. The non-evaporated portion is obtained as primary extract and placed in interim storage until further processing at a temperature of 6 to 20 °C, preferably 8 to 12 °C. c) Secondary extraction The secondary extraction is the extraction of the partially leached-out coffee obtained after stage b) with extraction water at a higher temperature than in stage b). The secondary extraction takes place with extraction water of a temperature of 100 to 215 °C, preferably 170 to 195 °C, at a pressure of 5 to 100 bar, preferably 35 to 60 bar, and with the same cycle time as in stage b) of 2 to 40 minutes, preferably 5 to 12 minutes, i.e. an overall time of 10 to 200 minutes. The secondary extract is drawn off from the last percolator of the extraction unit and immediately thereafter subjected to a treatment for removing or reducing negative taste substances. For this the secondary extract is passed to a pressure-relief stage under a pressure of 5 to 100 bar, preferably 35 to 60 bar, and at a temperature of 100 to 215 °C, preferably 150 to 195 °C. Lowering the pressure to 10 mbar abs to 2 bar abs, preferably 100 to 600 mbar abs, leads to partial evaporation, the evaporated portion being 2 to 25 %, preferably 5 to 15 % of the extract drawn off. This evaporated portion already contains unexpectedly many off-flavours which are removed from the extract in this way. This evaporated portion which is rich in off-flavours is discarded. The non-evaporated portion remains as secondary extract and, unlike the conventional plants, no longer contains any instant-typical taste characters. The extraction of the secondary extract unit is 10 to 27 %, preferably 13 to 18 %, with a draw-off ratio of 1:2 to 1:6, preferably 1:3 to 1:5, relative to the roast coffee input. Directly after pressure-relief, the non-evaporated portion of the secondary extract is cooled to 6 to 20 °C, preferably 8 to 12 °C. According to another preferred embodiment, with which an extraction of 25 to 27 % is realized with a draw-off ratio of 1:3 to 1:5, relative to the roast coffee input, the extraction takes place at a temperature of 195 to 215 °C. With this embodiment, off-flavour substances still remain in the non-evaporated portion of the secondary extract after the partial evaporation. In order to remove these off-flavour substances, the non-evaporated portion of the secondary extract is split while the partial evaporation is in progress into a first portion, preferably comprising approximately 70 % and not containing any instant-typical taste characters and into a second portion which comprises the remaining approximately 30 %. Off-flavour substances are removed with liquid or supercritical CO₂ from the second portion of the secondary extract. In order to further increase profitability, a tertiary extraction can follow the secondary extraction. d) Tertiary extraction The tertiary extraction is the extraction of the partially leached-out roast coffee obtained in stage c) with extraction water of a higher temperature than in stage c). The third extraction unit (tertiary extraction) serves to increase the profitability of the overall process. It is operated with extraction water of a temperature of 150 to 240 °C, preferably 195 to 230 °C, at a pressure of 5 to 100 bar, preferably 35 to 60 bar, and with a cycle time of 2 to 40 minutes, preferably 5 to 12 minutes, i.e. an overall time of 8 to 160 minutes. The tertiary extract is removed from the last percolator of the tertiary extraction stage and subjected to a treatment for removing undesired off-flavour substances. For this the tertiary extract with a temperature of 150 to 240 °C, preferably 180 to 225 °C, is conducted to a pressure-relief stage directly after the drawing-off. Lowering the pressure of 5 to 100 bar, preferably 35 to 55 bar, to 10 mbar abs to 5 bar, preferably 800 to 1200 mbar abs, leads to partial evaporation. The evaporated portion is 2 to 25 %, preferably 5 to 15 %, of the tertiary extract drawn off and contains to a large degree the off-flavours occurring in the tertiary extract stage. The evaporated and subsequently condensed portion is removed from the process and discarded. The non-evaporated portion remains as tertiary extract and is cooled to 20 °C directly after the pressure-relief. In this extraction unit an extraction of 5 to 15 %, preferably 10 to 15 %, is achieved with a draw-off ratio of 1:2 to 1:6, preferably 1:3 to 1:5, relative to the roast coffee input. Off-flavour substances which were not removed by partial evaporation are also removed from the non-evaporated portion of the tertiary extract in a stage f) by an extraction with liquid or supercritical CO₂. e) Extraction of off-flavour with liquid or supercritical CO₂ In order to further remove the substances responsible for off-flavour, depending on the embodiment, the second portion of the secondary extract from stage c) can be extracted either alone or together with the tertiary extract from stage e) in a high-pressure extraction plant with liquid or supercritical CO₂. The extraction is carried out in an extraction column in counter-flow. The extract is introduced in the upper region of the column and removed in the lower column region. Liquid or supercritical CO₂ is passed as extraction agent in counter-flow. Through suitable internals (Sulzer® packing) an intensive exchange between the extraction agent CO₂ and the extract is achieved. The extraction of the liquid extract with liquid or super-critical CO₂ is carried out at a pressure of 60 to 400 bar, preferably 80 to 160 bar, and a temperature of 20 to 120 °C, preferably 60 to 90 °C. The off-flavour substances can be separated from the CO₂ by lowering the pressure to 20 to 200 bar in a separator designed for the purpose or by adsorption onto suitable adsorbents, such as, e.g., ion-exchangers, activated carbon or molecular sieves. 1 to 15 % off-flavour substances, relative to the extract quantity used, are extracted and discarded. After this treatment, the raffinate obtained was virtually completely free from the off-flavours. Supercritical CO₂ proved itself to be an unexpectedly good selective solvent for the off-flavour substances. f) After the treatment of the second portion of the secondary extract and of the tertiary extract with CO₂, they are evaporated mixed together in a multi-stage evaporator to 40 to 60 %, preferably 45 to 50 % solids concentration and cooled to 6 to 20 °C, preferably 8 to 12 °C. Parallel to this, the qualitatively high-value primary extract is very carefully concentrated in a multi-stage evaporator to 25 to 40 %, preferably 30 to 35 % solids concentration and likewise cooled to 6 to 20 °C, preferably 8 to 12 °C. Also parallel to this, the secondary extract or optionally only the first portion of the secondary extract is carefully concentrated in a multi-stage evaporator to 40 to 60 %, preferably to 45 to 50 % solids concentration. The extract solutions are mixed and combined with the aromas from roast coffee and primary extract, which have been stored at 1 to 20 °C, preferably 1 to 12 °C. The finished extract has a solids concentration of 35 to 55 %, is stored at 6 to 20 °C and freeze- or spray-dried within 15 hours. Embodiment 1Example 1 describes the process of the two-stage extraction to obtain a profitability of up to about 50 % extraction. The process steps described below run simultaneously within a cycle of 8 minutes. The just emptied percolator, prepared for loading, with a diameter d = 400 mm and a length/diameter ratio of 2.5, is filled with 30 kg of ground roast coffee with a grain spectrum of 100 % < 1.8 mm, including 20 % < 0.5 mm mesh width, for the obtaining of aroma and subsequent extraction. The walls of the percolator are cooled to 65 °C. The roast coffee is moistened with water at 82 °C in 70 seconds to a water content of 45 %. There follows a residence time of 90 seconds before the percolator is evacuated to the process pressure of 100 mbar abs. Saturated steam of 0.1 bar is introduced from below into the percolator, flows through the roast coffee and exits at the top. Cooling takes place in a two-stage cooler, cooled in the first stage to 12 °C and in the second to 2 °C aroma condensate temperature. Until further processing, the aroma condensate ( a ) is stored for 4 hours maximum at 2 °C. 12.5 % aroma condensate (kg), relative to the roast coffee poured in (kg), is stripped off in 300 seconds. In the primary extraction stage, the percolator stripped in the previous cycle is extracted and the extract drawn off. The primary extraction unit comprises 7 percolators connected in series and is operated at a pressure of 45 bar. From the extraction water inlet to the extract drawing-off percolator, the flow-through percolators is in each case from below upwards. The inlet temperature of the extract into the drawing-off percolator is kept constant at 92 °C via a heat-exchanger. The temperature profile is set via the double-jacket heating of the percolators and is: 1st Percolator extraction water inlet:144 °C 2nd Percolator inlet140 °C 3rd Percolator inlet135 °C 4th Percolator inlet122 °C 5th Percolator inlet 112 °C 6th Percolator inlet 105 °C 7th Percolator inlet primary extract drawing-off92 °C The extract amount drawn off per cycle (kg) is 3.2 times the amount of roast coffee used (kg). The average solids concentration of 9.7 % results in the primary extraction unit, in an extraction of 31.0 %, relative to roast coffee. The primary extract is directly, coming from the drawing-off, reduced by a pressure-maintaining device, from the system pressure of 45 bar to a pressure of 5 bar, raised via a heat-exchanger to a temperature of 68 °C and spontaneously pressure-relieved in a separator at a pressure of 150 mbar abs. The released amount of steam, enriched with aroma substances, is condensed in a two-stage cooler at 12 °C and 2 °C as aroma b and stored at 2 °C until further use. The aroma condensate amount (kg) is 12.0 % of the amount of roast coffee used per cycle (kg). The two aroma condensates, aroma a , obtained from roast coffee and aroma b , from the primary extract, are added to the concentrated extract before drying. The non-evaporated portion of the primary extract is cooled to 8 °C, very carefully concentrated in a multi-stage evaporator to a solids concentration of 42 % and stored at 8 °C. The secondary extraction unit comprises 7 percolators, 6 of which are connected in series, are flowed through and undergo drawing-off of the secondary extract. In this cycle the seventh percolator was connected from the primary stage into the secondary stage, where it was isolated and raised, by jacket steam heating, to the temperature level of the secondary extraction unit. The secondary extraction unit is operated at a pressure of 50 bar and a temperature of 181 °C which is uniform for all percolators. The quantity of secondary extract drawn off (kg) is 3.1 times the amount of roast coffee used (kg), the average solids concentration in the drawn-off extract 5.2 %. An extraction of 16.0 %, relative to the amount of roast coffee used, is achieved. The secondary extract drawn off is continuously pressure-relieved in two steps in a separator. In the first stage, from 50 bar to 6 bar, and in the second stage from 6 bar to 600 mbar abs. The released steam portion of 40 % of the roast coffee used is highly enriched with off-flavour components and is liquefied at 76 °C in the condenser and drawn off continuously from the process. Downstream from the separator, the secondary extract is cooled to 8 °C and concentrated in a multi-stage evaporator to 50 % solids concentration and stored at 8 °C. The primary extract and the secondary extract together give an overall extraction of 47.0 %, relative to roast coffee. They are mixed with each other and reacted with the proportional amounts of aroma a = 200 g/1000 g dry substance and aroma b = 195 g/1000 g dry substance. The solids concentration of the thus prepared extract is 37.5 %. The thus concentrated and aromatized coffee extract has a solids concentration of 37.5 % and is processed on conventional freeze- or spray-driers. Embodiment 2The steam stripping of the ground roast coffee is carried out as described in Example 1. In the primary extraction stage, the percolator stripped in the previous cycle is extracted and the extract removed. The primary extraction unit comprises 7 percolators connected in series and is operated at a pressure of 45 bar. From the extraction water inlet to the extract drawing-off percolator, the flow through the percolators is in each case from below upwards. The inlet temperature of the extract into the drawing-off percolator is kept constant at 92 °C via a heat-exchanger. The temperature profile is set via the double-jacket heating of the percolators and is: 1st Percolator extraction water inlet:144 °C 2nd Percolator inlet140 °C 3th Percolator inlet135 °C 4th Percolator inlet122 °C 5th Percolator inlet112 °C 6th Percolator inlet105 °C 7th Percolator inlet primary extract drawing-off92 °C The extract amount drawn off per cycle (kg) is 3.2 times the amount of roast coffee used (kg). The average solids concentration of 9.7 % results, in the primary extraction unit, in an extraction of 31.0 %, relative to roast coffee. The primary extract is directly, coming from the drawing-off, reduced by a pressure-maintaining device, from the system pressure of 45 bar to a pressure of 5 bar, raised via a heat-exchanger to a temperature of 68 °C and spontaneously pressure-relieved in a separator at a pressure of 150 mbar abs. The released amount of steam, enriched with aroma substances, is condensed in a two-stage cooler at 12 °C and 2 °C as aroma b and stored at 2 °C until further use. The aroma condensate amount (kg) is 12.0 % of the amount of roast coffee used per cycle (kg). The two aroma condensates, aroma a , obtained from roast coffee and aroma b , from the primary extract, are added to the concentrated extract before drying. The non-evaporated portion of the primary extract is cooled to 8 °C, very carefully concentrated in a multi-stage evaporator to a solids concentration of 40.2 % and stored at 8 °C. The secondary extraction unit comprises 7 percolators, 6 of which are connected in series, are flowed through and undergo drawing-off of the secondary extract. In this cycle the seventh percolator was connected from the primary stage into the secondary stage, where it was isolated and raised, by jacket steam heating, to the temperature level of the secondary extraction unit. The secondary extraction unit is operated at a pressure of 50 bar and a temperature of 200 °C which is uniform for all percolators. The quantity of secondary extract drawn off (kg) is 3.5 times the amount of roast coffee used (kg), the average solids concentration in the drawn off extract 5.0 %. An extraction of 25.0 %, relative to the amount of roast coffee used, is achieved. The secondary extract drawn off is continuously pressure-relieved in two steps in a separator. In the first stage, from 50 bar to 6 bar, and in the second stage from 6 bar to 600 mbar abs. The released steam portion of 35 % of the roast coffee used is highly enriched with off-flavour components and is liquefied in the condenser at 76 °C and continuously removed from the process. The secondary extract is cooled to 8 °C downstream from the separator and split into two parts. The first part is 70 %, and the second part 30 %, of the secondary extract drawn off. The first part (70 %) is concentrated on a multi-stage evaporator in a known manner to a solids concentration of 48 % and stored at 8 °C. The second part (30 %) undergoes a CO₂ treatment to remove off-flavour components. For thin the second portion of the secondary extract is extracted in a CO₂ pressure extraction column (Sulzer® 13 BX packing) with a diameter d = 300 mm and a length/diameter ratio of 20:1 in counter-flow with CO₂ as extraction agent at a temperature of 70 °C and a pressure of 120 bar. The off-flavour extract is separated from the CO₂ by pressure-relief to 50 bar. The portion of extracted substances, relative to the extract quantity used, is 5 %. The thus treated extract is concentrated on a multi-stage evaporator in a known manner to a solids concentration of 48 % and cooled to 8 °C. The now present extracts, which together give an extraction of 56.0 %, relative to roast coffee, are mixed with each other and combined with the proportional amounts of aroma a = 200 g/1000 g dry substance and aroma b = 195 g/1000 g dry substance. The thus concentrated and aromatized coffee extract has a solids concentration of 37.5 % and is processed on conventional freeze- or spray-driers. Embodiment 3The process steps described below run simultaneously within a cycle of 8 minutes. The just emptied percolator (P16), prepared for loading, with a diameter d = 400 mm and a length/diameter ratio of 2.5, is filled with 30 kg of ground roast coffee with a grain spectrum of 100 % < 1.8 mm, including 20 % < 0.5 mm mesh width, for the obtaining of aroma and subsequent extraction. The walls of the percolator are cooled to 65 °C. The roast coffee is moistened with water at 82 °C in 70 seconds to a water content of 45 %. There follows a residence time of 90 seconds before the percolator is evacuated to the process pressure of 100 mbar abs. Saturated steam of 0.1 bar is introduced from below into the percolator, flows through the roast coffee and exits at the top. Cooling takes place in a two-stage cooler, cooled in the first stage to 12 °C and in the second to 2 °C aroma condensate temperature. Until further processing, the aroma condensate ( a ) is stored for 4 hours maximum at 2 °C. 12.5 % aroma condensate (kg), relative to the roast coffee poured in (kg), is stripped off in 300 seconds. In the primary extraction stage, the percolator stripped in the previous cycle is extracted and the extract drawn off. The primary extraction unit comprises 5 percolators (P6 to P2) connected in series and is operated at a pressure of 45 bar. From the extraction water inlet (P6) to the extract drawing-off percolator (P2), the flow through the percolators is in each case from below upwards. The inlet temperature of the extract into the drawing-off percolator is kept constant at 92 °C via a heat-exchanger. The temperature profile is set via the double-jacket heating of the percolators and is: 1st Percolator extraction water inlet:148 °C 2nd Percolator inlet135 °C 3rd Percolator inlet120 °C 4th Percolator inlet112 °C 5th Percolator inlet primary extract drawing-off92 °C The extract amount drawn off per cycle (kg) is 3.7 times the amount of roast coffee used (kg). The average solids concentration of 8.5 % results, in the primary extraction unit, in an extraction of 31.5 %, relative to roast coffee. The primary extract is directly, coming from the drawing-off, reduced by a pressure-maintaining device from the system pressure of 45 bar to a pressure of 5 bar, raised via a heat-exchanger to a temperature of 68 °C and spontaneously pressure-relieved in a separator at a pressure of 150 mbar abs. The released amount of steam, enriched with aroma substances, is condensed in a two-stage cooler at 12 °C and 2 °C as aroma b and stored until further use at 2 °C. The aroma condensate amount (kg) is 12.0 % of the amount of roast coffee used per cycle (kg). The two aroma condensates, aroma a , obtained from roast coffee and aroma b , from the primary extract, are added to the concentrated extract before drying. The non-evaporated portion of the primary extract is cooled to 8 °C, very carefully concentrated in a multi-stage evaporator to a solids concentration of 37.5 % and stored at 8 °C. The secondary extraction unit comprises 5 percolators (P11 to P8), 4 of which (P11 to P8) are connected in series, are flowed through and undergo drawing-off of the secondary extract (P8). In this cycle the fifth percolator (P7) was connected from the primary stage into the secondary stage, where it was isolated and raised, by jacket steam heating, to the temperature level of the secondary extraction unit. The secondary extraction unit is operated at a pressure of 50 bar and a temperature of 200 °C which is uniform for all percolators. The quantity of secondary extract drawn off (kg) is 3.5 times the amount of roast coffee used (kg), the average solids concentration in the extract drawn off 5.0 %. An extraction of 25.0 %, relative to the amount of roast coffee used, is achieved. The secondary extract drawn off is continuously pressure-relieved in two steps in a separator. In the first stage, from 50 bar to 6 bar, and in the second stage from 6 bar to 600 mbar abs. The released steam portion of 35 % of the roast coffee used is highly enriched with off-flavour components and is liquefied at 76 °C in the condenser and drawn off continuously from the process. Downstream from the separator, the secondary extract is cooled to 8 °C and split into two parts. The first part is 70 %, and the second part 30 %, of the secondary extract drawn off. The first part (70 %) is concentrated on a multi-stage evaporator in a known manner to a solids concentration of 48 % and stored at 8 °C. The second part (30 %) is conducted with the tertiary extract to a CO₂ treatment to remove off-flavour components. The tertiary extraction unit comprises 4 percolators (P15 to P12), of which 3 percolators (P15 to P13) are connected in series, are flowed through and undergo drawing-off of the tertiary extract (P13). In this cycle the fourth percolator (P12) was connected from the secondary unit into the tertiary unit, where it was isolated and raised to the temperature level of the tertiary extraction unit. The tertiary extraction unit is operated at a pressure of 55 bar and a temperature of 228 °C. The quantity of tertiary extract drawn off (kg) is 3.9 times the amount of roast coffee used and has an average solids concentration of 2.6 %. An extraction of 10 %, relative to roast coffee, results. The tertiary extract drawn off is pressure-relieved in two steps in a separator. 1st stage55 bar to 8 bar 2nd stage8 bar to 1 bar. The steam portion from the tertiary extract released by exploiting enthalpy is 35 % of the amount of roast coffee used and is liquefied at 80 °C and drawn off continuously from the process. The tertiary extract is cooled to 20 °C and extracted together with the 30 % portion of the secondary extract in a CO₂ pressure-extraction column (Sulzer® 13 BX packing) with a diameter d = 300 mm and a length/diameter ratio of 20:1 in counter-flow with CO₂ as extraction agent at a temperature of 70 °C and a pressure of 120 bar. The off-flavour extract is separated from the CO₂ by pressure-relief to 50 bar. The portion of extracted substances, relative to the amount of extract used, is 5 %. The thus-treated extract is concentrated on a multi-stage evaporator in a known manner to a solids concentration of 48 % and cooled to 8 °C. The now present extracts, which together give an extraction of 66.5 %, relative to roast coffee, are mixed with each other and combined with the proportional amounts of aroma a = 200 g/1000 g dry substance and aroma b = 195 g/1000 g dry substance. The thus-concentrated and aromatized coffee extract has a solids concentration of 37.5 % and is processed on conventional freeze- or spray-driers.	Process for preparing soluble coffee with roast bean coffee quality by multi-stage extraction of ground roast coffee including the steaming of the coffee before the extraction, followed by condensation of the distillate, a first extraction with water in at least two percolators at a temperature of up to more than 100°C, a second extraction with water in at least two percolators at a higher temperature than in the first extraction, the combining of the condensate from the steaming step with the concentrated extracts from the first and second extraction stages and the drying of the combined mixture, characterized in that a) ground roast coffee of a particle size of at most 1.8 mm, which has been moistened to a water content of 4 to 70 wt-%, relative to the ground dry roast coffee, is treated in a percolator with a length/diameter ratio of 3.2:1 to 0.9:1 with saturated steam at a pressure of 0.1 to 1 bar and a temperature of 30 to 100°C for 2 to 40 minutes, the steam loaded with coffee constituents is condensed at a temperature of 0 to 15°C to a condensate quantity of 3 to 20 wt-%, relative to the quantity of dry roast coffee used, and the condensate is obtained as aroma a , b) the coffee remaining from stage a), freed from aroma a , is subjected with extraction water to a primary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee, at a temperature of 20 to 150°C and a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.2:1 to 0.9:1 for 2 to 40 minutes per percolator and for an overall time of 10 to 200 minutes, followed by pressure-relief to 0.001 to 1 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is condensed at a temperature of 0 to 15°C and the condensate is obtained as aroma b and the non-evaporated portion as primary extract, c) the coffee remaining from stage b), freed from aroma b and from primary extract, is subjected with extraction water to a secondary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee at a higher temperature than in stage b) within a range of 100 to 215°C and at a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.2:1 to 0.9:1 for 2 to 40 minute per percolator and for an overall time of 10 to 200 minutes, followed by pressure-relief to 0.01 to 2 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is discarded, the non-evaporated portion is obtained as secondary extract, d) the primary extract is concentrated in a multi-stage evaporator to a solids concentration of 25 to 40%, and parallel to this, the secondary extract is concentrated in a multi-stage evaporator to a solids concentration of 40 to 60%, the concentrated extract solutions are combined and mixed with aromas a and b and the obtained extract, which has a solids concentration of 35 to 55%, is freeze- or spray-dried in the usual way. Process according to claim 1, characterized in that e) the coffee remaining from stage c), freed from the discarded evaporated portion and from the secondary extract, is subjected with extraction water to a tertiary extraction in a quantity of 2 to 6 parts by weight per part by weight of dry starting roast coffee at a higher temperature than in stage c) within a range of 150 to 240°C and at a pressure of 5 to 100 bar with the aid of at least 2 percolators with a length/diameter ratio of 3.1:1 to 0.9:1 for 2 to 40 minutes per percolator and for an overall time of 8 to 160 minutes, followed by pressure-relief to 0.01 to 5 bar, the evaporated portion obtained by spontaneous partial evaporation of the extract is discarded and the non-evaporated portion is obtained as tertiary extract, which itself is f) extracted, in order to remove off-flavour substances, with liquid or supercritical CO₂ at a temperature of 20 to 120°C and a pressure of 60 to 400 bar and the remaining extract being concentrated in a multi-stage evaporator to a solids concentration of 40 to 60%, and being combined with aromas a and b and the concentrated extracts from the primary and secondary extractions. Process according to claim 1, characterized in that the secondary extract is divided into a first portion of approximately 70% and a second portion of approximately 30%, the second portion being extracted, in order to remove off-flavour substances, with liquid or super-critical CO₂ at a temperature of 20° to 120°C and a pressure of 60 to 400 bar, the remaining extract being concentrated in a multi-stage evaporator to a solids concentration of 40 to 60% and being combined with aromas a and b and the concentrated extracts from the primary and secondary extractions. Process according to claims 1 to 3, characterized in that the second portion of the secondary extract and the tertiary extract are combined before being extracted with CO₂. Process according to claims 1 to 4, characterized in that the primary, secondary and tertiary extractions are carried out at a draw-off ratio of roast coffee used to extraction quantity of 1:2 to 1:6. Process according to claims 1 to 5, characterized in that the cycle time in the individual extraction stages b), c) and e) is 5 to 12 minutes. Process according to claims 1 to 6, characterized in that the pressure in the single extraction stages b), c) and e) is 35 to 60 bar. Process according to claims 1 to 7, characterized in that in stage a) one percolator and in stages b), c) and e) at least 2 percolators, preferably 4 to 7 percolators, are used. Process according to claims 1 to 8, characterized in that the percolators have length/diameter ratio of 3:1 to 2:1 particularly 2.5:1. Process according to claims 1 to 9, characterized in that the process is carried out semi-continuously using - preferably in circular arrangement - 7 to 22 percolators in stages a) to c) and e), with only one percolator being provided for stripping stage a) and at least 2 percolators for each of the three other stages b), c) and e), which are in contact with each other within the individual stages so that the outlet of each percolator is joined to the inlet of the following percolator and the fresh extraction water being introduced into the last percolator in each case with the relatively largely extracted coffee of stages b), c) and e) and being drawn off from the first percolator in each case with slightly extracted coffee and the plant being operated with cycle times - identical for all percolators - so that in each cycle time a percolator preceding the stripping percolator of stage a) is filled with fresh, ground roast coffee and the last percolator of stage e) is emptied of completely extracted coffee, whereby stages a) to c) and e) always move on one percolator at a time towards the newly poured, fresh roast coffee.	JACOBS SUCHARD AG	KOCH KLAUS DIETER; VITZTHUM OTTO DR; KOCH, KLAUS DIETER; VITZTHUM, OTTO, DR.
EP-0489402-B1	489,402	EP	B1	EN	19,940,420	1,992	20,100,220	new	A23F5	null	A23F5	A23F 5/18	Process for preparing soluble coffee with improved flavour	The invention relates to a process for preparing soluble coffee in which, to eliminate off-flavour substances, one or more extracts occurring during the aqueous extraction of roast coffee are extracted fully or partly at a temperature of approximately 20 to 120 °C and a pressure of approximately 60 to 400 bar with supercritical or liquid CO₂.	Process for preparing soluble coffee with improved flavourThe disadvantages of many commercially available instant coffees are undesired process-related off-flavour characters, which give the coffee a malty, yeasty aroma character. This differentiates it clearly from a roast coffee brew and is the reason for the reduced acceptance of most instant coffees by the consumer. Such off-flavour substances can form during the preparation process of the instant coffee if the roast coffee used for extraction remains in the percolator for too long under increased temperatures, if suitable precautions are not taken for the careful separation of the aroma fraction and, in the case of downstream part-extraction stages - the so-called secondary and tertiary extraction - more severe extraction conditions are applied. There have been many attempts to reduce or eliminate undesired flavour-impairing off-flavour substances. Thus, EP-A-O 151 772 (Bonne and Schweinfuth) describes a process with which the off-flavour substances of the secondary extract are bonded to weakly basic ion exchangers. EP-A-O 078 618 (Hamell, Zanno and Hickernell) proposes adsorption onto polymeric resins in order to extract the raw, bitter and metallic characters from instant coffee. In US-A-4 544 567 (Gottesman), the removal using coffee oil and in EP-A-78121 (Turek) the removal using an edible oil is recommended and according to EP-A-O 159 754 (Morrison) the off-flavour substances are removed from the secondary extract of the instant coffee process by means of steam distillation. The 95 % removal of furfural - allegedly an off-flavour indicator - was quoted as evidence of the efficiency of this process. The disadvantage with all known processes is that the flavour quality of the soluble coffee prepared in this way is still not satisfactory. The aim of the invention is to make available a process for preparing a soluble coffee whereby it is possible to remove even more effectively the off-flavour substances some of which are present in the aqueous extracts. It was found that this aim can be achieved by employing an extraction technique using supercritical or liquid carbonic acid at high pressure. The invention relates to a process for preparing a soluble coffee wherein for eliminating off-flavour substances from coffee extract, roast coffee is subjected to an at least two-stage aqueous extraction carried out under different temperatures increasing from stage to stage characterized in that the extract obtained in the second extraction stage or part of it and every extract obtained in an additional extraction stage are extracted at temperatures of approximately 20 to 120°C and at a pressure of approximately 60 to 400 bar with supercritical or liquid CO₂. The invention further relates to a process for preparing soluble coffee according to the above described process wherein to separate and obtain valuable aroma constituents, roast coffee is firstly treated with steam, the remaining roast coffee then subjected to the at least two-stage aqueous extraction including treating the second extract and any further extract according to the process of claim 1, the optionally concentrated extracts are combined and reacted with the aromas and the obtained extract is freeze- or spray-dried in the usual way. The process is preferably carried out at a temperature of 60 to 90°C and a pressure of 80 to 160 bar. It is known that, for the removal of caffeine, aqueous coffee extract solutions can be subjected to a CO₂ extraction. Thus, EP-A-O 010 637 (Margolis) describes a process for decaffeinating an aqueous roast coffee solution with supercritical carbonic acid of 450 bar at 80 °C, the CO₂ extraction taking place in a packed column. The same effect is described in US-A-4 341 804 (Prasad, Gottesman and Scarella), the decaffeination of the liquid extract taking place in an extractor provided with screen trays. US-A-4,246,291 (Prasad et al.) describes a process for decaffeinating aqueous coffee extracts with liquid or supercritical CO₂. EP-A-O,389,747 (Hubert) describes fluid extraction with carbonic acid with the aim of decaffeinating the aqueous roast coffee solution, the aqueous extract being added into the separation column at various heights by means of injection nozzles to the upwardly flowing compressed CO₂. Therefore, the process according to the invention - insofar as the simultaneous extraction of the caffeine is not desired - can only be applied to the extract occurring during a second extraction stage because in the first extraction stage practically all the caffeine goes into solution. It is surprising that the off-flavour substances can be removed with the aid of liquid or supercritical carbonic acid at high pressure. It was previously the view that the substances negatively influencing the flavour of the soluble coffee were those of average polarity which could be extracted with carbonic acid only with difficulty. The fact that they can nevertheless be extracted with carbonic acid indicates that they are lipophilic substances. Using gas-chromatographic mass spectrometric analyses it was confirmed that products to be found as off-flavour substances in the CO₂ phase include 2-hydroxy-alkyl-cyclopentene-1-one, which display strongly spicy characters. For the preparation of a high-quality soluble coffee in an economic yield, it is necessary to improve the taste of coffee extracts which are obtained for increasing the yield and correspondingly subjected over a lengthy period of time to an increased temperature. This applies in particular to the secondary and tertiary extracts. As previously mentioned, attempts were made in the prior art to remove the off-flavour substances contained in these extracts with weakly basic ion exchangers, polymeric resin and the like. The result, however, was not satisfactory. With the process according to the invention, i.e. by means of a high-pressure extraction of the secondary extract or of part of the secondary extract and of every further extract with liquid or supercritical CO₂, the off-flavour substances can removed very effectively, and a soluble coffee with virtually roast coffee quality is obtained. With the process according to the invention, ground roast coffee is preferably firstly stripped with steam in the usual way to separate essential aroma constituents. There follow a first and then a second extraction of the remaining roast coffee, which can likewise be carried out in the usual way as per the prior art. Aroma stripping and aqueous extractions can, for example, be carried out as described in EP-A-O 097 466, US-A-4 707 368 or EP-A-0 489 401. The extract obtained during the second extraction, which is carried out at higher temperatures than the first extraction, containing off-flavour substances, is completely or partly subjected to the CO₂ extraction according to the invention. The same happens with the extracts obtained in additional extraction stages. The extraction is carried out in an extraction column in counter-flow. The coffee extract solution containing off-flavour substances is fed into the upper region of the column and removed in the lower column region. Liquid or supercritical CO₂ as extraction agent is fed in at the lower end of the column. The off-flavour substances dissolve in the fluid phase and are discharged at the upper column end with the carbonic acid. Suitable CO₂ extraction plants are described, for example, in DE-A-29 05 078, the whole disclosure of which is intended to be encompassed here. Through suitable internals (Sulzer packing) an intensive exchange between the extraction agent CO₂ and the extract is achieved, so that the coffee extract solution emerging at the lower end of the column is free from off-flavour substances. This solution can then be processed in the known way with other part fractions from the instant procedure, to produce dry powder. The off-flavour substances can be separated from the CO₂ by lowering the pressure to 20 to 200 bar in a separator provided for the purpose or by adsorption onto suitable adsorbents, such as, e.g., ion exchangers, activated carbon or molecular sieves. The process of extracting the off-flavour substances from the coffee extract solution and the regeneration of the CO₂ is a recycling process. By means of a pump, the carbonic acid loaded with the off-flavour substances is guided over an activated-carbon column or other suitable column, such as e.g. a molecular sieve or an ion exchanger column, for the removal of the off-flavour substances. The regenerated CO₂ can then be used once more for extracting off-flavour substances from coffee extract solutions. Using this treatment, 1 to 15 % IC-typical, undesired coffee constituents, relative to the quantity of extract used, are extracted and discarded. After this treatment, the raffinate obtained is virtually completely free from the off-flavour substances. Example32 l secondary extract with a solids concentration of 5 %, which had been obtained in the usual way in the second stage of a two-stage extraction, were extracted in a CO₂ pressure-extraction column (Sulzer packing 13 BX) with a diameter of d = 300 mm and a length/diameter ratio of 20:1 in counter-flow, with CO₂ as extraction agent at a temperature of 70 °C and a pressure of 120 bar for a period of 30 to 40 min. The off-flavour substances were separated from the CO₂ by lowering the pressure to 50 bar. The proportion of the extracted substances, relative to the quantity of extract used, was 5 %. The thus treated extract was concentrated in the usual way in a multi-stage evaporator to a solids concentration of 48 % and cooled to 8 °C. Subsequently, the treated secondary extract together with the primary extract and the obtained aromas were further processed in the usual way by freeze- or spray-drying to produce soluble coffee powders. IC typical, undesired flavour characters were no longer ascertainable.	Process for preparing a soluble coffee wherein for eliminating off-flavour substances from coffee extract, roast coffee is subjected to an at least two-stage aqueous extraction carried out under different temperatures increasing from stage to stage characterized in that the extract obtained in the second extraction stage or part of it and every extract obtained in an additional extraction stage are extracted at temperatures of approximately 20 to 120°C and at a pressure of approximately 60 to 400 bar with supercritical or liquid CO₂. Process according to claim 1 wherein to separate and obtain valuable aroma constituents, roast coffee is firstly treated with steam, the remaining roast coffee then subjected to the at least two-stage aqueous extraction including treating the second extract and any further extract according to the process of claim 1, the optionally concentrated extracts are combined and reacted with the aromas and the obtained extract is freeze- or spray-dried in the usual way. Process according to claims 1 or 2, characterized in that the CO₂ extraction is carried out at a temperature of 60 to 90 °C. Process according to at least one of claims 1 to 3, characterized in that the CO₂ extraction is carried out at a pressure of 80 to 160 bar.	JACOBS SUCHARD AG	KOCH KLAUS DIETER; VITZTHUM OTTO G DR; KOCH, KLAUS DIETER; VITZTHUM, OTTO G., DR.
EP-0489403-B1	489,403	EP	B1	EN	19,990,602	1,992	20,100,220	new	B01D61	B01D39, A61M5	A61M5, A61K9, B01D63, B01D39, B01D61, B01D69, B01D36, B01D19	A61M 5/165, B01D 36/00D, B01D 39/16B4, B01D 63/08, B01D 19/00F, B01D 61/18, B01D 61/14, K61M5:165, B01D 69/12, A61K 9/00M5G	Filter for parenteral systems	A filter device (10) and method are provided for treating parenteral nutrient fluids, particularly TNA systems containing lipids, glucose, and amino acids. The filter device comprises a housing (11) and a microporous medium in the form of a synthetic polymeric microporous structure having a pore rating of less than 1.2 micrometers. A preferred microporous medium comprises, in series, a matrix of microfibers which has been radiation grafted to render the matrix wettable by parenteral nutrient fluids followed by a microporous membrane, also wettable by parenteral nutrient fluids, and having a finer pore rating than the microfibrous matrix.	This invention relates to a filter device and method for treating parenteral fluids. More particularly, this invention relates to a filter device and method for treating parenteral nutrient admixtures.Individuals at risk of malnutrition or who are unable to obtain sufficient nutrients by enteral means must be fed intravenously. The use of total parenteral nutrition (TPN) - the administration of nutrients via a peripheral or central vein - has grown rapidly over the past several years. Unfortunately, infection is a potential major complication of TPN. This is of particular concern with malnourished and debilitated patients with compromised immune systems.Microbiologic contamination of TPN mixtures may occur during preparation of the mixture, during administration, or via manipulation of the catheter. Accordingly, a total nutrient admixture (TNA) which contains all daily nutritional requirements in a single container is highly desirable because of the reduced likelihood of contamination due to the reduced number of manipulations of the intravenous delivery system. Reduced work loads of health care personnel are also a positive result of the use of single container TNA systems vis-a-vis conventional TPN systems requiring multiple nutrient containers. Typically, a TNA admixture contains three primary components: lipids in the form of an emulsion, glucose, and amino acids. Other components may include electrolytes, trace elements, and vitamins. The lipid emulsion is typically stabilized by an emulsifying agent such as a phospholipid which the filtering medium should not absorb.While TNA systems offer the benefits noted above, one potential drawback is that the TNA system provides a better growth media for potentially pathogenic microorganisms. For example, the growth of fungal organisms, such as Candida albicans, in parenteral nutrient formulations poses an infectious threat because they are able to thrive in a variety of nutrient systems. Further, while Candida albicans has been shown to proliferate in both conventional TPN formulations and TNA admixtures, in at least one study growth was found to be stimulated in TNA admixtures. Similarly, studies have shown that TNA systems support bacterial growth significantly better than conventional TPN solutions.In addition to the problems noted above, the lipid emulsion component results in the TNA admixture being opaque, making proper inspection of the mixture impossible. This may lead to a variety of problems including undetected fat particles having a size ranging from a few to as large as about 20 micrometers in diameter, creating the danger of fat embolus.While problems with TNA systems have been recognized for some time, the benefits of such systems have been found to outweigh the attendant difficulties, and their use has grown at a rapid rate. At present, in the vicinity of 80% of all TPN deliveries in Western Europe are in the form of TNA. The use of TNA systems also continues to expand in both the United States and Japan. Accordingly, there is an ongoing and growing need for means to alleviate difficulties with the use of TNA systems. Attempts to alleviate the problems associated with TNA systems have focused on the use of membrane filters with pore ratings of 1.2 micrometers. While such filters are presently being used, they suffer from limitations. Specifically, such filters have limited flow capacity such that they exhibit excessive pressure buildup and plugging with concomitant limited onstream filter life. Excessive pressure build up is a serious problem with parenteral nutrient systems since the liquid nutrient is typically administered using a pump designed only to operate at relatively low pressures, e.g., less than 1.76 X 104 kg/m2 (25 psi), typically less than 1.05 X 104 kg/m2 (15 psi), and, in many applications, at less than 0.70 X 104 kg/m2 (10 psi). Because these pumps are not engineered to operate at higher pressures, the parenteral fluid administration system typically includes an occlusion alarm which shuts down the pump at a relatively low pressure. Accordingly, excessive pressure build up and plugging of a filter device is a potentially serious problem. Additionally, membrane filters with pore ratings of 1.2 micrometers provide only limited ability to remove fine particulate and microbiological contaminants. DE-A-2 317 750 discloses a filter device for separating and filtering gases and liquids, wherein a microporous filter material having a pore rating of less than 100 microns is used. This filter device may be used in the field of medical applications, e.g. for preventing the introduction of air in a patient who has obtained a injection of a flowable medicament, e.g. a parenteral medium. There is, therefore, a need for a filter device having an enhanced capability for filtration of fine particulate matter and microorganisms and having the capability of removing significant amounts of bacteria, the capacity to remove pyrogenic matter, such as bacterial endotoxins, and which, in addition, has a relatively high volumetric capacity, typically up to 3 liters of TNA at a flow rate of up to about 300 milliliters per hour, coupled with low pressure drop and, thus, good onstream life. Ideally, such a device would also have a relatively small hold up volume of about 5 cubic centimeters or less.In accordance with this invention, a filter device for treating lipid-containing parenteral nutrient fluids, is provided as defined in claim 1. The filter device comprises a housing including an inlet and an outlet and defining a fluid flow path between the inlet and the outlet and a liquid filtration element comprising a synthetic, polymeric microporous structure positioned inside the housing across the flow path, wherein the liquid filtration element comprises first and second filter media in series, the first medium having a pore rating greater than the second medium, the second medium having a pore rating of less than 1.2 micrometers.Both media are preferably wettable by the parenteral nutrient fluid. Additionally, a preferred device also comprises one or more non-wetting or liquid-repellant microporous structures to provide for gas/liquid separation via gas venting.In accordance with the invention, a method for treating a parenteral nutrient fluid as defined in claim 15 is provided. In this method a lipid-containing parenteral nutrient fluid such as TNA admixtures, is treated by passing it through the filter device. The filter device comprises i.a. a liquid filtration element comprising a synthetic, polymeric microporous structure, wherein the element comprises first and second filter media in series with the second or downstream filter medium having a pore rating of less than 1.2 micrometers and preferably being finer than that of the upstream medium.In the accompanying drawings: Figure 1 is a top plan view of a filter device embodying the invention in which there are two liquid-repellant structures, one on each side of a liquid filtration element;Figure 2 is a bottom plan view of the filter device of Figure 1;Figure 3 is a longitudinal sectional view taken along the line III-III of the device of Figure 1; andFigure 4 is a cross-sectional view taken along the line IV-IV of the device of Figure 1.The present invention provides for a filter device falling under claim 1, for treating parenteral nutrient fluid containing a lipid comprising: (1) a housing including an inlet and an outlet and defining a fluid flow path between the inlet and the outlet; and (2) a liquid filtration element positioned inside the housing across the flow path comprising a synthetic polymeric microporous structure adapted to remove fine particulate and biological contaminants from the parenteral nutrient fluid.The present invention also provides for a filter device falling under claim 1, for treating parenteral nutrient fluid containing a lipid comprising: (1) a housing including a fluid inlet and a liquid outlet and defining a liquid flow path between the fluid inlet and the liquid outlet, the housing further including a gas vent outlet and defining a gas flow path between the inlet and the gas vent outlet; (2) a liquid filtration element positioned inside the housing across the liquid flow path, the liquid filtration element comprising a synthetic, polymeric, microporous structure adapted to remove fine particulate and biological contaminants from the parenteral nutrient fluid with a pressure drop of about 1.05 x 104 kg/m2 (15 psi) or less while passing the parenteral nutrient fluid at a flow rate of up to about 300 milliliters per minute; and (3) a non-wetting, liquid-repellant, microporous structure positioned inside the housing across the gas flow path adapted to vent gas from the parenteral nutrient fluid.The present invention further provides for a method for treating a parenteral nutrient fluid containing a lipid as defined in claim 20, comprising passing the parenteral fluid through a filter device comprising i.a. a liquid filtration element comprising a synthetic polymeric microfibrous matrix having a pore rating of less than 1.2 micrometers.A filter device for treating parenteral fluids embodying the invention generally comprises a housing including an inlet and an outlet and defining a fluid flow path between the inlet and the outlet and a liquid filtration element comprising a synthetic, polymeric microporous structure positioned inside the housing across the flow path, being comprised of first and second media. In a preferred embodiment of the filter device, the liquid filtration medium is wettable by the parenteral fluid, and the filter device further comprises a microporous non-wetting or liquid-repellant component to provide for gas/liquid separation.The liquid filtration element of the filter device of claim 1 comprises two media in series. The first or upstream medium is characterized by a pore rating of greater than that of the second or downstream medium. Preferably, the first medium comprises a synthetic polymeric microfibrous matrix. The first medium is preferably wettable by the parenteral fluid. A preferred way of rendering the first medium wettable is by covering the surfaces of the medium with a grafted superstrate polymer (that is, a layer of polymer formed at and covering the surfaces of the medium) to render the medium wettable by the liquid with which it comes in contact in carrying out the method of this invention.The second or downstream medium is characterized by a pore rating of less than 1.2 micrometers. In a preferred embodiment, the second medium comprises a microporous structure having a pore rating of less than about 1.0 micrometer, more preferably in the range of from 0.5 to 0.8 micrometer. As with the first medium, it is preferred that the second medium be wettable by the parenteral fluids with which it comes in contact. A variety of synthetic, polymeric, microporous structures may be used as the second or downstream medium provided they do not adversely affect the parenteral fluid being filtered, e.g., by releasing harmful components into the fluid, and they have the requisite physical properties to provide the desired filtration characteristics. Preferred materials include skinless, hydrophilic, microporous, polyamide membranes of the type described in U. S. Patent 4,340,479. Particularly preferred are skinless, hydrophilic, microporous nylon 66 membranes of this type available from Pall Corporation under the trademark ULTIPOR®. Microporous polyvinylidene difluoride membranes of the type disclosed in U. S. Patents 4,203,848 and 4,618,533 may also be used as may microporous media with low non-specific protein adsorption, such as those described in U. S. Patents 4,886,836, 4,906,374, and 4,964,989. Charge-modified polyamide membranes with a positive zeta potential in alkaline media, such as those described in U. S. Patent 4,702,840 and available from Pall Corporation under the trademark BIODYNE B® may also be used. Polyamide membranes with controlled surface properties such as those described in U. S. Patent 4,707,266, as well as other microporous, synthetic, polymeric structures with the requisite pore rating including microfibrous matrices, may also be used. As noted above, it is preferred that the liquid filtration element be wettable by the parenteral nutrient fluid. In those instances where the medium is not wettable by the parenteral nutrient fluid, it may be rendered wettable by any method which does not adversely affect the filtration process. In addition to radiation grafting, suitable surface active agents, such as polyether polyhydroxy block copolymers, may be employed.The liquid filtration element of the filter device of the present invention is preferably in the form of a flat web or sheet, although other forms including pleated, cylindrical, or other geometric shapes suitable for incorporation into a filter may be used. When the liquid filtration element comprises first and second media, a composite filter sheet may be formed and used as a flat, planar sheet. Alternatively, the composite sheet may be formed into a pleated or accordion form and used in that form. As another less preferable alternative, the first and second filter media can be formed as separate sheets which can be used independently in a series arrangement. The liquid filtration element has a pore rating of less than 1.2 micrometers, preferably less than about 1.0 micrometer, more preferably from 0.5 to 0.8 micrometer. Particularly preferred as a second or downstream medium are hydrophilic microporous nylon 66 membranes with a pore rating of about 0.65 micrometers.A microfibrous matrix, as the term is used herein, indicates a three-dimensional network of interconnected fibers, whether melt-blown, staple, or continuous, which together form a coherent structure suitable for use as a filter medium. Preferred microfibrous matrices are made from melt-blown thermoplastic polymeric fibers, such as polyolefins, particularly polypropylene, polyesters, particularly polybutylene terephthalate, and polyamides, such as nylon 66, where the fiber diameter is typically in the range of from 1 to 4 micrometers, typically having void volumes ranging from 60 to 90% and thicknesses in the range of from 0.13 to 2.54 mm (0.005 to 0.10 inch).While a liquid filtration element comprising two media is used in the filter device according to claim 1 and the method according to claim 15, the element consists of a single medium in the method according to claim 20. When a single medium is used, a microfibrous matrix is used because of the enhanced dirt capacity of such a structure vis-a-vis a microporous membrane formed from a synthetic plastic material having a continuous matrix structure and which has, relative to a microfibrous matrix, relatively uniform pore sizes and limited dirt capacity, making it more prone to pressure build up and clogging.Pore ratings, as that term is used herein, may be determined using the Latex Sphere Test. This test determines the removal rating of a filtration medium by measuring the efficiency of the medium in removing uniform diameter polystyrene microspheres in a liquid medium. Typically, a dilute suspension of spheres (0.01 to 0.1 weight percent) is prepared in water containing 0.1 weight percent Triton X-100, an octyl phenoxypolyethoxyethanol with about nine and one-half ethylene oxide units per molecule, available from Rohm & Haas Company. The size of the spheres can vary from 0.038 to 5 microns. They are commercially available from Dow Chemical Company. A volume of about 10 cubic centimeters of the suspension per 6.45 cm2 (per square inch) (of the filtration medium) is passed through the medium and the filtrate is collected in a test tube. The concentration of microspheres in the filtrate can be measured by any number of means, for example, visually, or by use of a nephelometry device (i.e., turbidity meter). The smallest diameter microsphere which is retained at a 99.9% efficiency, i.e., 999 out of 1,000, determines the pore rating. The filter device of the subject invention preferably further comprises a liquid-repellant or non-wetting component or structure acting in concert with the liquid filtration element which, as noted above, is preferably wetted by the parenteral nutrient liquid. Any liquid-repellant or non-wetting porous material may be used which is effective in repelling and, therefore, does not pass a liquid under the conditions encountered in carrying out the method of this invention, thereby providing for venting of gas which may be present in the parenteral nutrient fluid to be filtered. Generally, the pore size of such a material should be less than about 15 micrometers. To preclude bacteria from entering the device via the liquid-repelling structure of the filter device (which in use must be open to the atmosphere to allow the gas to be vented), the pore size should be less than about 0.3 micrometer, preferably 0.2 micrometer or less. Preferred materials are the liquid-repelling membranes disclosed in U. S. Patent 4,954,256. These membranes have a critical wetting surface tension (CWST) of less than about 28 dynes/centimeter, rendering them liquid-repelling or non-wetting by liquids with surface tensions well below that of water's surface tension of 72 dynes/centimeter. CWST is defined in U. S. Patent No. 4,954,256, and in greater detail in U. S. Patent No. 4,925,572. Of these, particularly preferred is a microporous, polymeric membrane having a pore rating of about 0.2 micrometer comprising a nylon 66 membrane substrate to which has been bonded to the surface a superstrate fluoropolymer formed from a monomer containing an ethylenically unsaturated group and a fluoroalkyl group. The housings for the porous medium can be fabricated from any suitably impervious material, including any impervious thermoplastic material. For example, the housing may preferably be fabricated by injection molding from a transparent or translucent polymer, such as an acrylic, polystyrene, or polycarbonated resin. Not only is such a housing easily and economically fabricated, but it also allows observation of the passage of the fluid through the housing. The filter device in accordance with this invention may be fashioned in a variety of configurations including those described in U. S. Patent 3,803,810. Preferably, the device will have a hold up volume of 20 cubic centimeters or less. A preferred configuration, as depicted in Figures 1-4, can be constructed with a hold up volume of less than 5 cubic centimeters. Indeed, a device as described in Figures 1-4 was used in Example 1 below which had a hold up volume of only about 1.5 cubic centimeters.Referring, then, to the drawings, a preferred general configuration is shown in Figures 1-4 which depict, in schematic form, the components of a filter device in accordance with the invention and which show the flow paths of the liquid and of gas which is separated from the liquid and vented to the atmosphere.In Figures 1 to 4, a filter device 10 embodying the invention generally comprises a transparent housing 11 and a liquid filtration element 12 positioned within the housing 11. In the liquid filtration element depicted in the drawings, the liquid filtration element 12 comprises a first filter medium 13 and a second filter medium 14 in flat, planar composite filter sheet form.The housing may have a variety of configurations. Preferably, liquid hold up volume is minimized. As depicted in the drawings, in a preferred device, an inlet 15 communicates with a first chamber 16 which is in fluid communication with the liquid filtration element 12 as well as with two non-wetting or liquid-repellant microporous structures 17 and 18 which allow gas to be vented from the device.The housing 11 includes an inlet 15 and an outlet 19 defining a fluid flow path between the inlet 15 and the liquid outlet 19 with the liquid filtration element 12 disposed across the liquid flow path. The inlet and outlet may be variously configured. For example, the inlet 15 may be configured as a spike which can be inserted into a container of parenteral fluid. Alternatively, as shown in the drawings, both the inlet and the outlet can be configured as tube connectors. In addition to the chamber 16 depicted in Figures 3 and 4, the housing 11 has interior walls 20 and 21 which, in combination with the exterior walls for the housing 11, the liquid-repellant, microporous structures 17 and 18, and the liquid filtration element 12, define three additional chambers 22, 23, and 24. Chambers 22 and 24 include gas vents or outlets 25 for venting to the atmosphere gas separated from the incoming parenteral nutrient fluid.The flow of parenteral nutrient liquid in the filter device 10 after entry of the parenteral nutrient fluid via the inlet 15 is depicted in Figure 3 by arrows in the chambers 16 and 23. As depicted in Figure 3, the liquid component of the parenteral fluid entering inlet 15 passes into the chamber 16, then through the liquid filtration element 12 into chamber 23, and then flows out of the filter device via the outlet 19.The flow path of gas that may be present in the incoming parenteral nutrient fluid is depicted in Figure 4 by arrows in chambers 16, 22, and 24. As depicted, the gas enters the chamber 16 and passes freely through the non-wetting or liquid-repellant structures 17 and 18 into the chambers 22 and 24 and then out the gas outlets or vents 25.The invention will be better understood by reference to the following examples which are offered by way of illustration and not by way of limitation. ExamplesExample 1:A microfibrous matrix comprised of approximately 1.6 micrometer diameter polypropylene fibers having a basis weight of 4.5 milligrams per square centimeter was prepared by melt blown fiber extrusion. A final web thickness of about 0.08 mm (0.003 inch) was achieved by hot calendering using commercially available calendering equipment. The microfiber web was then surface modified in order to render it hydrophilic. Gamma radiation (Cobalt 60) was used to graft co-polymerize hydroxypropyl acrylate and methacrylic acid in a monomer ratio of 9:1 with the polypropylene fiber surface and render the matrix wettable by a TNA parenteral admixture. A liquid filtration element in the form of a flat sheet comprising two layers of this grafted web and having a pore rating of 0.8 micrometer was assembled into the device described (in Figure 1) which had a hold up volume of about 1.5 cubic centimeters and an effective liquid filtration surface area of about 10.97 cm2 (1.7 square inches). The two non-wetting or liquid-repellant structures were polytetrafluoroethylene membranes with a nominal pore rating of 0.1 micrometer, each of about 0.97 square centimeters (0.15 square inch). This device was then subjected to a filtration test using 2.7 liters of a typical central formula TNA admixture which contained amino acid, dextrose, a lipid emulsion, a multi-vitamin solution, and electrolytes. Flow was provided by means of a peristaltic pump at a rate of 300 milliliters per hour, and the upstream applied pressure (effectively the pressure drop across the liquid filtration element) was monitored by means of a gauge upstream of the filter device. Throughout the duration of the test (2.7 liters total volume), the pressure did not rise significantly and remained between 5.6 X 103 kg/m2 and 6.3 X 103 kg/m2 (8 and 9 psi).Example 2: (Comparison)A microporous polyvinylidene fluoride (PVDF) membrane was solution cast under conditions which produced a 0.65 micrometer pore rating in its dry, unmodified state. A liquid filtration element in the form of a disc having a diameter of 2.86 cm. (1.125 inches) was cut from this membrane and assembled into a reusable plastic housing jig having an effective flow area of 4.97 cm2 (0.77 square inch). The membrane was prewetted in isopropyl alcohol prior to use since it was not wetted spontaneously by the TNA solution. The membrane was then tested for the filtration of TNA formulation of the same composition and in the same manner as in Example 1 except that flow was provided by means of a volumetric infusion pump (Model IMED 960 available from IMED Corporation) and the flow was adjusted to 150 milliliters per hour. During this test, the pressure was observed to increase steadily. At 170 milliliters of total volume throughput, the upstream pressure exceeded 1.05 x 104 kg/m2 (15 psi), the pump alarm sounded, and the pump shut down, ending the test.Example 3:The filtration test of Example 2 was repeated except that a prefilter consisting of a surface modified, polybutylene terephthalate polyester microfiber matrix microporous medium was positioned as a prefilter in the housing upstream of the downstream or second filter medium (PVDF membrane). The microfiber matrix was modified using a mixture of hydroxyethyl methacrylate and methacrylic acid in a monomer ratio of 0.35:1 using gamma radiation from a Cobalt 60 source. The prefilter had a voids percent of about 72%, a CWST equal to 94 dynes per centimeter rendering it readily wettable by the TNA formulation, an average fiber diameter of 2.4 micrometers, and a pore rating of about 2 micrometers. After pre-wetting of the PVDF membrane as in Example 2, a filtration test was run using a portion of the same TNA formulation used in Example 2. The same flow rate as in Example 2, 150 milliliters per hour, was also used. In contrast to Example 2, 620 milliliters of TNA solution were filtered without exceeding a pressure of about 4.9 X 103 kg/m2 (7 psi). In particular, the pressure leveled off at about 4.2 X 103 kg/m2 (6 psi) after 170 milliliters of TNA had been filtered and remained relatively constant for the entire remaining volume of filtered TNA admixture. The results clearly demonstrates the beneficial effect of the prefilter section which resulted in a significantly lower applied pressure and thus a larger volume filtered.Example 4: (Comparison)A nylon 66 membrane having a pore rating of 0.65 micrometer was tested in the same manner as was used in Example 2 except that the TNA admixture did not contain multi-vitamins and no prefilter section was utilized. The results showed the pressure drop to rise consistently as the TNA formulation was filtered. After 270 milliliters volume of throughput, the pressure exceeded 1.05 x 104 kg/m2 (15 psi) and the pump stopped.Example 5:The same TNA admixture was used as in Example 4 to test the membrane and prefilter combination described below and the same test method was also used. The prefilter was the same as that used in Example 3 and the membrane was the same as the nylon 66 membrane used in Example 4. The results showed that the pressure drop leveled off at about 3.16 x 103 kg/m2 (4.5 psi) and did not rise significantly (only about 0.70 X 103 kg/m2 (1 psi)) over the test period during which a total volume of 1.5 liters was filtered. A comparison of Examples 4 and 5 reveals the benefit of the prefilter in the latter example which greatly extends the volume of the TNA admixture that can be filtered without excessive pressure build up.Examples 4 and 5 demonstrate the benefits derived from the use of a prefilter.A particularly preferred filter device in accordance with the subject invention has the configuration depicted in Figures 1-4 and utilizes a hydrophilic nylon membrane with a pore rating of about 0.65 micrometer in combination with a prefilter as described in Example 3 above and two non-wetting or liquid-repellant structures of a nylon 66 membrane having a CWST of less than 28 and a pore rating of about 0.2 micrometer. Preparation of such a liquid-repellant membrane is described in U. S. Patent 4,954,256.	A filter device (10) for treating parenteral nutrient fluid containing a lipid comprising: a housing (11) including an inlet (15) and an outlet (19) and defining a fluid flow path between the inlet (15) and the outlet (19); anda liquid filtration element (12) comprising a synthetic polymeric microporous structure positioned inside the housing (11) across the flow path, wherein,the liquid filtration element (12) comprises a first filter medium (13) and a second filter medium (14) in series, the first medium (13) having a pore rating greater than the second medium (14), the second medium (14) having a pore rating of less than 1.2 µm.The filter device of claim 1 wherein the housing (11) further includes at least one gas vent outlet (25) and defines a gas flow path between the inlet (15) and the at least one gas vent outlet (25); and the liquid filtration element (12) is positioned inside the housing (11) across the fluid flow path; and wherein the filter device (10) further comprises a non-wetting, liquid-repellant, microporous structure (17) and/or (18) positioned inside the housing (11) across the gas flow path adapted to vent gas from the parenteral nutrient fluid.The filter device of claim 1 or 2 wherein the first filter medium (13) comprises a microfibrous matrix.The filter device of any of claims 1 to 3 wherein the second medium (14) comprises a microporous membrane.The filter device of any of claims 1 to 4 wherein the first filter medium (13) and the second filter medium (14) each comprises a microporous medium.The filter device of claim 2 wherein the non-wetting, liquid-repellant microporous structure (17) and/or (18) has a pore size of less than about 15 micrometers.The filter device of claim 6 wherein the non-wetting, liquid-repellant microporous structure (17) and/or (18) has a pore size of less than about 0.3 micrometers.The filter device of claim 7 wherein the non-wetting, liquid-repellant microporous structure (17) and/or (18) has a pore rating of about 0.2 micrometer.The filter device of any of claims 2 to 8 wherein the non-wetting, liquid repellant microporous structure (17) and/or (18) comprises a nylon 66 substrate.The filter device of any of the preceding claims wherein the first medium (13) comprises a microfibrous matrix of thermoplastic polymeric fibers selected from the group consisting of polyolefins, polyesters, and polyamides and the second medium (14) comprises a microporous membrane, both the first and second medium being wettable by the parenteral nutrient fluid. The filter device of any of the preceding claims wherein the second medium (14) has a pore rating of less than about 1.0 micrometer.The filter device of claim 11 wherein the second medium (14) has a pore rating in the range of from 0.5 to 0.8 micrometer.The filter device of any of claims 10 to 12 wherein the microfibrous matrix comprises surface modified polybutylene terephthalate microfibers and the microporous membrane comprises nylon 66.The filter device of any of the preceding claims wherein the liquid filtration element is wettable by a parenteral nutrient fluid. A method for treating a parenteral nutrient fluid containing a lipid comprising passing the parenteral fluid through a filter device according to any of the preceding claims.The method of claim 15 wherein the parenteral nutrient fluid comprises a total nutrient admixture comprising lipids, glucose, and amino acids.The method of any of claims 15 to 16 further comprising passing the parenteral nutrient fluid through the liquid filtration element (12) at a flow rate of up to about 300 ml per hour.The method of any of claims 15 to 17 further comprising passing the parenteral nutrient fluid through the liquid filtration element (12) with a pressure drop of about 1.05 x 104 kg/m2 or less.The method of any claims 15 to 18 further comprising separating gas from the parenteral nutrient fluid by providing at least one gas vent outlet (25). A method for treating a parenteral nutrient fluid containing a lipid comprising passing the parenteral fluid through a filter device (10) comprising a housing (11) including an inlet (15) and an outlet (19) and defining a fluid flow path between the inlet (15) and the outlet (19), and a liquid filtration element (12) positioned inside the housing (11) across the flow path, wherein said liquid filtration element (12) comprises a synthetic polymeric microfibrous matrix having a pore rating of less than 1.2 micrometers.	PALL CORP; PALL CORPORATION	BORMANN THOMAS J; GSELL THOMAS C; MATKOVICH VLADO I; BORMANN, THOMAS J.; GSELL, THOMAS C.; MATKOVICH, VLADO I.
EP-0489411-B1	489,411	EP	B1	EN	19,970,409	1,992	20,100,220	new	C23C18	null	C23C18, H05K3, B41J29	H05K 3/18B2C, C23C 18/16B2, C23C 18/30	Process for catalysis of electroless metal plating on plastic	A method of forming at least one electrically conductive path in a plastic substrate comprising providing a thermoplastic substrate having a melting point below 325° C, coating said substrate with a precursor of a catalyst for the electroless deposition of conductive metals, said catalyst precursor having a decomposition temperature below the melting point of said thermoplastic and within the temperature range where said thermoplastic softens, heating the portion of said coated thermoplastic substrate corresponding to said conductive path to a temperature sufficient to decompose said catalyst precursor to said catalyst and soften said thermoplastic; said substrate, catalyst precursor and temperature being selected such that on heating to the temperature the precursor decomposes to the catalyst, the thermoplastic softens and at least partially melts without substantial decomposition to enable the catalyst to penetrate the surface of the thermoplastic and become anchored thereto to provide nucleation sites for the subsequent electroless deposition of conductive metal and depositing conductive metal by electroless deposition on said heated portion to form said conductive path.	CROSS REFERENCE TO RELATED APPLICATIONAttention is directed to commonly assigned U.S. Patent No. 4970553 in the name of Thomas E.Orlowski et al., and entitled Electrical Component With Conductive Path. BACKGROUND OF THE INVENTIONThe present invention relates generally to electrical components, methods for making electrical components and the machines employing electrical components. In particular, it relates to electrical components having an electrically conductive path in a thermoplastic substrate formed by the electroless deposition of conductive metals on a path or pattern of nucleation sites of catalyst for the electroless deposition of conductive metals anchored in the thermoplastic. More specifically, the electrical component may be a planar member, a two-sided circuit board, or a frame or structural member in a machine such as automatic reprographic machines, including office copiers, duplicators and printers. In a typical electrostatographic reproducing machine, a photoconductive insulating member is uniformly charged and exposed to a light image which discharges the exposed or background areas and creates an electrostatic latent image on the member corresponding to the image contained within the original document. Alternatively, a light beam such as a laser beam may be modulated and used to selectively discharge portions of the photoconductive surface to record the desired information thereon. The electrostatic latent image is made visible by developing the image with developer powder referred to in the art as toner which may be subsequently transferred to a support surface such as paper to which it may be permanently affixed by the application of heat and pressure. In commercial applications of such products, it is necessary to distribute power and/or logic signals to various sites within the machine. Traditionally, this has taken the form of utilizing conventional wires and wiring harnesses in each machine to distribute power and logic signals to the various functional elements in an automated machine. While the conventional approach has been immensely effective in producing convenience products, with increasing demands on manufacturing cost and the desire for automated assembly, different approaches have to be provided. For example, since individual wires and wiring harnesses are inherently very flexible, they do not lend themselves to automated assembly such as with the use of robotics. Furthermore, such harnesses may have to be handled or moved several times to make all connections required. This is a highly labor intensive task, frequently requiring routing of the several harnesses through channels and around components manually with the final connections being also accomplished manually, thereby resulting in potential human error in the assembly. The potential for human error is reduced with the use of automated and in particular robotic assembly. In addition to the relatively high labor costs associated with harness construction and installation of electrical wiring harnesses it is well to note that they are less than totally reliable in producing their intended function. Furthermore, and with increasing sophistication of the capabilities of such products, a plurality of wiring harnesses may be required in any individual machine which can require a large volume of space thereby increasing the overall size of the machine. Accordingly, there is a desire to provide an alternative to the conventional wiring and wiring harnesses that overcomes these difficulties. PRIOR ARTIn U.S. Patent No. 4,841,099 to Epstein, et al. it has recently been proposed to provide electrical components and support members for a machine with continuous electrically conducting paths between electrical components formed by the in situ heat conversion of electrically insulating fibrous filler material held within an electrically insulating structural polymer matrix. The electrically conductive pattern may be formed by exposure of the component or the support member to a laser beam through a mask containing the desired pattern or by moving the laser or support member appropriately to achieve the desired pattern. Subsequent to the formation of the electrically conductive trace or path, the pattern may be electroplated if desired to attain metallic conductivity. Another recent development is the laser irradiation of organometallic palladium compounds with an argon ion laser to selectively deposit catalytic amounts of palladium on polyimide. Subsequent immersion of the irradiated samples in an electroless copper solution results in copper deposition. Since a few monolayers of palladium are sufficient to catalyze the electroless copper process fast laser writing speeds of several centimeters per second are obtained. For further details of this technique, attention is directed to Laser Direct Write Copper on Polyimide for High Speed Interconnections by Cole et al., G.E. Research and Development Center, Power Electronics Laboratory, 88CRD323, February 1989; Laser-Induced Selective Copper Deposition on Polyimide by Cole et al., Applied Physics Letters 53(21), November 21, 1988, pages 2111-2113. LASER PROCESSING FOR INTERCONNECT TECHNOLOGY by Cole et al., SPIE, Volume 877, Micro-Optoelectronic Materials, 1988, pages 92-96. Laser Activated Copper Deposition on Polyimide Abstract #445, The Electrical Chemical Society, for meeting October 18-23, 1987. Extended Abstracts, Volume 87-2. One advantage of this process, discussed at page 2112, left column, is that since the polyimide is thermally stable to a temperature greater than 400° Centigrade and the palladium compounds decompose at about 225° Centigrade, a large process window is available where decomposition to palladium metal occurs without damage to the underlying polyimide. A particularly troublesome difficulty with this process is the poor adhesion between the metals and the polyimide substrate. This poor adhesion may be simply determined through use of the adhesive tape test, wherein the plated area of the plastic is contacted with a piece of adhesive tape, which upon removal, removes the metal from the plastic, thereby interrupting the continuity of the conductive path. Conventional ways of eliminating this problem include mechanically roughening the surface of the plastics, such as with sand or glass bead blasts, plasma etching of the surface or hot chemical treatment, such as with chromic acid to roughen the plastic surface. Most of these techniques require several steps to produce a finished product. SUMMARY OF THE INVENTIONThe present invention is directed to electrical components, methods for making electrical components and machines employing such electrical components. In a specific aspect of the present invention, the surface of a thermoplastic substrate is modified to promote adhesion of the metal to the substrate. More specifically, the surface of the thermoplastic substrate is modified by heating to enable decomposition of a catalyst precursor to the catalyst together with sufficient softening of the thermoplastic surface to enable the catalyst to penetrate the surface of the softened plastic and be anchored in place by the thermoplastic. In a principle aspect of the present invention, a thermoplastic substrate having a melting point below 325° Centigrade is coated with a precursor of a catalyst for the electroless deposition of conductive metals, the precursor having a decomposition temperature below the melting point of the thermoplastic, and within the temperature range where the thermoplastic softens and a portion of the coated thermoplastic substrate corresponding to the conductive path is heated to a temperature sufficient to decompose the catalyst precursor to the catalyst and soften the thermoplastic substrate to partially melt without substantial decomposition and thereby anchor the catalyst to the substrate to provide nucleation sites for the electroless deposition of conductive metal to form the conductive path. In a further aspect of the present invention, the coated plastic substrate is heated by directing a laser beam, preferably a focused carbon dioxide laser, to the portion of the substrate corresponding to the conductive path. In a further aspect of the present invention, the coated catalyst precursor is removed from the unheated areas of the coated thermoplastic substrate before the electroless deposition step. In the further aspect of the present invention, the melting point of the thermoplastic substrate is below 300° Centigrade and is within 50°, preferably 30°, of the decomposition temperature of the catalyst precursor. In the further aspect of the present invention, the thermoplastic substrate is a polyamide, preferably nylon 66 or nylon 6. In a further aspect of the present invention, the catalyst precursor is applied to thermoplastic substrate from a solvent solution, the solvent of which wets but does not dissolve the thermoplastic. In a further aspect of the present invention, the catalyst precursor is selected from the group consisting of: copper acetate, copper oxalate, copper carbonate, copper salicylate, copper butyrate, palladium diamine hydroxide, palladium acetate, palladium acetylacetate and palladium hexafluoroacetate. In a further aspect of the present invention, the laser beam is directed to the coated thermoplastic substrate in a predetermined pattern comprising a plurality of paths. In a further aspect of the present invention, the thermoplastic substrate is a three-dimensional member, which is moved relative to the laser beam to create a pattern of catalyst corresponding to the desired conductive path. In a further aspect of the present invention, the thermoplastic substrate has at least one structural groove therein in a pattern corresponding to the conductive path. Other features of the present invention will become apparent as the following description proceeds and upon reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGSFigure 1 is an isometric view partially exploded of a portion of the framed section of an electrostatographic printing apparatus with a representative illustration of a circuit pattern formed according to the practice of the present invention. Figures 2A-2E are views in cross section of the thermoplastic substrate during different stages in the process of forming the conductive path. Figure 3 is an isometric view of a three-dimensional part with enlarged cutaway view 3A illustrating grooves on both sides connected with a via and enlarged cutaway view 3B illustrating an electroless pattern in a groove. Figure 4 is a schematic illustration of a system performing the exposure of the electrically conductive paths in a structural member. DESCRIPTION OF THE PREFERRED EMBODIMENT The invention will now be described with reference to a preferred embodiment of an electrical component according to the present invention. In accordance with the present invention, an electrical component having greatly improved adhesion of the conductive metal path, pattern or circuit to the substrate is provided. The component is made by heating a thermoplastic substrate having a melting point below 325°C which has been coated with a precursor of a catalyst for electroless deposition of conductive metals to a temperature to decompose the catalyst precursor to the catalyst, soften and at least partially melt without substantial decomposition, the thermoplastic substrate to enable the catalyst to penetrate the surface of the substrate and be firmly anchored in place when the plastic is cooled. The component may be a structural or non structural element, may have a single conductive path or a circuit. Referring now to Figures 1 and 2, the significance of the present invention will be appreciated. In Figure 1 a structural frame 10, together with drive module 12 and platen drive module 14, are illustrated as parts of an electrostatographic reproducing apparatus. For further description of the machine elements and its manner of operation, attention is directed to U.S. Patent 4,563,078. Also illustrated are electroconductive paths or traces 20 which may be formed directly into the machine support frame 10 with the technique according to the present invention. Also illustrated are conductive traces 21 through vias 24. Figures 2A to 2E are enlarged cross sectional representations of the electrical component during several stages of its manufacture according to the technique of the present invention. In Figure 2A the substrate 26 has been coated on one surface with the catalyst precursor 28. Figure 2B illustrates the condition of the substrate after it has been exposed to a pattern of heat, such as, for example, by exposure to a laser beam to decompose the catalyst precursor to volatile gases and catalyst particles 30 which penetrate the surface of the thermoplastic substrate 26 and become anchored thereto as the substrate cools. Figure 2C illustrates the embodiment wherein the catalyst precursor 28 has been removed from the unheated portions of the thermoplastic substrate. Figure 2D illustrates the structure including a conductive metal layer 32 which has been electrolessly deposited on the exposed catalyst 30 which is thermally adhered to the plastic substrate 26. Figure 2E illustrates the alternative embodiment wherein catalyst precursor 28 has not been removed from the unheated areas. Any suitable thermoplastic substrate may be used in the practice of the present invention which has a melting point below 325° Centigrade and preferably has a melting point below 300° Centigrade. The catalyst precursors employed in the practice of the present invention typically have thermal decomposition temperatures below about 260°C and generally in the range of 200°-260°C. We have found that the optimum adhesion is achieved by selecting a thermoplastic having a melting point which is within 50° of the decomposition temperature of the catalyst precursor and preferably is within 30° of the decomposition of the catalyst precursor. This enables the decomposition of the catalyst precursor to volatile materials and catalyst at about the same temperature that the thermoplastic is substantially softened with partial but not substantial melting nor decomposition. This enables the catalyst particles to penetrate the surface of the thermoplastic and become anchored there when the thermoplastic cools. Typical thermoplastics include the engineering grade plastics such as, polyvinyl chloride, polyphenylene oxide such as Noryl, polycarbonates, ABS, blends of ABS with polycarbonate and other plastics and polyamide. The polyamides nylon 66, and nylon 6, are particularly preferred for their superior adhesion properties. If desired, the thermoplastic may be in pure form or can be filled with conventional fillers such as glass fibers and clays or foamed to reduce weight in a conventional manner. In an alternative embodiment, substrates made from thermosetting plastics may be employed when they are precoated with a suitable thermoplastic layer. The catalyst is typically selected to participate in the electroless deposition of conductive metals by providing nucleation sites for the metals. Typical catalyst precursors having decomposition temperatures between 200° and 260° Centigrade, include copper acetate, copper oxalate, copper carbonate, copper salicylate, copper butyrate, palladium diamine hydroxide, palladium acetate, palladium acetyl acetate, palladium hexa fluroacetylacetate, bis(acetonitrile)palladium(ll) chloride, bis(benzonitrile)palladium(ll) chloride, allylpalladium chloride dimer, and the platinum analogs of the above palladium compounds. Palladium acetate is particularly preferred because it is commercially available and decomposes cleanly and predictably at one of the lower decomposition temperatures of 220°C to carbon dioxide and acetic acid. Further, it is soluble in solvents such as acetone and alcohols which are harmless to thermoplastics. The catalyst precursor may be coated on the thermoplastic substrate in any suitable manner in either a pattern corresponding to the final conductive path desired or over the entire surface of the thermoplastic substrate. Typically, it is applied as a solvent solution in concentrations of from 1 to about 5 percent in water or organic solvents such as acetone, methyl ethyl ketone, ethyl alcohol, methyl alcohol, isopropyl alcohol, butyl alcohol, methyl isobutyl ketone, toluene, ammonia, chlorobenzene and methylene chloride. The solvent should be selected so that it dissolves the catalyst precursor but does not dissolve or otherwise tackify the thermoplastic substrate. The solvent solution may be applied by brushing, spin coating, dip coating to provide a substantially uniform coating on the surface of the thermoplastic substrate which upon decomposition provides the nucleation sites anchored in the softened thermoplastic substrate for the subsequent metal plating. After applying the solvent solution to the thermoplastic substrate, the solvent typically is permitted to evaporate without heating. Typically, the coated plastic substrate is heated in a pattern corresponding to the desired conductive trace by exposure to a laser beam. The laser is selected to have a wave length that the thermoplastic substrate can absorb. The carbon dioxide laser is particularly preferred as all the standard engineering thermoplastics mentioned above, absorb at its wave length of 10.6 microns. Typically, a low powered 20-25 watts per cm2., focused 1 mm. diameter spot, carbon dioxide laser can be scanned across the plastic surface at speeds from 0.5 mm. per second to 5 cm. per second to heat the catalyst precursor to a temperature above the thermal decomposition temperature where precursor is voltalized with gases coming off and the metallic catalyst deposit is left to penetrate the softened and partially melted thermoplastic surface and become anchored in the thermoplastic surface as it cools. As previously discussed above, optimum adhesion is obtained when the difference between the melting point of the thermoplastic and the decompositioned temperature of the catalyst precursor is less than 50° Centigrade and preferably less than 30° Centigrade. Following exposure to the laser beam and creation of the anchored catalyst path in the thermoplastic surface, the catalyst precursor in the unexposed or unheated areas may be removed with a solvent, such as the solvent from which the catalyst precursor was originally supplied. The final step in the formation of the electrical component according to the present invention is the electroless plating of conductive metal, such as, copper or nickel on the catalyst nucleation sites anchored in the thermoplastic substrate. Standard electroless plating techniques from a bath of, for example, copper sulfate for copper plating the catalyzed path are in accordance with the following, generally accepted mechanism: CuSO4.5H2O25 g/l Sodium gluconate60 g/l Na OH20 g/l Formaldehyde (37% solution)15 m/l Temperature23.9°C (75° F) Copper deposits of 0.76mm (30 microinch) thickness are typically produced in about 20 minutes. For low power applications this may be sufficient. However in many applications, thickness of up to 25,4 mm (1000 microinch) may be required. The additional copper thickness is most effectively accomplished by further electrolytically plating in an acid copper sulphate solution under the following conditions: CuSO4.5H2O250 g/l H2SO475 g/l CL-40 ppm gelatin40 ppm Temperature54.4°C (130°F) Current Density1 to 10 amps/square decimeter Attention is now directed to Figures 3 and 4. Figure 3 illustrates a three dimensional part having a continuous electroless pattern on multiple faces shown to transcend a corner as illustrated by 35 and 36. The trace continues down and is illustrated to pass through two vertical walls one of which is shown in enlarged cutaway 3A with via 34. The via of Figure 3A has a tapered wall configuration from one side to the other side with constantly changing cross section of the passage way, wherein the passage way can taper down from a maximum cross section on one side to a minimum cross section on the other side or alternatively, it can taper down from a maximum cross section at both sides to a minimum cross section between the first and second sides. With this kind of geometry the walls of the via may be coated from the side having a maximum cross section or alternatively from both sides to form a catalyst path from one side to the other, whereby during subsequent electroless plating the conductive metal is plated in the via. Enlarged cutaway Figure 3B also illustrates the use of grooves 37 in the thermoplastic substrate as the location of the conductive path in the thermoplastic substrate, which will be coated with the catalyst precursor exposed to the laser beam and subsequently electrolessly plated to form a continuous electroless pattern, thereby providing additional protection for the plated pattern against damage from abrasion. Attention is directed to Figure 4 which schematically illustrates a manner in which a plurality of conductive paths representing circuit patterns can be prepared in a part. The part 40 is secured to table 42 which is rotatably mounted about the center axis 43 of a motor shaft (not shown) in the motor box 44. In addition, the table is movable in the XY plane by movement of worm gear 46 by another motor (not shown) in the motor box 44. The laser scanning carriage 48 has three laser ports 50, 52, 54, one directed in each direction with the carriage movable vertically by worm gear 56 and motor 58 and horizontally by worm gear 60 and motor 62. The movement of the table 42 and the scanning carriage 48 is controlled by a programmable controller 64 to form the preselected pattern of conductive traces in the part 40. If desired, a mask 66 having a predetermined pattern may be placed on the part. The laser scanning operation may be carried out in an input duct to bathe the part in an inert gas such as nitrogen, or in a vacuum chamber. Alternatively or in addition, an exhaust hose may be placed adjacent the part being marked to remove any noxious materials produced by the heating. EXAMPLE IA thermoplastic substrate of polyvinyl chloride was thin coated with a solution (less than 50 mg. per ml.) of palladium (II). acetate as a catalyst precursor in acetone. Following coating the substrate acetone was permitted to evaporate. A focused one mm. spot diameter carbon dioxide laser beam, 20-25 watts per cm sq. was scanned across the coated substrate at a rate of 0.5 mm. per second, which heated the thermoplastic substrate above the thermal decomposition temperature of 220° Centigrade of the palladium acetate, thereby liberating decomposition gases such as carbon dioxide and acetic acid while leaving reduced palladium metal on the softened plastic surface. The thermoplastic substrate was then rinsed in acetone to remove the palladium acetate in the unexposed areas. Subsequent immersion of the plastic in a standard commercial electroless copper plating solution, provided a thick durable copper plating of 25 microns in only 15 hours in the laser exposed regions. Adhesion of the resulting conductor pattern was checked using IPC-L-108 Test Method. Accordingly, pressure sensitive tape (F.S. A-A-113), 12.7 mm (1/2 inch) wide x 50.8 mm (2 inch) long strips were firmly applied across the surface of the conductor pattern. The tape was then removed by rapidly applying manual force roughly perpendicular to the circuit pattern. This test was repeated two times. On visual inspection of both the circuit and tape specimens, a good bond of the plated circuit to the thermoplastic substrate was indicated by the lack of any evidence of adhesive failure. EXAMPLES II AND IIIThe procedure of Example I was repeated for nylon 66 and nylon 6 substrates under the same conditions except that the laser power was 30-35 watts/cm2 Both nylon 66 and nylon 6 passed the above described adhesive tape test. Adhesion for both samples was better than Example I in that the electrolessly deposited traces were difficult to physically scrape off with a metal edge without removing some of the substrate EXAMPLE IVThe procedure of Example I was repeated for a polyimide substrate except that the laser power was 40-45 watts/cm2. Electroless traces were formed on the polyimide but they did not pass the adhesive tape test since the traces came right off the substrate when the adhesive tape was removed. Since this polyimide decomposes at a temperature greater than 800°C the laser exposure was insufficient to soften the substrate to enable the catalyst to penetrate the surface and adhere to it. Accordingly, the present invention provides a simple, economical alternative to conventional wiring and the construction of electrical components. It further provides improved adhesion between a substrate and an electroless plated metal path. The electrical component is produced in a very simple process with few steps and an economical process wherein the catalyst precursor in the unexposed areas on the substrate may be recovered and reused. Furthermore, there is no surface treatment other than the simple coating and the width of the trace can be easily controlled by controlling the laser spot size or mask configuration. In addition, the manufacturing process lends itself to automation and that it may be used in a programmable, controllable process. The disclosures of the patents and other references as well as the co-pending application referred to herein are hereby specifically and totally incorporated herein by reference. While the invention has been described with specific reference to elastostatographic copier and printer machines, it will be appreciated that it has application to a large array of machines with electrical components. Accordingly, it is intended to embrace all such alternatives and modifications, as may fall within the scope of the appended claims.	A method of forming at least one electrically conductive path in a plastic substrate comprising providing a thermoplastic substrate having a melting point below 325° C, coating said substrate with a precursor of a catalyst for the electroless deposition of conductive metals, said catalyst precursor having a decomposition temperature below the melting point of said thermoplastic and within the temperature range where said thermoplastic softens, heating the portion of said coated thermoplastic substrate corresponding to said conductive path to a temperature sufficient to decompose said catalyst precursor to said catalyst and soften said thermoplastic; said substrate, catalyst precursor and temperature being selected such that on heating to the temperature the precursor decomposes to the catalyst, the thermoplastic softens and at least partially melts without substantial decomposition to enable the catalyst to penetrate the surface of the thermoplastic and become anchored thereto to provide nucleation sites for the subsequent electroless deposition of conductive metal and depositing conductive metal by electroless deposition on said heated portion to form said conductive path. The method of claim 1 including the step of removing the coated catalyst precursor from the unheated areas of the thermoplastic substrate before the electroless deposition step. The method of claim 1 wherein said heating comprises directing a laser beam to the portion of the substrate corresponding to said conductive path. The method of claim 3 wherein said laser beam is from a focused carbon dioxide laser. The method of claim 1 wherein the melting point of the thermoplastic substrate is below 300° C. The method of claim 1 wherein the melting point of the thermoplastic substrate is within 50° C of the decomposition temperatures of the catalyst precursor. The method of claim 6 wherein the melting point of the thermoplastic substrate is within 30° C of the decomposition temperature of the catalyst precursor. The method of claim 1 wherein the thermoplastic substrate is a polyamide. The method of claim 8 wherein the polyamide is selected from the group consisting of nylon 66 and nylon 6. The method of Claim 1 wherein said catalyst precursor is applied to the thermoplastic substrate from a solvent solution the solvent of which wets but does not dissolve the thermoplastic. The method of Claim 2 wherein the catalyst precursor is removed from the unheated areas of the thermoplastic substrate by rinsing with a solvent to dissolve the catalyst precursor, said solvent wetting but not dissolving the thermoplastic. The method of Claim 1 wherein said catalyst precursor is selected from the group consisting of copper acetate, copper oxalate, copper carbonate, copper salicylate, copper butyrate, palladium diamine hydroxide, palladium acetate, palladium acetylacetate, palladium hexafluoroacetate and palladium nitrate. The method of claim 12 wherein said catalyst precursor is palladium acetate. The method of claim 13 wherein the palladium acetate is applied to the substrate from an acetone solution thereof and said conductive metal is copper. The method of claim 3 wherein said laser beam is directed to said coated thermoplastic substrate in a predetermined pattern. The method of claim 15 wherein said predetermined pattern comprises a plurality of paths. The method of claim 3 wherein said coated thermoplastic substrate is a three dimensional member and including the step of moving said substrate and said laser beam relative to each other to create a pattern of catalyst corresponding to said conductive path. The method of claim 1 wherein said thermoplastic substrate has at least one structural groove therein, in a pattern corresponding to said conductive path. An electrical component comprising a thermoplastic substrate having a melting point below 325° C, an electrically conductive path in said substrate comprising a continuous electrolessly deposited conductive metal path adhering to electroless deposition catalyst nucleation sites strongly anchored in said thermoplastic substrate, said catalyst being derived from heating a coating on said substrate of a catalyst precursor having a decomposition temperature below the melting point of said thermoplastic and within the temperature range where said thermoplastic softens, said substrate, catalyst precursor and temperature having been selected such that on heating to the temperature the precursor decomposes to the catalyst, the thermoplastic softens and partially melts without substantial decomposition and anchors the catalyst providing nucleation sites. A machine including a plurality of electrical components each requiring the supply of electrical components for proper functioning; said machine including at least one component comprising a thermoplastic substrate having a melting point below 325° C, an electrically conductive path in said substrate comprising a continuous electrolessly deposited conductive metal path adhering to electroless deposition catalyst nucleation sites strongly anchored in said thermoplastic substrate, said catalyst being derived from heating a coating on said substrate of a catalyst precursor having a decomposition temperature below the melting point of said thermoplastic and within the temperature range where said thermoplastic softens, said substrate, catalyst precursor and temperature having been selected such that on heating to the temperature the precursor decomposes to the catalyst, the thermoplastic softens and melts without substantial decomposition and anchors the catalyst providing nucleation sites.	XEROX CORP; XEROX CORPORATION	BAILEY RAYMOND E; DUFF JAMES; EWING JOAN R; ORLOWSKI THOMAS E; SWIFT JOSEPH A; BAILEY, RAYMOND E.; DUFF, JAMES; EWING, JOAN R.; ORLOWSKI, THOMAS E.; SWIFT, JOSEPH A.
EP-0489412-B1	489,412	EP	B1	EN	19,950,927	1,992	20,100,220	new	H02M3	null	H02M3, H02J1	H02M 3/07	A constant current integrated power supply	A positive energizing voltage, preferably in a CMOS circuit, is converted, primarily by a pair of buffer capacitors and secondarily by a filter capacitor, to a particular negative potential. One buffer capacitor is charged through first switches by the positive voltage during the positive half cycles of a clock signal. The buffer capacitor is discharged to a load during the negative half cycles of the clock signal through a circuit including such buffer capacitor, second switches, a third switch, a reference voltage (e.g. ground) line and a negative potential line. The other buffer capacitor is charged through fourth switches by the positive voltage during the negative half cycles of the clock signals. This buffer capacitor is discharged to the load during the positive half cycles of the clock signals through a circuit including such other buffer capacitor, fifth switches, the third switch, the reference voltage line and the negative potential line. The third switch has at each instant a variable state of conductivity dependent upon the magnitude of the negative potential at that instant. The magnitude of the negative potential is varied in accordance with the variations in the state of conductivity of the third switch to regulate the negative potential at a particular value. The filter capacitor is charged by the negative potential and is discharged to the load when the second and fifth switches are simultaneously open. This occurs for a brief interval every time that the polarity of the clock signal changes.	This invention relates to apparatus for converting a positive voltage into a negative voltage. More particularly, the invention relates to CMOS circuits for converting a positive energizing voltage into a regulated negative voltage for energizing a load. Complementary metal-oxide (CMOS) circuits in integrated circuit chip generally employ positive voltages to energize transistors and other components on the integrated circuit chip and control the operation of transistors on the integrated circuit chip. One advantage of CMOS circuits over other types of circuits (such as bi-polar) is that only positive voltages (and not negative voltages) have to be used to energize the circuits in the integrated circuit chip. Other advantages of CMOS chips over other types of chips is that they consume relatively low amounts of power and that the components such as the transistors are closely packed on the chips. It may sometimes be desired to provide a negative voltage on a CMOS integrated circuit chip to perform certain functions not capable of being performed when only a positive voltage is available. For example, it may sometimes be desired to energize a load on a CMOS chip with a negative voltage. Furthermore, it may be sometimes desired to regulate this negative voltage so that the negative voltage remains constant even when current flows from the source of the negative voltage to the load. Circuits have been devised in the prior art for obtaining a negative voltage in a CMOS integrated chip and for introducing this negative voltage to a load to obtain a flow of current to the load. The negative voltage in prior art CMOS circuits has generally been obtained by charging a buffer capacitor connected in the circuit to provide the negative voltage and by charging a filter capacitor connected in the circuit to energize the load. One problem with the prior art CMOS circuits has been that the negative voltage from the filter capacitor tends to change as the filter capacitor discharges to the load so that the negative voltage does not remain constant. As will be appreciated, such variations in the negative voltage tend to affect the operations of the circuits controlled by the negative voltage. This problem has existed for some time even though considerable effort has been devoted, and significant financial resources have been provided, to resolve the problem. From US-A- 4,636,930 an integrated circuit containing an inverting non-inverting voltage doubler charge pump circuit is known for converting a unipolar supply voltage to a bipolar supply voltage of a greater magnitude. The unipolar input voltage is placed across a first transfer capacitor by a first set of switches during a first time period. The unipolar input voltage source is placed in series with the first transfer capacitor and this series combination of voltages is placed across a first reservoir capacitor by a second set of switches during a second time period. The voltage appearing across the first reservoir capacitor is placed on a second transfer capacitor during the first time period. The voltage across the second transfer capacitor is placed onto a second reservoir capacitor with its polarity inverted by a further set of switches during the second time operation period. The voltage appearing between output terminals will be approximately twice the input voltage supplied by the voltage source and depends on the relative sizes of the transfer capacitors and reservoir capacitors as well as on the impedance of the switches. This invention provides a CMOS circuit which converts a positive energizing voltage into a stable and regulated voltage for energizing a load. The negative voltage remains substantially constant even during the time that the load is being energized. The invention employs a pair of buffer capacitors and a filter capacitor. However, the buffer capacitors primarily discharge to the load. This discharge occurs on a push-pull basis in synchronism with successive half cycles of a clock signal. The filter capacitor discharges to the load only during the time that neither of the buffer capacitors is discharging to the load. This occurs at the transition between the successive half cycles in the clock signals. In one preferred embodiment of the invention, a positive energizing voltage, preferably in a CMOS circuit, is converted, primarily by a pair of buffer capacitors and secondarily by a filter capacitor, to a particular negative potential. One buffer capacitor is charged through first switches by the positive voltage during the positive half cycles of a clock signal. This buffer capacitor is discharged to a load during the negative half cycles of the clock signal through a circuit including the buffer capacitor, second switches, a third switch, a reference voltage (e.g. ground) line and a negative potential line for providing a negative biasing potential. The second buffer capacitor is charged through fourth switches by the positive voltage during the negative half cycles of the clock signals. This buffer capacitor is discharged to the load during the positive half cycles of the clock signals through a circuit including this buffer capacitor, fifth switches, the third switch, the reference voltage line and the negative potential line. The third switch has at each instant a variable state of conductivity dependent upon the magnitude of the negative potential at that instant. The magnitude of the negative biasing potential is varied in accordance with the variations in the state of conductivity of the third switch to regulate the negative potential at a particular value. The filter capacitor is charged by the negative biasing potential and is discharged to the load when the second and fifth switches are simultaneously open. This occurs for a brief interval every time that the polarity of the clock signal changes. In the drawings: Figure 1 is a circuit diagram schematically illustrating a circuit in the prior art for converting a positive energizing voltage in a CMOS integrated circuit chip into a negative potential for energizing a load; Figure 2 illustrates voltage waveforms at strategic terminals in the circuit shown in Figure 1; Figure 3 is a circuit diagram of one embodiment of the invention for converting a positive energizing voltage in a CMOS integrated circuit chip into a stable and regulated negative potential for energizing a load; Figures 4a and 4b illustrate waveforms of voltages at strategic terminals in the circuit shown in Figure 3 for driving the output of such circuit; and Figures 5a and 5b illustrate waveforms of output voltages at strategic terminals in the embodiment shown in Figure 3. Figure 1 illustrates a circuit which has been used in the prior art to convert a positive energizing voltage in a CMOS integrated circuit chip into a negative potential for energizing a load. The prior art circuit includes a source 10 of clock signals which are illustrated at 12 in Figure 2. The clock signals are introduced to a level shifter 14 which may be constructed in a conventional manner. The level shifter 14 is energized by a positive voltage from a source 16. The level shifter 14 is also connected to a source 20 of a reference potential such as ground. The level shifter 14 is also connected to one terminal of a buffer capacitor 22, the other terminal of which is common with the anode of a diode 24 and the cathode of a diode 26. The cathode of the diode 24 has a common terminal with one terminal of a filter capacitor 28, this terminal being connected to the reference potential such as ground. The anode of the diode 26 has a common terminal with the other terminal of the filter capacitor 28. The filter capacitor 28 has a significantly higher value than the buffer capacitor 22. A load 30 indicated schematically by a resistor is connected across the filter capacitor 28. As previously indicated, the clock signals from the source 10 are indicated at 12 and are represented by alternate half cycles of positive and negative polarities. The positive half cycles may have a positive potential of approximately five volts (5V) and the negative half cycles may be at the reference potential such as ground. This is indicated at 12 in Figure 2. The voltage from the level shifter is indicated at 32 in Figure 2. This voltage charges the buffer capacitor 22 through a circuit including the buffer capacitor and the diode 24 so that a positive potential is produced at the upper terminal of the capacitor. Because of the potential drop such as sixth tenths of a volt (0.6V) across the diode 24, a positive potential is also produced on the lower terminal of the capacitor 22 as indicated at 34 in Figure 2. In the negative half cycles of the clock signal 12, the voltage on the lower terminal of the buffer capacitor becomes negative because of the drop in the voltage across the buffer capacitor. This is indicated at 36 in Figure 2. As will be seen, the upper terminal of the filter capacitor 28 is at ground. The filter capacitor 28 becomes charged during the negative half cycles of the clock signal 12 to produce a negative voltage at its lower terminal. This results from the inclusion of the diode 26, which is back biased to pass the negative voltage 36 on the lower terminal of the buffer capacitor 22 to the lower terminal of the filter capacitor. The negative voltage on the lower terminal of the filter capacitor 28 is accordingly about three and eight tenths volts (3.8V). When the load 30 is relatively small, the filter capacitor 28 discharges to the load. The voltage across the filter capacitor 28 varies slightly as a result of this discharge. This is indicated at 38 in Figure 2. The charge in the filter capacitor 28 becomes replenished at the beginning of each negative half cycle in the clock signal 12 as indicated at 40 in Figure 2. When the load 30 is relatively large, the discharge of the filter capacitor 26 becomes more pronounced. This causes the voltage at the lower terminal of the filter capacitor 28 to vary at a sharper rate than the variation in the voltage 38. This is indicated in broken lines at 44 in Figure 2. Furthermore, the buffer capacitor 22 discharges to the load 30 during the negative half cycles of the clock signal 12 to aid the discharge of the filter capacitor 28. As a result, the voltage on the lower terminal of the buffer capacitor 22 varies during the negative half cycles of the clock signal. This is indicated at 46 in Figure 2. The variations in the voltages at the lower terminal of the buffer capacitor 22 and on the lower terminal of the filter capacitor 28 are not desirable because they affect the voltage across the load 30. Figure 3 illustrates an embodiment of the invention, this embodiment being preferably constructed on a CMOS integrated chip. In this embodiment, level shifters 100 and 102 are provided, each operative in a manner similar to the level shifter 14 of Figure 1. The level shifter 100 is adapted to receive clock signals on a line 104 from a source 106 as indicated at 108 in Figure 4a. These signals may vary in amplitude between + 2.75 volts and -2.25 volts. The level shifter 100 is adapted to produce signals 110 (Figure 4a) on a line 112 (Figure 3), signals 114 (Figure 4a) on a line 116 (Figure 3) and Signals 118 (Figure 4a) on a line 120 (Figure 3). The signals 110 on the line 112 may vary between +5 volts and 0 volts; the signals 114 on the lines 116 may vary between +2.75 volts and -2.25 volts; and the signals 118 on the line 120 may vary between + 2.25 volts and - 2.75 volts. As will be seen, the signals 114 on the line 116 are opposite in phase to the signals 108, 110 and 118 and may be obtained from an invertor (not shown). The clock signals from the source 106 are inverted at 122 and the inverted signals are introduced through a line 124 to the level shifter 102. This is indicated at 126 in Figure 4b. The level shifter 102 is adapted to produce signals 130 (Figure 4b) on a line 132 (Figure 3), signals 134 (Figure 4b) on a line 136 (Figure 3) and signals 138 (Figures 4b) on a line 140 (Figure 3). The signals on the line 112 are introduced to the gate of a transistor 144, which may be of the p type. The source of the transistor 144 receives a suitable positive voltage such as five volts (5V) from a source 146 of positive voltage. The drain of the transistor 144 is connected to the drain of a transistor 148, which is preferably of the n type. The gate of the transistor 148 is common to the line 120. The source of the transistor 148 has a common connection with the drain of a transistor 150, which may be of the n type. The gate of the transistor 150 receives the output from an operational amplifier 152 having input terminals respectively connected to a reference potential such as a ground 154 and to a common terminal between a pair of resistances 156 and 158. The other terminal of the resistance 156 receives a reference voltage from the positive terminal of a source which is schematically illustrated as a battery 160. The second terminal of the battery 160 is common with the reference potential such as the ground 154. The other terminal of the resistance 158 is common with a line 162 which receives a negative biasing potential such as -2.75 volts. The source of the transistor 150 and the drain of a transistor 166 (which may be an n type) receive the reference potential such as ground. The gate of the transistor 166 is connected to receive the signals 114 on the line 116. The source of the transistor 166 is connected to one terminal of a buffer capacitor 168, the other terminal of which is common with the drains of the transistors 144 and 148. The source of the transistor 166 and the drain of a transistor 170 (which may be of the n type) have a common connection. The gate of the transistor 170 receives the signals 118 on the line 120. The source of the transistor 170 is common with the line 162 providing the negative biasing potential. A filter capacitor 172 is connected between the line 162 and the ground 154. A load schematically illustrated as a resistance 174 is connected across the filter capacitor 172. The signals 130 on the line 132 are introduced to the gate of a transistor 176 which may be of the p type. the source of the transistor 176 is energized by the positive voltage from the source 146. The drain of the transistor 176 is common with the drain of a transistor 178, which may be of the n type, and with one terminal of a buffer capacitor 180. The buffer capacitor 180 may have the same value as the capacitor 148. The gate of the transistor 178 receives the signals 138 on the line 140. The source of the transistor 178 is connected to the source of the transistor 148 and the drain of the transistor 150. The drain of a transistor 182 (which may be of the n type) is common with the reference potential such as the ground 154. The gate of the transistor 182 receives the signals 134 on the line 136. Connections are made from the source of the transistor 182 to the drain of a transistor 184, which may be the n-type, and to the second terminal of the buffer capacitor 180. The signals 138 on the line 140 are introduced to the gate of the transistor 184. The source of the transistor 184 is common with the line 162. As previously indicated, Figures 4a and 4b illustrate the waveforms of signals for driving the embodiment shown in Figure 3. Figures 5a and 5b illustrate the waveforms of output voltages in the embodiment shown in Figure 3. The voltage waveform 108 on the line 104 in Figure 4a is repeated in Figure 5a as is the voltage waveform 110 on the line 112. When the voltage waveform 110 on the line 112 is negative, the transistor 144 passes a current. The transistor 166 also passes a current at the same time because of the introduction to the gate of the transistor of the positive voltage 114 on the line 116. This causes the buffer capacitor 168 to be charged through a circuit including the voltage source 146, the transistor 144, the buffer capacitor, the transistor 166 and the ground 154. Similarly, the positive half cycles of the clock signals from the source 106 become inverted by the invertor 122. In these half cycles, the buffer capacitor 180 becomes charged through a circuit including the voltage source 146, the transistor 176, the buffer capacitor and the transistor 182 and the ground 154. In the positive half cycle of the clock signal 108 on the line 104, the signal 118 on the line 120 becomes positive. This causes the transistors 148 and 170 to become conductive. Current accordingly flows through a circuit including the buffer capacitor 168, the transistor 148, the transistor 150, the ground 154, the filter capacitor 172, the line 162 and the transistor 170. The resultant discharge of the buffer capacitor 168 causes a negative potential to be produced on the line 162. The discharge of the buffer capacitor 168 also causes the load 174 to be energized. In like manner, current flows in the negative half of the clock signals from the source 106 through a circuit including the buffer capacitor 180, the transistor 178, the transistor 150, the ground 154, the filter capacitor 172, the line 162 and the transistor 184. The filter capacitor 172 becomes charged during the discharge of the buffer capacitors 168 and 180. The filter capacitor 172 becomes discharged to the load 174 only during the time that both of the transistors 170 and 184 are simultaneously non-conductive. This occurs only in the transitions between the positive half cycles and the negative half cycles of the clock signal 108 from the source 106. As a result, the load is energized primarily by the buffer capacitors 168 and 180 and only secondarily by the filter capacitors 172. This is in contrast to the circuit shown in Figure 1 where the load 30 is energized primarily by the filter capacitor 30 and only secondarily by the buffer capacitor 22. As illustrated at 190 in Figure 5a, the upper terminal of the buffer capacitor 168 is at a potential of +5 volts during the half cycles of the clock signal when the buffer capacitor is being charged from the voltage source 146. During the half cycles of the clock signal when the buffer capacitor 168 is discharging to the load 174, the voltage on the upper terminal of the buffer capacitor progressively decreases toward ground. This is illustrated at 192 in Figure 5a. Although the voltage on the upper terminal of the buffer capacitor 168 progressively decreases toward ground during the discharge of the buffer capacitor, the negative terminal of the buffer capacitor 168 remains substantially constant during the discharge of the buffer capacitor. This is illustrated at 194 in Figure 5a. This is in contrast to the circuit shown in Figure 1. In the circuit shown in Figure 1, the voltage on the lower terminal of the buffer capacitor 22 varies when the load 30 is low. This is illustrated by the broken lines 46 in Figure 2. As will be appreciated, the voltage on the lower terminal of the buffer capacitor 180 also remains constant during the discharge of the buffer capacitor. This is illustrated at 198 in Figure 5b. The transistor 150 regulates the currents through the circuits specified in the previous paragraph, providing for the discharge of the buffer capacitors 168 and 180 to the load. This regulation is provided by adjustments in the bias voltage applied to the gate of the transistor 150 from the output of the operational amplifier 152. The operational amplifier 152 operates to produce the variations in the output voltage by comparing the reference voltage such as the ground 154 and the voltage on the line 162 as adjusted by the voltage dividing network represented by the resistors 156 and 158. By regulating the current through the discharge circuit for the buffer capacitors 168 and 180, the transistor 150 operates to maintain the voltage on the line 162 at a particular magnitude such as -2.75 volts. The circuit shown in Figure 3 and described above has certain important advantages. One advantage is that the circuit provides on the line 162 a negative potential which remains substantially constant regardless of the magnitude of the load 174. This results from the fact that changes in the potential across the buffer capacitances 168 and 180 occur primarily at the upper terminals of the buffer capacitors during the discharge of the buffer capacitors. Another advantage is that the energizing of the load occurs primarily from the buffer capacitors 168 and 180 and only secondarily from the filter capacitor 172. Since the voltage across the filter capacitor 172 remains substantially constant and one of the terminals of the filter capacitor is at ground, this assures that the negative potential on the line 162 will remain substantially at a particular magnitude such as approximately -2.75 volts.	Circuit for converting a positive energizing voltage into a regulated negative voltage for energizing a load (174) comprising: clock-generating means (106) for providing at a particular frequency clock signals having first and second opposite polarities, a first and second buffer capacitor (168, 180), first switching means (144,166) responsive to the clock signals for connecting the first buffer capacitor (186) between a voltage source (140) and a ground potential (154) during the first polarity of the clock signal, second switching means (176,182) responsive to the clock signals for connecting the second buffer capacitor (180) between the voltage source (140) and the ground potential (154) during the second polarity of the clock signals,characterized by a first discharging means (148,170) for discharging the first buffer capacitor (168) to the load (174) and to a filter means (172) being connected in parallel thereto during the second polarity of the clock signals, second discharging means (178,184) for discharging the second buffer capacitor (180) to the filter means (172) and the load (174) during the first polarity of the clock signals and means (152) regulating the discharge current of the first and second buffer capacitors to the filter means (172) and the load (174) during the first and second polarity of the clock signals. Power supply circuit according to claim 1, wherein said first and second discharging means comprise means (150, 152) for regulating the discharge of the first and second buffer capacitors (168, 180) to the load (174) in the alternate half cycles. Power supply circuit according to claim 2, characterized by the filter means (172) being operative to provide a bias voltage, means (146) for providing an energizing voltage, means (154) for providing a reference voltage and the regulating means including means (152) for providing a control voltage in accordance with difference between the bias voltage and the reference voltage and means (150) for varying the discharge of the first and second buffer capacitors (168, 180) to the load (174) in accordance with the variations in the control voltage. Power supply circuit according to one of claims 1 to 3, characterized by the first and second discharging means being operative to discharge the first buffer capacitor (168) in a negative potential to the load (174) during the second polarity of the clock signals and for discharging the second buffer capacitor (180) in a negative potential to the load (174) during the first polarity of the clock signals. Power supply circuit according to one of claims 1 to 4, characterized by said filter means (172) comprising a capacitor having a larger capacitance value than the buffer capacitors (168, 180). Power supply circuit according to one of claims 1 to 5, characterized by the first and second discharging means being operative to discontinue the discharge of each of the first and second buffer capacitor (168, 180) before providing for the discharge of the other one of the first and second buffer capacitors. Power supply circuit according to claim 3, characterized in that the means for providing the control voltage comprise an operational amplifier (152). Power supply circuit according to at least one of claims 1 to 7, wherein said load (174) being connected in parallel to said filter means (172). Power supply circuit according to one of claims 1 to 8, wherein said first and second discharging means (148, 150, 170, 178, 184) constitute switches. Power supply circuit according to at least one of claims 1 to 8, wherein the filter means (172) provide a discharge only in the period between the discharges of the first and second discharging means (148, 150, 170, 178, 184).	BROOKTREE CORP; BROOKTREE CORPORATION	LEWYN LANNY L; LEWYN, LANNY L.
EP-0489418-B1	489,418	EP	B1	EN	20,010,314	1,992	20,100,220	new	B01D69	null	B01D71, C08L77, B01D69, B01D67	B01D 71/56, C08L 77/00+B4P, B01D 69/08, C08L 77/00+B4N6, B01D 71/64, C08L 77/00+B4N4, B01D 69/12, C08L 77/00+B4K	Novel multicomponent fluid separation membranes	A process for preparing multicomponent gas separation membranes is disclosed. The process involves casting two or more solutions of polymer, and partially removing solvent from the side of the cast polymer that is to form the gas separation layer of the membrane. The membrane is then quenched to freeze its structure and then the remainder of the solvent removed to form the gas separation membrane.	FIELD OF THE INVENTIONThe present invention relates to fabrication of composite gas separation membranes.BACKGROUND OF THE INVENTIONThe separation of one or more gases from a complex multicomponent mixture of gases is necessary in a large number of industries. Such separations currently are undertaken commercially by processes such as cryogenics, pressure swing adsorption and membrane separations. In certain types of gas separations, membrane separations have been found to be economically more viable than other processes.In a pressure driven gas membrane separation process, one side of the gas separation membrane is contacted with a complex multicomponent gas mixture and certain of the gases of the mixture permeate through the membrane faster than the other gases. Gas separation membranes thereby allow some gases to permeate through them while serving as a barrier to other gases in a relative sense. The relative gas permeation rate through the membrane is a property of the membrane material composition. It has been suggested in the prior art that the intrinsic membrane material selectivity is a combination of gas diffusion through the membrane, controlled in part by the packing and molecular free volume of the material, and gas solubility within the material. It is highly desirable to form defect free dense separating layers in order to retain high gas selectivity.The preparation of commercially viable gas separation membranes has been greatly simplified with asymmetric membranes. Asymmetric membranes are prepared by the precipitation of polymer solutions in solvent-miscible nonsolvents. Such membranes are typified by a dense separating layer supported on an anisotropic substrate of a graded porosity and are generally prepared in one step. Examples of such membranes and their methods of manufacture are shown in US-A-4,113,628; 4,378,324; 4,460,526; 4,474,662; 4,485,056; and 4,512,893. US-A-4,717,394 shows preparation of asymmetric separation membranes from selected polyimides.A shortcoming of asymmetric gas separation membranes concerns the stability of these membranes under end use environmental conditions because asymmetric membranes are typically composed of homogeneous materials. That is to say, the dense separating layer and the porous substrate layer of the membrane are compositionally the same.For some gas separations, such as acid gas separations, it has been found advantageous in the prior art to employ separating membranes comprising materials which have high intrinsic acid gas solubility. However, asymmetric membranes prepared from materials with high acid gas solubilities tend to plasticize and undergo compaction under acid gas separation end use conditions. In addition, asymmetric membranes may be plasticized and compacted due to components such as water which may be in the gas mixtures to be separated. As a result, asymmetric gas separation membranes prepared from hydrophilic materials may be adversely affected under such conditions.Composite gas separation membranes typically have a dense separating layer on a preformed microporous substrate. The separating layer and the substrate are usually different in composition. Examples of such membranes and their methods of manufacture are shown in US-A-4,664,669; 4,689,267; 4,741,829; 2,947,687; 2,953,502; 3,616,607; 4,714,481; 4,602,922; 2,970,106; 2,960,462; and 4,713,292, as well as in JP-A-63-218213.US-A- discloses hollow fiber composite membranes of a dense, polyorganosilane polymer and an ultra-microporous layer supported on a porous substrate. US-A- and 4,714,481 show hollow fiber composite membranes that include a dense coating of a poly(silylacetylene) on a porous hollow fiber support. US-A-4,741,829 shows bicomponent, melt-spun hollow fiber membranes. US-A-4,826,599 shows forming hollow fiber composite membranes by coating a porous hollow fiber substrate with a solution of membrane forming material, and coagulating the membrane forming material. JP-A-63-218,213, published September 12, 1988, shows coextruding two solutions of polysulfone to form a composite membrane. US-A-2,947,687 shows composite membranes that include a thin layer of ethyl cellulose. US-A-2,953,502 shows thin, nonporous plastic membranes. US-A-2,970,106 shows composite membranes that include modified cellulose acetate-butyrate. US-A-3,616,607 shows dense polyacrylonitrile film onto a nonporous preforms. US-A-4,602,922 shows a polyorganosiloxane layer between a porous substrate and the dense separation layer of a composite membrane. US-A-4,713,292 melt-spun, multi-layer composite hollow fiber membranes. US-A-2,960,462 shows a non-porous selective film laminated onto a thicker, non-porous permeable film.Composite gas separation membranes have evolved to a structure of an ultrathin, dense separating layer supported on an anisotropic, microporous substrate. These composite membrane structures can be prepared by laminating a preformed ultrathin dense separating layer on top of a preformed anisotropic support membrane by a multistep process. Examples of such membranes and their methods of manufacture are shown in US-A- patents 4,689,267; 4,741,829; 2,947,687; 2,953,502; 2,970,106; 4,086,310; 4,132,824; 4,192,824; 4,155,793; and 4,156,597.US-A-4,086,310 shows preparation of composite membranes from supported, ultra-thin, dense polycarbonate. US-A-4,132,824 and 4,192,842 show ultra-thin dense 4-methylpentene film composite membranes. US-A-4,155,793 shows composite membranes that include a ultra-thin, dense film on a porous substrate. US-A-4,156,597 shows a composite membrane that includes an ultra-thin, dense polyetherimide separation layer.Composite gas separation membranes are generally prepared by multistep fabrication processes. Typically, the preparation of composite gas separation membrane requires first forming an anisotropic, porous substrate. This is followed by contacting the substrate with a membrane-forming solution. Examples of such methods are shown in US-A- patent 4,826,599; 3,648,845; and 3,508,994.US-A-3,508,994 shows contacting a porous substrate with a membrane forming solution. US-A-3,648,845 shows coating a porous substrate with a buffer layer followed by solution casting a separating layer of'cellulose acetate. Dip coating a polymer solution onto the substrate also may be employed. Examples of such methods are shown in US-A-4,260,652; 4,440,643; 4,474,858; 4,528,004; 4,714,481; and 4,756,932. US-A-4,260,652 dip coats a polymer onto a substrate. US-A-4,440,643; 4,474,858; and 4,528,004 show composite polyimide membranes formed by coating a substrate. US-A-4,714,481 dipcoats polyacetylene onto a substrate to form a composite membrane. US-A-4,756,932 shows forming composite hollow fiber membranes by dip coating.EP-A-0,390,992 describes an aromatic polyimide double layered hollow filamentary membrane having an excellent heat resistance, chemical resistance, pressure-resistance, and gas-permeating and separating properties and comprising (A) an aromatic imide polymer hollow filamentary microporous inner layer and (B) an aromatic imide polymer tubular filamentary asymmetric outer layer composed of (a) tubular filamentary microporous intermediate layer covering and united with the outside surface of the inner layer (A) and (b) a thin dense outside surface layer covering and united with the intermediate layer (a). There are no compatibility problems because all layers consist in each case of aromatic polyimide.EP-A-0,219,878 describes an asymmetric polyaramide mono layer membrane useful in separating mixtures of gases.Patent Abstracts of Japan, vol. 11, no 193(C-430)(2640) 20. June 1987 & JP-A-62 001 925 (NOK CORP.), 28 January 1987 & WPI/Derwent, AN87-067507, JP-A-62 019 205 describe composite membranes formed from a combination of high molecular polymer without polar groups and high molecular polymer with polar groups, and desirably from a combination of polysulfone and sulfonated polysulfone. The sulfonated polysulfone serves as the gas separation layer while the polysulfone serves as the support. Those bicomponent membranes are used as ultrafiltration membranes for the elimination of trace oil components, microorganisms and other minute particles dispersed in liquids, and other fields where ultrafiltration membranes may be used and where the membrane strength in water is reduced during an ultrafiltration process.The multistep fabrication processes of the prior art tend to be expensive and time consuming. In addition, the composite membranes produced by these multistep processes can experience failure and poor performance due to defects in the substrate and separating layer. A need therefore exists for a membrane and a process of manufacture which avoids the above shortcomings of the prior art membranes and processes.SUMMARY OF THE INVENTIONThe invention provides a process for manufacture of a multicomponent gas separation membrane, comprising providing a solution comprising a film forming polymer I as a first supporting layer, polymer I being selected from the group consisting of polysulfones, polyethersulfones, polyetherimides, polyimides, polyamides, copolymers thereof, and blends thereof,applying to a surface of said first supporting layer a second solution comprising a film forming polymer II to provide a separating layer to form a nascent membrane of at least two layers, wherein polymer I and polymer II are different polymers, and polymer II being selected from the group consisting of polyetherimides, polyimides, polyamides, polyesters, and mixtures thereof, wherein said providing of said first layer and said applying of said second solution is performed by coextruding said first solution and said second solution, coagulating said nascent membrane, anddrying said nascent membrane to form a multicomponent gas separation membrane.The invention provides a multicomponent gas separation membrane prepared by novel process of simultaneously coextruding at least two film forming polymer solutions to form a nascent membrane, followed by precipitation to form a composite multicomponent membrane comprised of a dense or asymmetric gas separating layer and a microporous layer which structurally supports the separating layer. The nascent membrane can be optionally partially dried prior to coagulating of the membrane in a fluid bath. The nascent membrane is quenched and then the remainder of the solvent is removed to form the gas separation membrane. The polymer solutions can be coextruded to form a multicomponent membrane with either of the polymer solutions forming the separating or support portion of the fiber. The multicomponent membrane may be formed into hollow fibers as well as shapes such as films. The multicomponent membranes have at least two components comprising a first layer material for supporting a second, separating layer for separating gases. The second layer can be in the form of an asymmetric membrane which contains a dense gas separating layer on the exterior surface of the membrane.DETAILED DESCRIPTION OF THE INVENTIONThe present invention allows for ease of manufacture of multicomponent gas separation membranes. In manufacture of the membranes, the gas separating layer membrane materials are selected from the group consisting of polyetherimides, polyimides, polyamides, polyesters and mixtures thereof. Preferred materials for the dense gas separating laye include aromatic polyamide and aromatic polyimide compositions.The preferred aromatic polyimides for the gas separating layer have the formula wherein R and R' are selected from the group of and where Z is a carbon-carbon bond, or alkylene groups of 1 to 5 carbon atoms; where Ar is one of either or mixtures thereof where Z', Z'', Z''' independently are a carbon-carbon bond, or alkylene groups of 1 to 5 carbon atoms; X, X1, X2, and X3 independently are hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups; Y, Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9, Y10, Y11, Y12, Y13, Y14, and Y15 independently are X, X1, X2, X3 or halogen, Ar' is or mixtures thereof where Z' has the above-defined meaning, m is 0 to 100 mole percent, preferably 20 to 100%, n is 0 to 100 mole percent, preferably 20 to 80%, and (m + n) = 100%.The preferred aromatic polyamides useful as the dense separating layer have the formula: where R is one of either where Z', Z , Z''' independently are a carbon-carbon bond, or mixtures thereof; Ar is one of either where Z is a carbon-carbon bond, or mixtures thereof, n is an integer such that the polymer is of film forming molecular weight, X, X1, X2, and X3 are independently, hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups; and Y, Y1, Y2, Y3, Y4, Y5, Y6 Y7, Y8, Y9, Y10, Y11, Y12, Y13, Y14, and Y15 independently are X, X1, X2, X3, halogen, or alkyl groups of 1 to 6 carbon atoms.Suitable substrate layer materials for the membranes of the present invention are selected from the group consisting of polysulfones, polyethersulfones, polyetherimides, polyimides, polyamides, copolymeres thereof and blends thereof. The preferred polyethersulfones are aromatic polysulfones of the formula: which is available under the trade name Victrex from ICI Corp.The preferred polyethersulfones have the formula: which are available from Amoco Corp. under the tradename Udel . Other preferred polysulfones have the formula: available from Amoco Corp. under the tradename Radel .The preferred polyetherimides have the formula: available from the General Electric Company under the tradename Ultem .The polymers for both the substrate or gas separating layer have a sufficiently high molecular weight to be film forming.For the purpose of illustrating the invention, we exemplify forming multicomponent membranes with two components, that is, a gas separating component and a substrate component. This should not be considered limiting however, since the multicomponent membranes of the present invention may incorporate more than two component layers. The additional layers may function as gas separating layers, structural layers, substrate layers, layers which reduce environmental concerns, or combinations thereof. These additional layers may contain the materials employed in the gas separating layer and the substrate layer. The materials of each layer are sufficiently compatible to ensure integrity of the composite membrane during processing or when employed in fluid separations such as gas separations.Multicomponent gas separation membranes of the present invention may be in the form of various shapes such as flat membranes or hollow fiber membranes. The membrane is preferably in the form of a hollow fiber due to the surface area advantages available. The flat film membranes are prepared through coextrusion of the polymer solutions for the separating and support layers to form a nascent multilayer membrane. The nascent multilayer membrane is optionally dried under specified conditions and then precipitated in a coagulating bath that is a non-solvent for the film forming polymer but is a solvent of the polymer solvent. Coextrusion may be performed by use of well known multiple slit dies. For example, a bicomponent film membrane can be coextruded through a two-slit die. The nascent bicomponent film membrane can be supported on a plate, continuous roller, or fabric backing. Such a nascent bicomponent film can be optionally dried at from 10`C to 200`C, preferably 25`C to 100`C, for 0.01 to 10 minutes, preferably for 0.05 to 1.0 minutes, by passing the nascent bicomponent film through an oven. The nascent bicomponent film is then precipitated in the coagulating bath.Multicomponent hollow fiber membranes in the form of hollow fibers are formed by coextrusion of the support polymer and separating polymer solutions. For example, polymer solutions for the layers may be coextruded through a multiple channel spinneret while maintaining a gas pressure or a bore fluid in the nascent hollow fiber bore to maintain the fiber's structural integrity. Such multiple channel spinnerets have been described in the prior art for use in melt extrusion of multicomponent fibers.The nascent coextruded hollow fiber membrane optionally may be dried by passing the nascent fiber through an air gap of from 0.1 cm to 6 m, preferably from 0.1 cm to 20 cm, at a temperature of from 10°C to 250°C, preferably from 20°C to 100°C, for a time dependent on the coextrusion rate and the fiber takeup speed, generally between 10-6 to 5 minutes, preferably between 0.001 to 1 minute. The nascent fiber is then drawn into a coagulating bath. The thus formed multicomponent hollow fiber membranes are wound onto a drum or other suitable collection device.During fabrication of the hollow fiber membranes, the separating layer is preferably formed on the outside surface of the fiber to maximize the membrane surface area exposed to the gas. However, the separating layer also may be formed as the inner layer of the fiber. The multicomponent hollow fiber membrane of the present invention may have an outside diameter of about 75 to 1,000 microns, preferably 100 to 350 microns, and a wall thickness of about 25 to 300 microns, preferably 25 to 75 microns. Preferably the diameter of the bore of the fiber is about one-half to three-quarters of the outside diameter of the fiber.The porosity of the resultant membrane is sufficient so that the void volume of the membrane is within the range of 10 to 90 percent, preferably about 30 to 70 percent, based on the volume contained within the gross dimensions of the overall multicomponent membrane.Coextrusion, and the apparatus and processes therein, of polymers is well known in the art. Use of solution coextrusion techniques as in the present invention for the fabrication of multicomponent gas separation membranes wherein the components are of the same polymer type is also known. The optional drying step and the coagulation processes described above also are well known in the prior art for manufacture of monolithic asymmetric membranes. The application of such processes for the fabrication of multicomponent membranes wherein the components are of different polymer types, however, is surprising and novel.In order to select suitable materials for use as the separating layer and/or substrate layer of the multicomponent membranes, a two step process for the fabrication of bicomponent membranes may be employed. This process entails casting a polymer solution onto a glass plate at a specified temperature with a casting knife, for example, a knife gap of 15 mils (3.8 x 10-4m) to form a nascent substrate layer. After drying on the plate for a specified time, the separating layer polymer solution is cast on top of the substrate layer through use of a larger knife gap, for example, a knife gap of 20 mils (5.1 x 10-4m). After drying for a specified time and temperature, the resultant nascent bicomponent film is coagulated in a bath that is a nonsolvent for the polymers but which is a solvent for the solvents of the polymeric solutions employed to form the separating and substrate layers.Selection of the polymer solutions for use in the production of the various layers of the multicomponent membrane may be made depending on, for example, the solubility characteristics of the polymer and the desired end use of the layer. Typically, such polymer solutions are similar to those described in the prior art for asymmetric membranes. The amount of polymer in each solution independently may vary from about 1 to 60 weight percent, preferably 15 to 35 weight percent.Typical solvents for the polymer solutions include solvents such as dimethyl formamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like. These solvents are useful with the preferred polymer materials of the present invention, that is polysulfone, polyethersulfone, polyamide, polyimide and polyetherimide. These solvents, however, are merely illustrative and should not be considered limiting.Mixtures of solvents also may be used in the polymer solutions employed to form the layers of the membrane. The specific mixture of solvents may vary depending on the solubility parameters of the polymer and the desired use of the layer. For example, two or more solvents may be used which vary in volatility or solvation power. Specific examples of polymer solutions which include mixtures of solvents for use with a variety of polymeric materials are exemplified herein.The solvent mixture also may contain additional components such as polymer swelling agents, and nonsolvent components. These added components may be useful, for example, to achieve a desired anisotropy in a layer by moving the polymer solution closer to its point of incipient gelation. These additional components may be characterized as extractable or nonextractable in the coagulation bath. Extractable components, that is, materials which are extractable in an aqueous-based coagulation bath, may be useful, for example, as pore formers in a layer. Examples of extractable components include inorganic salts, and polymers such as polyvinyl pyrrolidone. Nonextractable components may find utility as, for example, membrane permeation modifiers. Nonextractable materials vary in composition dependent on the end use desired for the layer and the composition of the polymer, solvent mixture and coagulation bath. Examples of the additional components which may be employed include, for example, discrete monomeric materials which are insoluble in the composition of the coagulation bath, polymerizable materials such as moisture-curable siloxanes, and compatible or non-compatible polymers. The foregoing examples of additional components are merely illustrative and should not be considered limiting.Suitable coagulation baths for the nascent multicomponent membranes vary depending on the composition of the polymer solutions employed and the results desired. Generally, the coagulation bath is miscible with the solvent of the solvent mixture, but is a non solvent for the polymers of each layer. However, the coagulation bath may be varied to achieve desired properties in the layer. This may be desirable depending on the solubility parameters of the separating layer polymer, or when specialized membrane configurations are desired. For example, the solvent of the separating layer polymer solution may be immiscible in the coagulation bath whereas the solvent of the substrate layer polymer solution may be miscible in the coagulation bath. A coagulation bath therefore may be a multicomponent mixture of water and an organic solvent that is miscible with water and the solvent to be removed from the polymer. The temperature and composition of the bath also may be controlled to affect the extent and rate of coagulation.The Nascent multicomponent membranes can be dried by air drying or other prior art processes. For example, water-wet monolithic asymmetric hollow fiber membranes can be dehydrated by the methods shown in U.S. 4,080,743, U.S. 4,080,744, U.S. 4,120,098, and EPO-219,878.A surprising advantage provided by the present invention is its ability to produce multicomponent membranes of a wide range of compositions and configurations. In the simplest case, the invention can produce bicomponent membranes of a separating layer and a porous substrate layer. The separating layer may be dense or asymmetric. In addition, the present invention offers the advantage of forming separating materials which are otherwise impossible or very difficult to fabricate by prior art techniques into commercially useful membranes. The present invention also surprisingly enables the use of other membrane materials which have not been easily fabricated into useful commercial membranes due to solubility, solution viscosity or other rheological problems.The fabrication processes employed to form the multicomponent membranes of the present invention depend on the major component of the membrane. For example, in manufacture of bicomponent hollow fiber membranes, selection of the spinning parameters depends on the spinnability of the substrate layer solution. This means that bicomponent membranes formed by the present invention readily can be spun essentially under the same conditions as the underlying substrate layer. However, the preferred spinning conditions are selected to optimize the morphology of the separating layer.The multicomponent fiber membranes formed in the present invention possess the superior gas separation properties of the separating layer while maintaining the ease of fabrication of the substrate layer. This ease of fabrication allows for simplified membrane production. For example, one can start by spinning the bicomponent hollow fiber membranes under conditions already established for spinning of the substrate layer. Process modifications then may be made to provide the desired combination of properties for the multicomponent membrane.Another surprising benefit of the present invention is the improved adhesion achieved between the layers of the membrane. A major drawback of prior art composite membranes has been delamination of the dense separating layer from the porous support under end use operating conditions. This shortcoming has been overcome, in part, in the prior art through addition of adhesion promoters between the separating and support layers. This, however, complicates fabrication of these membranes. Surprisingly, the material layers of the present multicomponent membranes do not require the use of adhesion promoters and do not delaminate under end use conditions.The novel membranes of the invention have use in a wide variety of gas separations. For example, the membranes of the present invention are useful for the separation of oxygen from air to provide enriched oxygen to provide enhanced combustion, and for the separation of nitrogen from air to provide inerting systems; in recovery of hydrogen from hydrocarbon gas in refinery and ammonia plants; separation of carbon monoxide from hydrogen in syngas systems; for separation of nitrogen from ammonia; and separation of carbon dioxide or hydrogen sulfide from hydrocarbons.Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. In the following examples, all temperatures are set forth uncorrected in degrees Celsius; unless otherwise indicated, all parts and percentages are by weight. All hollow fiber membranes are tested by flowing the feed gas along the exterior of the fiber. EXAMPLESExample 1An aromatic polyamide is prepared by polycondensation of 1,4-bis(4-aminophenoxy)-2-tertbutylbenzene (122.0g, 0.35 mole) and a mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar), in dimethylacetamide (DMAc) 69.63g, 0.343 mol under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. To the resulting very viscous reaction solution is added lithium hydroxide (25g) and the resulting reaction mixture is stirred overnight at room temperature. The reaction solution is precipitated in water. The resulting solid is collected and washed three times with water, washed twice with methanol, washed once with acetone and allowed to air dry overnight. The resulting light tan solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 110°C overnight to yield 163.5g of polyamide product.Films of the polyamide prepared above are cast from a 15% polymer solution (based on weight) in N,N-dimethylacetamide onto a glass plate treated with Du Pont Teflon® dry lubricant at 90°C ± 2°C with a 15-mil (3.8 x 10-4m) (38.4 x 10-5 m) knife gap. Du Pont Teflon® dry lubricant contains a fluorocarbon telomer which reduces the adhesion of the membrane to the glass plate. After drying on the plate at 90°C ± 2°C for 0.25 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 200°C for 48 hours. The films are tough and flexible and can be creased without cracking.A film, prepared as above which is 1.1 mils (2.8 x 10-5m) thick, is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 483.2 psig (3332kPa), 26.3°C. The results are reported below: O2 Productivity125 centiBarrersO2/N2 Selectivity6.6A centiBarrer is the number of cubic centimeters of gas passed by the membrane at standard temperature and pressure multiplied by the thickness of the membrane in centimeters multiplied by 10-12 divided by the product of the permeating area of the membrane in square centimeters, the time in seconds times for permeation and the partial pressure difference across the membrane in centimeters of Hg, that is, centiBarrer = 10-12 X cm3 (STP) cmcm2 sec cmHgA hollow-fiber composite membrane is prepared from polyether sulfone as the first substrate layer and the above polyamide as the second separating layer. A solution is prepared of 37.5% (weight) VICTREX 600P polyether sulfone (ICI corporation), 15% (weight) polyvinylpyrrolidone (average MW: 10,000, AIDRICH) and 47.5% (weight) DMAC as the solvent. A solution of 20 weight % of the polyamide, 6% (weight) lithium nitrate, 74% DMAc as the solvent is prepared. A third solution of 80% (volume) of DMAC in 20% water is prepared as the bore solution. The hollow fiber spinneret consisted of a needle with dimensions of 16 mils (4.1 x 10-4)m OD and 10 mils (2.5 x 10-4m) ID inserted in an annulus with dimensions of outer diameter of 33 mils (8.4 x 10-4m) and inner diameter of 16 mils (4.1 x 10-4m). The spinneret temperature is maintained at 91°C. The first substrate polymer solution is extruded at a rate of 263 cc/hr through the annulus. The bore of the fiber is maintained by means of supply of the DMAC solution into the needle at a rate of 60 cc/hr. The second separating layer polymer solution is simultaneously applied at a rate of 32 cc/hr over the first substrate polymer solution using the mesa metering technique described in U.S. patent 2,861,319.The spun bicomponent fiber is passed through an air gap length of 8.0 cm at room temperature first into a water coagulation bath followed by a methanol bath. The water bath is at 18°C and the methanol bath is at 18°C. The fiber is wound onto a drum at the rate of 43 meters per minute. The fiber is further washed with methanol and then allowed to air dry.The resulting bicomponent fiber membrane contains about 5% by weight of the polyamide separating layer is treated as taught in U.S. 4,230,463 to seal any defects in the polyamide dense separating layer. Treatment involves contacting the outer surfaces of the fiber with a 5.0% (weight) SYLGARD® 184 solution in FREON® 113 (1,1,2-trichloro-1,2,2-trifluoroethane), decanting the solution and drying the fiber in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. SYLGARD® 184 (Dow Corning Corporation) is an elastomeric silicone material which thermally cures to a crosslinked silicone material.The bicomponent fiber treated as above is tested for pure gas hydrogen and methane permeabilities at 200 psig (1379kPa), 25°C. The results are reported below: H2 Productivity42 GPUH2/CH4 Selectivity315GPU = 10-6 X cm3 (STP) cm2 sec (cmHg)As an alternative treatment to seal defects in the polyamide dense separating layer, the outer surfaces of the fiber can be contacted sequentially with a 0.1% (weight) 2,4,6-diethyltoluene-1,3-diamine (mixture of isomers, a commercial product of Ethyl Corporation) solution in FREON® 113 and a 0.1% (weight) 1,3,5-benzenetricarboxylic acid chloride solution in FREON® 113. After the final solution is decanted, the fiber is dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight.The bicomponent fiber treated as above is tested for pure gas helium and nitrogen permeabilities at 400 psig (2758kPa), 23.0°C. The results are reported below: He Productivity190 GPUHe/N2 Selectivity135The bicomponent fiber treated as above is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 120 psig (827kPa), 28°C. The results are reported below: O2 Productivity26 GPUO2/N2 Selectivity6.6The bicomponent fiber treated as above is tested for mixed gas carbon dioxide/methane (50/50, mole) permeabilities at 250 psig (1723kPa), 25°C. The results are reported below: CO2 Productivity101 GPUCO2/CH4 Selectivity21The bicomponent fiber treated as above is tested for mixed gas hydrogen/methane (50/50, mole) permeabilities at 600 psig (4137kPa), 92°C. The results are reported below: H2 Productivity350 GPUH2/CH4 Selectivity49The foregoing example demonstrates the invention herein. As shown above, a multicomponent, hollow fiber gas separation membrane can be prepared in essentially one step. The multicomponent hollow fiber membrane that is formed combines a gas separating layer, prepared from the separating polymer solution, on the outside surface of an anisotropic substrate membrane prepared from the substrate polymer solution. Although the separating polymer and the substrate polymer may differ compositionally, the multicomponent hollow fiber membrane does not suffer from delamination problems often encountered in the prior art membranes.The foregoing example also illustrates another aspect of the present invention wherein, the separating polymer, although it is the minor component of the membrane, compositionally incorporates the dense gas-separating layer. This is demonstrated by comparing the relative gas separation properties of the separating polymer and the substrate polymer components versus the gas separation properties of the final multicomponent membrane. As shown above, the separating polymer component has a relatively high O2/N2 selectivity of 6.6 whereas the substrate polymer component has a substantially lower O2/N2 selectivity. Surprisingly, the O2/N2 selectivity of the final multicomponent membrane more closely approximates the selectivity of the outer polymer than the selectivity of the substrate polymer layer. The foregoing example also illustrates the variety of gas separations, such as hydrogen separations from hydrocarbons, helium separations, air separations and carbon dioxide separations from hydrocarbon streams, in which the present multicomponent membranes find utility.Example 2To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (372.8g, 1 mol) in N,N-dimethylacetamide (2600 ml) is dropwise added melted isophthaloyl dichloride (204.0g, 1.005 mol) under an inert atmosphere. The reaction temperature is maintained at under 52°C by control of the addition rate. The resulting very viscous solution is stirred for 4 hours at 50°C and then lithium hydroxide (88.14g, 3.7 mol) is added. The resulting reaction mixture is allowed to cool to room temperature and stirred overnight. The reaction solution is diluted with N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed twice with water and twice with methanol. After air-drying overnight, the solid is dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours and at 250°C for 4 hours to yield 506.7g product.The polyamide prepared above is found to be soluble in dimethylsulfoxide, m-cresol, N,N-dimethylacetamide and N-methylpyrrolidone. Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (38.4 x 10-5 m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from a dense separating layer of the polyamide prepared above on top of a substrate of VICTREX 600P polyether sulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000, based on polymer weight) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C ± 3°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polyamide prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the polyethersulfone at 100°C ± 3°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the time noted below, the membrane layers are co-coagulated in a water bath at 27°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit excellent adhesion between the component layers. The only distinction between the layers is coloration. The top polyamide layer is light tan while the polyethersulfone substrate layer is white.The membrane fabrication procedure employed above demonstrates the applicability of the simplified sequential casting process for the rapid assessment of the utility of materials for multicomponent membranes.Example 3To a stirred solution of 4,4'-[1,4-phenylenebis(1-methylethylidene)] bisaniline (50g, 0.145 mol) and pyridine (27.6g, 0.349 mol) in N-methylpyrrolidone (1 L) at room temperature under an atmosphere of nitrogen is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (70:30, mol, 29.51g, 0.145 mol). The reaction temperature is controlled at ≤40°C by the rate of addition. After the final addition, the reaction mixture is warmed to 50°C for 2 hours. The viscous golden-yellow solution is precipitated in water and the resulting solid is washed four times with 3 L water and twice with 2 L methanol. The white solid is air dried and then dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature for 4 hours and at 150°C for 4 hours to give 66.0g product.Differential Scanning Calorimetry (DSC) is performed on the polymer using a Du Pont Thermal Analyzer Model 990 with a Du Pont cell, baseline scope = 50 in a nitrogen atmosphere at a 10°C/minute progress rate. A transition is observed with an onset at 259.6°C, midpoint at 264.7°C, and an end at 269.8°C.Thermogravimetric Analysis (TGA) is performed on the polymer using a Du Pont Thermogravimetric Analyzer Model 99 with a Du Pont cell in an air atmosphere at 10°C/minute progress rate. A 5% weight loss is observed at 400°C and a 40% weight loss is observed at 550°C.Films are cast from a 15% polymer solution (weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 85°C with a 15 mil (3.8 x 10-4m) knife gap. The films are dried on the plate at 85°C for 35 minutes, cooled to room temperature and dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 h.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyether sulfone (a product of ICI). A 25% VICTREX polyether sulfone solution (based on a weight) with 7.5% polyvinylpyrrolidone (M.W. 10,000, based on weight) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the polyethersulfone substrate at 100°C with a 20-mil knife gap. After drying at 100°C ± 3°C for the time noted below, the membranes are coagulated in a water bath at 27°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit excellent adhesion between the component layers.The membrane fabrication procedure shown above demonstrates the applicability of the materials described therein for gas separation membranes.Example 4An aromatic polyamide is prepared by polycondensation reaction of (344 grams, 1 mol) 4,4'-[1,4-phenylenebis(1-methylethylidene)] bisaniline and a mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 203.02g, 1 mol) under an inert atmosphere in N-methylpyrrolidone. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous, clear, tan solution is stirred for 2.5 hours after the final addition. To the stirred reaction solution is added lithium hydroxide monohydrate (92.31g, 2.2 mol) and the resulting reaction mixture is stirred overnight at room temperature. The reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting white solid is collected, washed twice with water, washed twice with methanol and air-dried overnight. The solid is then further dried in a vacuum oven at 20 inches (0.51m) mercury and 120'C for 6 hours to yield 497.7g product.A separating polymer solution is prepared with 25% (weight) solids of the polyamide prepared above and 7.5% (weight) of lithium nitrate in 67.5 weight percent N,N-dimethylacetamide. A substrate polymer solution is prepared with 37.5% (weight) UDEL polysulfone (a product of Amoco Corporation) and 3.8% (weight) formamide in 58.7% by weight of N,N-dimethylacetamide. The first substrate solution is supplied at a rate of 140 cc/hour and the second separating layer is supplied at the rate of 16 cc/hour. The needle of the spinneret has a 2.5 x 10-4m outer diameter and 1.1 x 10-4m inner diameter, and an annulus of 5.59 x 10-4m outer diameter. A solution of 80% (weight) N,N-dimethylacetamide in water is injected into the fiber bore at a rate of 67.5 cc/hour. The spinneret temperature is 115`C. The spun bicomponent fiber is passed through an air gap length of 5.0 cm at room temperature into an aqueous coagulation bath at 18`C. The fiber is wound onto a cylindrical drum at 100 m/minute. The fiber is further washed with water and then allowed to air dry.A fiber made in accordance with the above procedure, and that contains about 10% by weight of polyamide separation layer, is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 21`C. The results are reported below: O2 Productivity19 GPUO2/N2 Selectivity5.1Example 5An aromatic polyimide is prepared by polycondensation of a mixture of 2,3,5,6-tetramethyl-1,4-phenylene diamine and 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline with 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)-ethylidene]-1,3-isobenzofurandione (135.86g, 0.306 mol) under an inert atmosphere at room temperature. The reaction solution became a very viscous light yellow solution. After the clear viscous yellow solution had stirred for 1.5 hours at room temperature, a solution of acetic anhydride (122.5g, 1.2 mol) and triethylamine (121.4g, 1.2 mol) is added with rapid stirring at room temperature. The solution immediately turned yellow-orange with some white solid precipitating out of solution and then slowly redissolving. After stirring for 65 hours at room temperature, the resulting very dark red viscous solution is precipitated in methanol. The resulting off white solid is collected and washed with methanol and allowed to air dry. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight, at 100°C for 4 hours and at 200°C for 4 hours to yield 178.5g product.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 85°C ± 2°C with a 15-mil (3.8 x 10-4m) (38.4 x 10-5m) knife gap. After drying on the plate at 85`C ± 2`C for 20 minutes, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches mercury and 120`C for 4 hours. The films are tough and flexible and can be creased without cracking.A 1.2 mil (3.5 x 10-5m) thick film, is tested for mixed gas oxygen/nitrogen (21/79,mole) permeabilities at 502 psig (3.46 x 106 Pa), 25`C. The results are reported below: O2 Productivity4000 centiBarrersO2/N2 Selectivity3.7A separating polymer solution is prepared with 25% (weight) solids of the polyimide prepared as above in N,N-dimethylacetamide. A substrate polymer solution is prepared with 37.5% (weight) solids VICTREX 600P polyether sulfone and 15.0% polyvinylpyrrolidone (M.W. = 10,000) in N,N-dimethylacetamide. Hollow fiber membranes are prepared by extruding the above polymer solutions through a hollow fiber spinneret as described in Example 1. The separating polymer solution is extruded at a rate of 48 cc/hour and the substrate solution is extruded at a rate of 140 cc/hour. A bore fluid of a solution of 80% (volume) N,N-dimethylacetamide in water is injected into the fiber bore at a rate of 72 cc/hour. The spinneret temperature is 60`C. The spun bicomponent fiber is passed through an air gap length of 8.0 cm at room temperature into an aqueous coagulation bath at 23`C. The fiber is wound up on a drum at the rate of 34 meters per minute. The fiber is further washed in water and then allowed to air dry. The fiber membrane is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity43 GPUO2/N2 Selectivity3.5Example 6A bicomponent fiber membrane is prepared as in Example 5 except the aqueous coagulation bath temperature is 36°C. The fiber is then treated as in Example 5.The fiber membrane is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity40 GPUO2/N2 Selectivity3.0Example 7A bicomponent fiber membrane is prepared as in Example 5 except the aqueous coagulation bath temperature is 15°C and the fiber is wound up on the drum at a rate of 35 meters per minute. The fiber is then treated as in Example 5.The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity43 GPUO2/N2 Selectivity3.5Example 8A bicomponent fiber membrane is prepared as in Example 5 except the separating polymer solution is extruded at the rate of 24 cc/hour and the bore fluid is injected at a rate of 68 cc/hour. Further, the water-wet fiber is washed for 2 hours in methanol and then washed in pentane for 2 hours. The fiber then is allowed to air dry. The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25`C. The results are reported below: O2 Productivity260 GPUO2/N2 Selectivity2.8Example 9A bicomponent fiber membrane is prepared as in Example 5 except for the following changes. The separating polymer solution is extruded at a rate of 24 cc/hour and the bore fluid is injected at a rate of 68 cc/hour. The aqueous coagulation bath temperature is 14'C. Further, the water-wet fiber is washed for 2 hours in methanol and then washed for 2 hours in pentane. The fiber is then allowed to air dry.The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25`C. The results are reported below: O2 Productivity200 GPUO2/N2 Selectivity3.0Example 10The same separating polymer solution, substrate polymer solution, and bore fluid compositions are used as described in Example 5. Further, the same spinneret design is used as in Example 5. The separating polymer solution is extruded at a rate of 32 cc/hour and the substrate solution is extruded at a rate of 263 cc/hour. The bore fluid is injected into the fiber bore at a rate of 80 cc/hour. The spinneret temperature is 60`C. The spun bicomponent fiber is passed through an air gap length of 5.0 cm at room temperature into an aqueous coagulation bath at 13`C. The fiber is wound up on a drum at the rate of 50 meters per minute. The water-wet fiber is consecutively washed in methanol and pentane and then allowed to air dry. The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25'C. The results are reported below: O2 Productivity330 GPUO2/N2 Selectivity2.5Example 11Bicomponent fiber membranes are prepared as in Example 10 except the separating polymer solution is extruded at a rate of 15 cc/hour and the aqueous coagulation bath temperature is 6'C. The fiber is treated as in Example 9.The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25`C. The results are reported below: O2 Productivity120 GPUO2/N2 Selectivity3.2Example 12The same separating polymer solution, substrate polymer solution, and bore fluid compositions are used as described in Example 5. Further, the same spinneret design is used as in Example 5. The separating polymer solution is extruded at a rate of 40 cc/hour and the substrate solution is extruded at a rate of 350 cc/hour. The bore fluid is injected into the fiber bore at a rate of 120 cc/hour. The spinneret temperature is 90`C. The spun bicomponent fiber is passed through an air gap length of 8.0 cm at room temperature into a quench bath composed of 20% (weight) N,N-dimethylacetamide in water at 10`C. The fiber is wound up on a drum at the rate of 56 meters per minute. The water-wet fiber is consecutively washed in methanol and pentane and then allowed to air dry. The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity215 GPUO2/N2 Selectivity3.0Example 13Bicomponent fiber membranes are prepared as in Example 12 except the separating polymer solution is extruded at a rate of 20 cc/hour. The fiber is then treated as in Example 12.The fiber is tested for mixed gas oxygen/nitrogen (21/79,mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity140 GPUO2 Selectivity3.4 and O2 Productivity170 GPUO2/N2 Selectivity3.3Example 14A polyimide is prepared through the polycondensation of 2,4,6-trimethyl-1,3-phenylene diamine with 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl) ethylidene]-1,3-isobenzofurandione. A process for the preparation of this polyimide is taught in U.S. 4,705,540 and is incorporated herein by reference. Dense film gas permeation properties of the polyimide are also disclosed therein.A polyamide is prepared through the polycondensation of 2,4,6-diethyltoluene-1,3-diamine (a mixture of isomers, a commercial product of the Ethyl Corporation) and a 7:3 molar mixture of isophthaloyl dichloride: terephthaloyl dichloride. The process for the preparation of this polyamide is similar to such processes as described in European Patent Number 219,878. A separating polymer solution is prepared with 24% (weight) solids of the polyimide prepared as above and 7.2% (weight) lithium nitrate in N,N-dimethylacetamide. A substrate polymer solution is prepared with 27% (weight) solids of the polyamide prepared as above and 8.1%. (weight) lithium nitrate in N,N-dimethylacetamide. The above polymer solutions are extruded through a hollow fiber spinneret with fiber channel dimensions as set forth in Example 1. The separating polymer solution is extruded at a rate of 22 cc/hour and the substrate solution is extruded at a rate of 100 cc/hour. A solution of 70% (volume) N,N-dimethylacetamide in water is injected into the fiber bore at a rate of 40 cc/hour. The spinneret temperature is 80°C. The spun bicomponent fiber is passed through an air gap length of 6.0 cm at room temperature into a coagulation bath composed of a 1:1 water:methanol (weight) solution at 20°C. The fiber is wound up on a drum at the rate of 34 meters per minute. The fiber is further washed in methanol and then allowed to air dry.The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 26°C. The results are reported below: O2 Productivity44 GPUO2/N2 Selectivity2.5Example 15A bicomponent fiber membrane is prepared as in Example 14 with the following changes. The separating polymer solution is extruded at a rate of 12 cc/hour. The spinneret temperature is 75°C. The spun bicomponent fiber is passed through an air gap length of 7.0 cm at room temperature into the previous coagulation bath and wound onto a drum at the rate of 20 meters per minute. The fiber is treated as before in Example 14.The fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 26`C. The results are reported below: O2 Productivity68 GPUO2/N2 Selectivity2.4Example 16A bicomponent fiber membrane is prepared as in Example 14 with the following changes. The separating polymer solution is extruded at a rate of 12 cc/hour. The spinneret temperature is 71`C. The spun bicomponent fiber is passed through an air gap length of 8.0 cm at room temperature into an aqueous coagulation bath at 25`C. The fiber is wound up on a drum at the rate of 30 meters per minute. The fiber is further washed with water and then allowed to air dry.The bicomponent fiber is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25`C. The results are reported below: O2 Productivity25 GPUO2/N2 Selectivity4.2Example 17Multicomponent membranes are prepared from the polyimide prepared in Example 14 on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyether sulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 110`C. After drying on the plate for 0.5 minutes at 100'C, a 24% polymer solution (based on weight) of the polyimide prepared in Example 14 in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-5m) knife gap. After drying at 100 ± 3°C for the time noted below, the membranes are coagulated in a water bath at 27°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. The water-wet membranes exhibit adhesion between the layers which ranges from poor to good.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit poor to moderate adhesion between the component layers. The dry membranes curled slightly and the layers can be pulled apart.The membrane prepared above which had a dry time of 1.00 minute is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported below: He Productivity150 GPUHe/N2 Selectivity4.6This example demonstrates the importance in matching of the properties of the materials employed to form the present multicomponent membranes. The poor to moderate adhesion found in this example is possibly due to the greater hydrophilicity of the polyimide material which forms the separating layer over the polyether sulfone substrate material. Greater adhesion of this polyimide separating material is found when the substrate material is matched more closely as in Examples 14, 15, and 16. Examples 18-21Bicomponent membranes are prepared from ULTEM®1000 polyetherimide (a commercial product of G. E. Corporation) on top of VICTREX 600P polyethersulfone. ULTEM®1000 is believed to have the structure shown below: A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C for 0.5 minutes, a 22% ULTEM 1000 polyetherimide solution (weight) in N-methylpyrrolidone is cast on top of the above nascent film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C for the time noted in Table 1, the membranes are coagulated in a water bath at 19°C. The water-wet membranes exhibit good adhesion between the layers. ExampleDry Time (min)Treated MembranesPHe (GPU)PHe/PN2180.59336191.090113202.02255213.06310The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers.The bicomponent membranes prepared as above are treated as taught in U.S. 4,230,463 to seal defects in the polyetherimide dense separating layer. This involves contacting the membrane with a 5.0% (weight) SYLGARD 184 (available from Dow Corning Corp.) solution in cyclohexane, removing the membrane from the solution and drying the membrane in a vacuum oven (20 inches mercury) at 55°C ± 5°C overnight.The bicomponent membranes, treated as above, are tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported in Table 1.Example 22Bicomponent membranes are prepared from ULTEM 1000 polyetherimide (a commercial product of G. E. Corporation) on top of VICTREX 600P polyethersulfone. A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate at 100°C for 0.5 minutes, a 24% ULTEM 1000 polyetherimide (weight) solution in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C for 0.5 minutes, the membranes are coagulated in a water bath at 13°C. The water wet membranes exhibit good adhesion between the layers.The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours, and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers.The bicomponent membranes prepared as above are treated as taught in U.S. 4,230,463 to seal defects in the polyetherimide dense separating layer. This involves contacting the membrane with a 5.0% (weight) SYLGARD 184 solution in cyclohexane, removing the membrane from the solution and drying the membrane in a vacuum oven at 20 inches (0.51m) mercury and 55°C ± 5°C overnight.A bicomponent membrane treated as above is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported below: He Productivity117 GPUHe/N2 Selectivity195This bicomponent membrane is further tested for mixed gas oxygen/ nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 23°C. The results are reported below: O2 Productivity7 GPUO2/N2 Selectivity4.5Example 23To a stirred solution of bis[4-(4-aminophenoxy)phenyl]sulfone (49.71g, 0.115 mol) in pyridine (70 ml) and N,N-dimethylacetamide (350 ml) is dropwise added melted isophthaloyl dichloride (23.26g, 0.115 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting reaction solution is stirred for 3 hours after the final addition and then lithium hydroxide monohydrate (10.0g, 0.24 mol) is added. The resulting reaction mixture is stirred overnight at room temperature and then precipitated in methanol. The resulting solid is soaked in water overnight, washed with water, washed twice with methanol, and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 6 hours to yield 67.0g of polymer product.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil knife gap. After drying at 100°C for 0.05 minutes, the membranes are coagulated in a water bath at 13°C. The water-wet membranes exhibit good adhesion between the layers.The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers.The bicomponent membranes prepared as above are treated as taught in U.S. 4,230,463 to seal defects in the polyamide dense separating layer. This involves contacting the membrane with 5.0% (weight) SYLGARD 184 solution in cyclohexane, removing the membrane from the solution and drying the membrane in a vacuum oven at 20 inches (0.51m) mercury and 55°C ± 5°C overnight.A membrane treated as above is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported below: He Productivity77 GPUHe/N2 Selectivity64Example 24To a stirred solution of 2,2-bis[4-(4-aminophenoxy)phenyl]propane dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 20.3g, 0.10 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. After the very viscous, golden reaction solution had stirred for 4 hours, lithium hydroxide monohydrate (10.49g, 0.25 mol) is added and the resulting reaction mixture is allowed to stir overnight at room temperature. The reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed 3 times with water, washed 3 times with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 6 hours to yield 50.9g of polymer product. The polymer prepared above is found to be soluble in m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above with 6.8% lithium nitrate in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for 0.50 minute, the membranes are coagulated in a water bath at 27°C ± 1°C. All water-wet membranes exhibit very good adhesion between the layers.The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers.The procedure of this example demonstrates the applicability of the materials described therein for for fabrication into gas separation membranes. Example 25To a stirred solution of 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (50.0g, 0.145 mol) in pyridine (27.6g, 0.35 mol) and N-methylpyrrolidone (600 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 29.51g, 0.145 mol) under an inert atmosphere. The reaction temperature is maintained under 50°C by control of the addition rate. The resulting viscous solution is stirred at 53°C ± 4°C for 1 hour and then precipitated in water. The resulting white solid is collected and washed four times with water, washed twice with methanol, and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 150°C for 4 hours to yield 66.9g of polymer product.Films of the polymer prepared above are cast from 10% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 85°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 85°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Films are cast from a 15% polymer solution (weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 80°C with a 15-mil (3.8 x 10-4m) knife gap. The films are dried on the plate at 80°C for 30 minutes, cooled to room temperature and dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above with 6.8% lithium nitrate in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 15°C ± 1°C. Two membranes are prepared with dry times of 0.05 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers. The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers. The procedure employed in this example demonstrates the applicability of the materials described therein for fabrication into gas separation membranes. Example 26To a stirred solution of 4,4'-methylene-bis(3-chloro-2,6-diethylaniline) (37.94g, 0.10 mol) and 1,4-bis(4-aminophenoxy)biphenyl (37.28g, 0.10 mol) in N-methylpyrrolidone (350 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 40.69g, 0.20 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous light brown solution is stirred for 4.5 hours and then lithium hydroxide monohydrate (21g, 0.5 mol) is added. The resulting reaction mixture is stirred at room temperature overnight. After dilution with additional N-methylpyrrolidone, the reaction solution is precipitated in water. The resulting solid is collected and soaked in water overnight, washed three times with water, washed three times with methanol and allowed to air dry overnight. The polymer is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 6 hours to yield 106.2g product. The polymer prepared above is soluble in dimethyl sulfoxide, m-cresol, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above with 6.8% (weight, based on polymer) lithium nitrate in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 23°C ± 2°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers. The procedure of this example demonstrates the applicability of the materials described therein for fabrication into gas separation membranes.Example 27To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.4g, 0.50 mol) and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (172.0g, 0.50 mol) in N-methylpyrrolidone (2,600 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 203.0g, 1.0 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous solution is stirred 2.0 hours at 42°C and then lithium hydroxide monohydrate (92.3g, 2.2 mol) is added. The resulting reaction mixture is stirred at room temperature overnight and then precipitated in water. The resulting solid is collected, washed twice with water, washed twice with methanol and air-dried overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 7 hours to yield 502.6g product. The polymer prepared above is soluble in dimethylsulfoxide, m-cresol, N,N-dimethyl acetamide, and N-methylpyrrolidone.Films of the polymer prepared above are cast from 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) (38.4 x 10-5 m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 27°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. All water-wet membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit excellent adhesion between the layers.The procedure of this example demonstrates the applicability of the materials described therein for fabrication into gas separation membranes.Example 28To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.4g, 0.50 mol) and (4-aminophenyl) ether (100.12g, 0.50 mol) in N,N-dimethylacetamide (2,600 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 203.02g, 1.0 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous solution is stirred 1.75 hours at 50°C and then lithium hydroxide (88.14, 3.7 mol) is added. The resulting reaction mixture is stirred at room temperature overnight and then precipitated in water. The resulting solid is collected, washed twice with water, washed twice with methanol and air-dried overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours to yield 424.2g of polymer product. The polymer prepared above is soluble in dimethyl sulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from 10% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 20-mil (5.1 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above with 6.8% (weight) lithium nitrate in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 26°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting bicomponent membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The dry bicomponent membranes exhibit good adhesion between the layers.The procedure of this example demonstrates the applicability of the materials described therein for fabrication into such gas separation membranes.Example 29To a stirred solution of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (41.0g, 0.10 mol) in N-methylpyrrolidone (350 ml) is added 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis-1,3-isobenzofurandione (44.84g, 0.101 mol) under an inert atmosphere at room temperature. The reaction became very viscous and is allowed to stir overnight at room temperature. A solution of acetic anhydride (40.84g, 0.40 mol) and triethylamine (40.48g, 0.40 mol) in N-methylpyrrolidone (200 ml) is added with rapid stirring at room temperature. After stirring over the weekend (48 hours) at room temperature, the very viscous reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed twice with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 145°C for 4 hours and at 225°C for 3 hours to yield 88.6g product. The polymer prepared above is soluble in dichloromethane, m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) (38.4 x 10-5m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 97.5°C ± 3°C. After drying on the plate for 0.5 minutes at 97.5°C ± 3°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 97.5°C ± 3°C with a 20-mil knife gap. After drying at 97.5°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 27°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting membranes are washed-in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit excellent adhesion between the layers.The bicomponent membrane which is dried 0.5 minutes is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported below: He Productivity168 GPUHe/N2 Selectivity17.3The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Examples 30-37To a stirred solution of 2,7-bis(4-aminophenoxy)naphthalene (25.00g, 0.073 mol) in N-methylpyrrolidone (200 ml) is added 5,5'-[2,2,2-trifluoro-l(trifluoromethyl)ethylidene]-bis-1,3-isobenzofurandione (32.78g, 0.74 mol) under an inert atmosphere at room temperature. The very viscous golden-brown reaction solution is stirred overnight at room temperature. A solution of acetic anhydride (29.85g, 0.29 mol) and triethylamine (29.58g, 0.29 mol) is added with rapid stirring at room temperature. After stirring for 2 hours at room temperature, the very viscous reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed three times with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven (20 inches mercury) at 120°C for 4 hours and at 250°C for 4 hours. The polymer prepared above is soluble in dichloromethane, dimethylsulfoxide, meta-cresol, N,N-dimethylacetamide, and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.A film, prepared as above which is 1.30 mils (3.3 x 10-5m) thick, is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 491.2 psig (3.39 x 106 Pa), 22.8°C. The results are reported below: O2 Productivity140 centiBarrersO2/N2 Selectivity5.5Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based.on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C for the times noted in Table 2, the membranes are coagulated in a water bath at 25°C ± 1°C. All membranes exhibit excellent adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit excellent adhesion between layers.The membranes are tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The results are reported in Table 2. ExampleDry Time (min)PHe (GPU)PHe/PN2300.055703.2310.505807.6321.006308.5332.002206.4343.001007.3354.0016010.3364.505011.7375.003035.3The bicomponent membranes prepared as above are treated as taught in U.S. 4,230,463 to seal defects in the polyimide dense separating layer. This involves contacting the membrane with a 5.0% (weight) SYLGARD 184 solution in cyclohexane, removing the membrane from the solution and drying the membrane in a vacuum oven (20 inches mercury at 55°C ± 5°C overnight. The treated bicomponent membrane of Example 31 is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 24°C. The treated bicomponent membrane of Example 32 is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 23°C. The treated bicomponent membrane of Example 35 is tested for pure gas carbon dioxide permeability at 100 psig (689kPa), 25°C. The results are reported in Table 3. ExamplePHe (GPU)PHe/PN2PO2 (GPU)PO2/PN2PCO2 (GPU)PCO2/PN2318622321393419.44.63581512415The procedure of this example demonstrates the applicability of the materials described therein for fabrication into gas separation membranes.Example 38To a stirred solution of 4,4'-methylene-bis(2,6-diisopropyl aniline) (55.0g, 0.15 mol) and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (17.2g, 0.05 mol) in N-methylpyrrolidone (400 ml) is added 3,3',4,4'-benzophenonetetracarboxylic dianhydride (65.1g, 0.202 mol) under an inert atmosphere at room temperature. The dark, viscous solution is stirred overnight at room temperature. A solution of acetic anhydride (75.5 ml, 0.80 mol) and triethylamine (111.5 ml, 0.80 mol) is added with rapid stirring at room temperature. After stirring for 7 hours at room temperature, the viscous, orange reaction solution is precipitated in water. The resulting solid is washed three times with water and two times with methanol. The polymer is air-dried overnight and then dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours and at 250°C for 4 hours to yield 134.8g of polymer product.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 25°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. All membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight at at 100°C for 4 hours. All dry membranes exhibit good adhesion between the component layers.The procedure of this example demonstrates the applicability of the materials described therein for fabrication into gas separation membranes.Example 39A stirred solution of 4,4'-[1,4-phenylenebis(1-methylethylidene)] bisaniline (68.8g, 0.20 mol), 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl) ethylidene]-bis-1,3-isobenzofurandione (97.2g, 0.2025 mol) and N-methylpyrrolidone (900 ml) is slowly heated to reflux under an inert atmosphere while collecting distillates. After heating at reflux for 4 hours, a total of 346 ml distillate is collected. The viscous reaction solution is cooled to room temperature, diluted with N-methyl pyrrolidone, and precipitated in water. The resulting solid is collected and washed twice with methanol. After air-drying overnight, the solid is dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 3 hours and at 210°C for 4 hours to yield 139.4g of polymer product.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking. Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinyl pyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 28°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute, and 1.00 minute, as described above. All membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight at 100°C for 4 hours. All dry membranes exhibit good adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes. Examples 40-46To a stirred solution of 1,4-bis(4-aminophenoxy)benzene (116.8g, 0.4 mol) in N-methylpyrrolidone (1000 ml) is added 5,5'-[2,2,2-trifluoro-l(trifluoromethyl)ethylidene]-bis-1,3-isobenzofurandione (179.38g, 0.404 mol) under an inert atmosphere at room temperature. The gold-colored reaction solution became very viscous and is allowed to stir overnight at room temperature. A solution of acetic anhydride (163.34g, 1.6 mol) and triethylamine (161.90g, 1.6 mol) is added with rapid stirring at room temperature. After mixing over the weekend at room temperature, the very viscous reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed three times with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 130°C for 5 hours an at 240°C for 3 hours to yield 278.06g product. The polymer prepared above is found to be soluble in dimethylsulfoxide, meta-cresol, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C for the times noted in Table 4, the membranes are coagulated in a water bath at 24°C ± 1°C. All membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperatures overnight at 100°C for 4 hours. All dry membranes exhibit good adhesion between the component layers.The membranes prepared as above are tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 25°C. The results are reported in Table 4. ExampleDry Time (min)PHe (GPU)PHe/PN2400.054683.6410.506752.6421.005423.8432.003397.9443.003022.8454.001733.7464.505763.3Example 46 is further tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 25°C. The results are reported below: O2 Productivity8 GPUO2/N2 Selectivity3.2The bicomponent membranes of Examples 42, 43, and 44 prepared as above are treated as taught in U.S. 4,230,463 to seal defects in the polyimide dense separating layer. This involves contacting the membrane with 5.0% (weight) SYLGARD 184 solution in cyclohexane, removing the membrane from said solution and drying the membrane in a vacuum oven at 20 inches (0.51m) mercury and 55°C ± 5°C overnight. The treated bicomponent membrane of Example 42 is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 23°C. The results are reported below: He Productivity141 GPUHe/N2 Selectivity78.3The treated bicomponent membrane of Example 43 is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 23°C. The results are reported below: He Productivity98 GPUHe/N2 Selectivity54The treated bicomponent membrane of Example 45 is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 23°C. The results are reported below: He Productivity66 GPUHe/N2 Selectivity39The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 47To a stirred solution of 4,4'-bis(4-aminophenoxy)biphenyl (25.0g, 0.068 mol) in N-methylpyrrolidone (200 ml) is added 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-isobenzofurandione (30.45g, 0.069 mol) under an inert atmosphere at room temperature. The reaction became very viscous and additional N-methylpyrrolidone (200 ml) is added. After stirring overnight at room temperature, a solution of acetic anhydride (27.70g, 0.27 mol) and triethylamine (27.4g, 0.27 mol) is added with rapid stirring at room temperature. After stirring at room temperature for 2.5 hours, the reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and washed three times with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours and at 250°C for 3 hours to yield 40.8g product. The polymer prepared above is found to be soluble in dichloromethane, m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 95°C. After drying on the plate for 0.5 minutes at 95°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 95°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 95°C for four seconds, the membrane is coagulated in a water bath at 18°C. The membrane exhibits good adhesion between the polymer layers.The resulting membrane is washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membrane is dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours.Example 47 is tested for pure gas helium and nitrogen permeabilities at 100 psig (689kPa), 25°C. Results are reported in Table 5. ExampleDry Time (min)PHe (GPU)PHe/PN2470.0641317Example 48To a stirred solution of 4,4'-(methylethylidene)bisaniline-A (45.2g, 0.20 mol) in N-methylpyrrolidone (350 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 40.69g, 0.20 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting reaction solution is stirred for 4 hours. To the resulting very viscous reaction solution is added lithium hydroxide monohydrate (20.98g, 0.5 mol) and the resulting reaction mixture is mixed overnight at room temperature. The reaction solution is diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is collected and soaked in water overnight, washed three times with water, washed three times with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 6 hours to yield 76.0g product. The polymer prepared above is found to be soluble in dimethylsulfoxide, N-methylpyrrolidone, m-cresol, and dimethylacetamide.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) (38.4 x 10 m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (based on weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the time noted below, the membranes are coagulated in a water bath at 27°C ± 1°C Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the polymer layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit excellent adhesion between layers.The membrane fabrication procedure of this example demonstrates the applicability of the material described therein for gas separation membranes.Example 49To a stirred solution of 3,4'-aminophenylether (20.02g, 0.10 mol) in N-methylpyrrolidone (200 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3,molar, 20.50g, 0.101 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous gold solution is stirred for 6.0 hours and then lithium hydroxide monohydrate (10.5g, 0.25 mol) is added. The resulting reaction mixture is stirred overnight and then diluted with additional N-methylpyrrolidone and precipitated in water. The resulting solid is washed three times with water, washed twice with methanol, and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours. The polymer prepared above is found to be soluble in dimethylsulfoxide, N,N-dimethylacetamide, and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (based on weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the time noted below, the membranes are coagulated in a water bath at 20°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit good adhesion between the polymer layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit good adhesion between layers.The membrane fabrication procedure of this example demonstrates the applicability of the material described therein for gas separation membranes.Examples 50-51To a stirred solution of 2,4,6-trimethyl-1,3-phenylene diamine (15.02g, 0.10 mol) and 1,3-bis(4-aminophenoxy)benzene (29.2g, 0.10 mol) in dimethylsulfoxide (500 ml) is added 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl) ethylidene]-1,3-isobenzofurandione (89.69g, 0.202 mol) under an inert atmosphere at room temperature. The very viscous,light orange reaction solution is stirred at room temperature for 1.25 hours and then a solution of acetic anhydride (81.67g, 0.80 mol) and triethylamine (80.95g, 0.80 mol) is added with rapid stirring at room temperature. After stirring at room temperature overnight, the reaction solution is precipitated in water. The resulting solid is collected and washed twice with water, washed twice with methanol and allowed to air dry. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 3 hours and at 250°C for 5 hours to yield 122.6g product. The polymer prepared above is soluble in acetone, dichloromethane, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.A film, prepared as above which is 1.1 (2.8 x 10-5m) mils thick, is tested for mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 499 psig (3.44 x 106 Pa), 25.0°C. The results are reported below: O2 Productivity200 centiBarrersO2/N2 Selectivity4.6Multicomponent membranes are prepared from the polymer prepared above on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. 10,000) in N-methylpyrrolidone is cast onto a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife. gap. After drying at 100°C for the time noted in Table 6, the membranes are coagulated in a water bath at 21°C. The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. Examples 50 and 51 are tested for pure gas helium, nitrogen, and carbon dioxide permeabilities at 100 psig (689kPa), room temperature. The results are reported in Table 6. Example 50 is tested for mixed gas oxygen/nitrogen (21/ 79, mole) permeabilities at 100 psig (689kPa), 23°C. Results are reported in Table 6. ExampleDry Time (min)PHe (GPU)PHe/ PN2PCO (GPU)PCO2/ PN2PO2 (GPU)PO2/ PN2500.53233615517.3363.3511.040013.61966.7The membrane fabrication procedure of these examples demonstrates the applicability of the material described therein for gas separation membranes.Example 52To a stirred solution of 2,4,6-trimethyl-1,3-phenylene diamine (15.02g, 0.10 mol) and 1,4-bis(4-aminophenoxy)benzene (29.2g, 0.10 mol) in N-methylpyrrolidone (500 ml) is added 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-benzofurandione (89.69g 0.202 mol) under an inert atmosphere at room temperature. The very viscous reaction solution is stirred at room temperature for 3.5 hours and then a solution of acetic anhydride (81.67g, 0.80 mol) and triethylamine (80.95g, 0.80 mol) is added with rapid stirring at room temperature. After stirring overnight at room temperature, the reaction solution is precipitated in water. The resulting solid is collected and washed twice with water, washed twice with methanol, and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 3 hours and at 250°C for 5 hours to yield 123.1g of polymer product. The polymer prepared above is soluble in acetone, dichloromethane, dimethylsulfoxide, N,N-dimethylacetamide, and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 21C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.A film, prepared as above which is 1.1 mils (2.8 x 10-5m) thick, is tested for mixed gas oxygen/nitrogen (21/79,mole) permeabilities at 512 psig (3.53 x 106 Pa), 24.5°C. The results are reported below: O2 Productivity400 centiBarrersO2/N2 Selectivity4.5Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyether sulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 97.5°C ± 3.0°C. After drying on the plate for 15 seconds, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 97.5°C ± 3.0°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 97.5°C ± 3.0°C one minute, the membrane is coagulated in a water bath at 25.0°C ± 1.0°C. Good adhesion between the polymer layers is apparent.The resulting membrane is washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membrane is dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit good adhesion between the polymer layers.The membrane is tested for pure gas helium, nitrogen, and carbon dioxide permeabilities and mixed gas oxygen/nitrogen (21/79, mole) permeabilities at 100 psig (689kPa), 24°C. The results are reported in Table 7. ExampleDry Time PSF (min)Dry Time PI (min)PHe (GPU)PHe/PN2PCO2 (GPU)PCO2/PN2PO2 (GPU)PO2/PN2520.251.04282023111603.1The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 53To a stirred solution of 4,4'(methylethylidene)bisaniline (45.2g, 0.20 mol) in N-methylpyrrolidone (500 ml) is added 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]-1,3-isobenzofurandione (89.69g, 0.202 mol) under an inert atmosphere at room temperature. After stirring at room temperature for 5 hours, a solution of acetic anhydride (81.67g, 0.8 mol) and triethylamine (80.95g, 0.80 mol) is added with rapid stirring. The resulting viscous reaction solution is stirred at room temperature overnight and then precipitated in water. The resulting solid is collected and washed twice with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours and at 250°C for 4 hours to yield 130.4g product. The polymer prepared above is soluble in acetone, dichloromethane, m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 22% polymer solution (based on weight) of the polymer prepared above in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the time noted below, the membranes are coagulated in a water bath at 15°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All membranes exhibit excellent adhesion between the polymer layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit excellent adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 54To a stirred solution of 4,4'-(methylethylidene) bisaniline (22.6g, 0.10 mol) and 1,4-bis(4-aminophenoxy)biphenyl (37.28g, 0.10 mol) in N-methylpyrrolidone (350 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 40.69g, 0.20 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous light brown solution is stirred for 4.5 hours and then lithium hydroxide monohydrate (21g, 0.5 mol) is added. The resulting reaction mixture is stirred overnight and then diluted with additional N-methylpyrrolidoneand precipitated in water. The resulting solid is collected and washed three times with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 117°C ± 2°C for 6 hours to yield 85.5g product. The polymer prepared above is soluble in dimethylsulfoxide, m-cresol, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above with 6.8% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 25°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All membranes exhibit excellent adhesion between the polymer layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit excellent adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 55To a stirred solution of 2,7-bis(4-aminophenoxy)naphthalene (25.Og, 0.073 mol) in N-methylpyrrolidone (200 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3,molar, 15.14g, 0.075 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting viscous solution is stirred for 1 hour after the final addition and then lithium hydroxide monohydrate (10.50g, 0.25 mol) is added. The resulting reaction mixture is stirred overnight at room temperature, diluted with N-methylpyrrolidone and precipitated in water. The resulting white solid is collected and washed three times with water and twice with methanol. The resulting solid is air-dried overnight and then dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 h to yield 34.64g product. The polymer prepared above is soluble in N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 20% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 23°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit excellent adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit excellent adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 56To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.4g, 0.5 mol) and 3,3'-aminophenylsulfone (124.2g, 0.5 mol) inN,N-dimethylacetamide (2600 ml) is dropwise added a melted mixture of isophthaloyl dichloride: terephthaloyl dichloride (7:3, molar, 203.0g, 1.0 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous dark solution is stirred 3.5 hours and then lithium hydroxide (88.1g, 3.7 mol) is added. The resulting reaction mixture is stirred overnight at room temperature. The reaction solution is precipitated in water and the resulting solid is collected, washed twice with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours to yield 457.2g product. The polyamide prepared above is found to be soluble in dimethylsulfoxide, N,N-dimethylacetamide, and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 10% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 20-mil (5.1 x 10 4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking. Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 19°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. All dry membranes exhibit good adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 57To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (279.57g, 0.75 mol) and 2,4,6-trimethyl-1,3-phenylene diamine (37.56g, 0.25 mol) in N,N-dimethylacetamide (2600 ml) and pyridine (200 ml) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (7:3, molar, 205.05g, 1.01 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting very viscous reaction solution is stirred 2.5 hours and then lithium hydroxide (88.14g, 3.7 mol) is added. The resulting reaction mixture is mixed overnight at room temperature. The reaction solution is diluted with N-methylpyrrolidone and precipitated in water. The resulting solid is collected, washed twice with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours to yield 448.4g product. This polymer is found to be soluble in dimethylsulfoxide, N-methylpyrrolidone and N,N-dimethylacetamide.Films of the polymer prepared above are cast from a 10% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 20-mil (5.1 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 23°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All membranes exhibit excellent adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit good adhesion between. the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.Example 58To a stirred solution of 1,4-bis(4-aminophenoxy)biphenyl (186.38g, 0.50 mol) and 2,4,6-dithiomethyltoluene-1,3-diamine (a mixture of isomers, sold by Ethyl Corporation under the trade name ETHACURE 300, 107.25g, 0.50 mol) in a solution of pyridine (200 ml) and N,N-dimethylacetamide (2600 m]) is dropwise added a melted mixture of isophthaloyl dichloride:terephthaloyl dichloride (209.11g, 1.03 mol) under an inert atmosphere. The reaction temperature is maintained at under 50°C by control of the addition rate. The resulting reaction solution is stirred for 5.0 hours and then lithium hydroxide (88.14g, 3.7 mol) is added. The resulting reaction mixture is stirred overnight at room temperature and then precipitated in water. The resulting solid is collected, washed twice with water, washed twice with methanol and allowed to air dry overnight. The solid is further dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 5 hours to yield 452.6g product. The polyamide prepared above is found to be soluble in m-cresol, dimethylsulfoxide, N,N-dimethylacetamide and N-methylpyrrolidone.Films of the polymer prepared above are cast from a 15% polymer solution (based on weight) in N-methylpyrrolidone onto a glass plate treated with Du Pont TEFLON® dry lubricant at 100°C ± 2°C with a 15-mil (3.8 x 10-4m) knife gap. After drying on the plate at 100°C ± 2°C for 0.5 hour, the films are further dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight. The films are stripped off the plate and dried in a vacuum oven at 20 inches (0.51m) mercury and 120°C for 4 hours. The films are tough and flexible and can be creased without cracking.Multicomponent membranes are prepared from the above polymer on top of VICTREX 600P polyethersulfone (a product of ICI). A 25% VICTREX 600P polyethersulfone solution (based on weight) with 7.5% polyvinylpyrrolidone (M.W. = 10,000) in N-methylpyrrolidone is cast on a glass plate with a 15-mil (3.8 x 10-4m) knife gap at 100°C. After drying on the plate for 0.5 minutes at 100°C, a 24% polymer solution (based on weight) of the polymer prepared above in a 8.5% lithium nitrate solution (weight) in N-methylpyrrolidone is cast on top of the above film at 100°C with a 20-mil (5.1 x 10-4m) knife gap. After drying at 100°C ± 3°C for the times noted below, the membranes are coagulated in a water bath at 17°C ± 1°C. Three membranes are prepared with dry times of 0.05 minute, 0.50 minute and 1.00 minute, as described above. All water-wet membranes exhibit good adhesion between the layers.The resulting membranes are washed in water for 24 hours, washed in methanol for 2 hours and washed in FREON® 113 for 2 hours. The membranes are dried in a vacuum oven at 20 inches (0.51m) mercury and room temperature overnight and at 100°C for 4 hours. The membranes exhibit good adhesion between the component layers.The membrane fabrication procedure of this example demonstrates the applicability of the materials described therein for gas separation membranes.From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.	A process for manufacture of a multicomponent gas separation membrane, comprising providing a solution comprising a film forming polymer I as a first supporting layer, polymer I being selected from the group consisting of polysulfones, polyethersulfones, polyetherimides, polyimides, polyamides, copolymers thereof, and blends thereof,applying to a surface of said first supporting layer a second solution comprising a film forming polymer II to provide a separating layer to form a nascent membrane of at least two layers, wherein polymer I and polymer II are different polymers, and polymer II being selected from the group consisting of polyetherimides, polyimides, polyamides, polyesters, and mixtures thereof, wherein said providing of said first layer and said applying of said second solution is performed by coextruding said first solution and said second solution, coagulating said nascent membrane, anddrying said nascent membrane to form a multicomponent gas separation membrane.The process of Claim 1 wherein said coextruding yields a membrane in the form of a hollow fiber having said separating layer on the exterior of said fiber.The process of Claim 2 wherein said separating layer is in the form of an asymmetric membrane. The process of Claim 1 wherein said nascent membrane is dried to remove solvent from said separating layer prior to said coagulating.The process of Claim 2 wherein said first layer is from about 25 to about 300 microns in thickness.The process of Claim 5 wherein said separating layer is from about 0.05 to about 150 µm in thickness, preferably from about 0.05 to about 25 µm in thickness.The process of Claim 1 wherein said second solution contains from about 5 to about 50 weight percent film forming polymer.The process of Claim 1 wherein said first solution contains from about 15 to about 50 weight percent film forming polymer.The process of Claim 1 wherein said film forming polymer of said first solution is selected from the group of polyether sulfones, polysulfones, polyimides, or mixtures thereof, and said film forming polymer of said second solution is a polyamide.The process of Claim 9 wherein said polyamide has the formula: where R is one of either or mixtures thereof where Z', Z , Z''' are independently a carbon-carbon single bond, or mixtures thereof, Ar is where Z is a carbon-carbon single bond, or mixtures thereof, n is an integer such that the polymer is of film-forming molecular weight, -X, -X1, -X2 and -X3 are independently hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, and -Y, -Y1, -Y2, -Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, -Y15 independently are X, X1, X2, X3, halogen, or alkyl groups of 1 to 6 carbon atoms. The process of Claim 10 wherein Ar is or mixtures thereof.The process of Claim 11 wherein R is or or or or or or a mixture of and or a mixture of and or a mixture of and or or a mixture of and or or a mixture of and or a mixture of and or a mixture of and The process of Claim 1 wherein said polyimide is an aromatic polyimide comprising repeating units of the formula: wherein R and R' are selected from the group and where -Z- is a carbon-carbon single bond or alkylene groups of 1 to 5 carbon atoms, -Ar- is one of either or mixtures thereof where Z', Z'', Z''' independently are a carbon-carbon single bond, or alkylene groups of 1 to 5 carbon atoms, X, X1, X2 and X3 are independently, hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, -Y, -Y1, -Y2, -Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9, ,Y10, -Y11, -Y12, -Y13, -Y14, and -Y15 independently are -X, -X1, -X2, -X3 or halogen, -Ar'- is or mixtures thereof where Z' has the above-defined neaning, m is 0 to 100 mole percent, n is 0 to 100 mole percent, and (m + n) = 100%.The process of Claim 13 wherein n is 0 to 20 percent and m is 0 to 80-100 percent.The process of Claim 13 wherein R is The process of Claim 15 wherein -Ar- is a mixture of and or or or or or or or or a mixture of and The process of Claim 13 wherein R is The process of Claim 17 wherein -Ar- is a mixture of and or wherein -Ar- is A multicomponent membrane obtainable according to the process of claim 1 comprising, a porous polymeric substrate wherein the substrate is selected from the group of polysulfones, polyether sulfones, polyetherimides, polyimides, polyamides, polyesters, or mixtures thereof and a polyamide separating layer for separating gases, wherein said polyamide has the formula where R is one of either or mixtures thereof where Z', Z'', and Z''' are independently a carbon-carbon single bond, or mixtures thereof, Ar is where Z is a carbon-carbon single bond, or mixtures thereof, n is an integer such that the polymer is of film-forming molecular weight, -X, -X1, -X2 and -X3 are independently hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, and -Y, -Y1, -Y2, -Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, -Y15 independently are X, X1, X2, X3, halogen, or alkyl groups of 1 to 6 carbon atoms.The multicomponent membrane of Claim 19 wherein Ar is or mixtures thereof.The multicomponent membrane of Claim 19 wherein R is or or or or or or or a mixture of and or a mixture of and or a mixture of and or or a mixture of and or or a mixture of and or a mixture of and or a mixture of and A multicomponent membrane obtainable according to the process of claim 1 comprising a porous polymeric substrate which is formed of a majority amount of a polymer which other than an aromatic polyimide which is selected from the group of polysulfones, polyether sulfones, polyetherimides, polyimides, polyamides, polyesters, or mixtures thereof and a polyimide separating layer for separating gases wherein said polyimide is an aromatic polyimide comprising repeating units of the formula: wherein R and R' are selected from the group and where -Z- is a carbon-carbon single bond, or alkylene groups of 1 to 5 carbon atoms, -Ar- is or mixtures thereof where Z', Z'', Z''' independently are a carbon-carbon single bond, or alkylene groups of 1 to 5 carbon atoms, X, X1, X2 and X3 are independently, hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, -Y, -Y1, -Y2, -Y3, -Y4, -Y5, -Y6, -Y7, -Y8, -Y9, -Y10, -Y11, -Y12, -Y13, -Y14, and -Y15 independently are -X, -X1, -X2, -X3 or halogen, -Ar'- is or mixtures thereof where Z' has the above-defined meaning, m is 0 to 100 mole percent, n is 0 to 100 mole percent, and (m + n) = 100%.The membrane of Claim 22 wherein m is 20 to 100 mole percent and n is 20 to 100 mole percent. The membrane of claim 22 wherein R is The membrane of claim 22 wherein -Ar- is a mixture of and or wherein -Ar- is or mixtures thereof, or wherein -Ar- is or or or or or or a mixture of and The membrane of claim 22 wherein R is The membrane of claim 26 wherein -Ar- is a mixture of and or wherein -Ar- is	AIR LIQUIDE; L'AIR LIQUIDE, SOCIETE ANONYME POUR	EKINER OKAN MAX; HAYES RICHARD ALLEN; MANOS PHILIP; EKINER, OKAN MAX; HAYES, RICHARD ALLEN; MANOS, PHILIP
EP-0489424-B1	489,424	EP	B1	EN	19,960,501	1,992	20,100,220	new	C08B31	A61L31, A61K7, A61B19	A61B19, A61L31, C08B31, A61Q1, C08J3, A61K8	A61K 8/73F, A61L 31/04D+C08L3/00, A61Q 1/12, C08B 31/00B, K61B19:04	Absorbable dusting powder derived from starch	Absorbable dusting powders suitable for medical applications such as lubricating surgical gloves are prepared by treating starch with a hypochlorite to remove protein and oxidize some of the hydroxyl groups, and partially cross-linking the hypochlorite-treated starch with phosphorus oxychloride. The modified starch dusting powders are free flowing and are characterized by a protein content of less than about 0.15% by weight, hydroxyl groups oxidized to a level of from about 0.5 to about 0.05% by weight and a degree of cross-linking of other hydroxyl groups characterized by bound phosphorus levels of from about 200 to about 1200 ppm.	BACKGROUND OF THE INVENTIONField of The InventionThe present invention relates to dusting powders of the type used for lubricating surgical gloves. More particularly, the invention has to do with absorbable dusting powders made from starches having reduced protein content, a low level of carboxyl groups generated through the slight oxidation of hydroxyl groups, and other hydroxyl groups cross-linked using a relatively low level of phosphorus oxychloride (POCl₃). Description of Related ArtDusting powders used by the medical profession have been associated with numerous problems. Such powders have traditionally been based on talc. However, it has been discovered that talc causes granulomas in the body. Talc also has come under increasing scrutiny as possibly containing asbestos, a carcinogenic substance. While pure mineral talc is composed of a group of hydrous magnesium silicates, commercial talc has varying compositions depending on the source and method of production. Some of these compositions may be contaminated with asbestos. Talc has effectively been replaced by starch-based powders, but the starch-based powders have a number of disadvantages too. The use of starch has been associated with peritonitis flowing from the use of corn starch on or in surgeons' gloves and has been associated with infections which occur from glove-borne particles during optical surgery which may cause the cornea to turn opaque. Microbial problems are associated with starch because it is an excellent nutrient medium for virtually all vegetative bacteria such as various pathogenic microorganisms. Despite the aforementioned disadvantages associated with starch-based powders, they are still used by the medical profession because starch is an inexpensive and readily available raw material. There is a need, therefore, for improved starch dusting powders which overcome many of the foregoing problems. Starch-based dusting powders used for surgical gloves and other medical apparatus (e.g., tubing, catheters and drains) which may be exposed to internal parts of the body, such as the peritoneal cavity during surgery, must meet strict United States Pharmacopoeia (USP) standards for Absorbable Dusting Powders. These standards are published by the United States Pharmacopeial Convention, Inc., 12601 Twin Brook Parkway, Rockville, MD 20852 USA. All references to the USP or to USP Standards are to the official standards from January 1, 1990 entitled USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary. The USP Standards require cross-linking of the starch to prevent gelatinization which would otherwise occur during sterilization when an autoclave is used. Epichlorohydrin can be used for cross-linking as disclosed in U.S. Patent No. 4,853,978 to Stokum. The patent relates to antimicrobial medical gloves which can be coated with epichlorohydrin cross-linked corn starch. The starch serves as an antimicrobial agent and a donning assist. The starch powder is believed to be bioabsorbable if left in a wound site. In some applications, antimicrobials (e.g., compositions having fungicidal, bactericidal and/or bacteriostatic properties) having an affinity for the cross-linked starch can be absorbed on the starch. When epichlorohydrin is used for cross-linking, there is some risk that residual quantities of toxic chlorohydrins can remain in the product. Thus, alternative types of absorbable dusting powders have been developed. U.S. Patent No. 4,540,407 to Dunn, for example, discloses the use of a polyol powder which also avoids the problem of starch peritonitis. A chitin-derived, finely divided biodegradable powder is described in U.S. Patent No. 4,064,564 to Casey for use as a lubricant on surgical gloves. Derivatized chitin, however, is believed to be expensive relative to modified starch and is difficult to obtain in commercial quantities. Other medical lubricants are disclosed in U.S. Patent No. 4,773,902 to Lentz et al. which is directed to the use of oxidized cellulose, and U.S. Patent No. 4,152,783 to Choski which is directed to a surgeon's glove provided with a sodium bicarbonate powder. It has now been discovered in accordance with the present invention that a new modified starch can be prepared which meets USP Standards for absorbable dusting powders while avoiding many of the problems associated with prior art products. The starch is modified in two steps. First, it is treated with sodium hypochlorite to remove protein, oxidize some of the hydroxyl groups and whiten the product. Second, the hypochlorite treated starch is cross-linked with POCl₃ at a low level to allow better assimilation while meeting USP Standards. The use of POCl₃ for cross-linking avoids any risk of residual chlorohydrins associated with the use of epichlorohydrin. U.S. Patent No. 4,562,086 to Smolka et al. discloses a modified starch for use in food applications which is prepared by etherification with an alkylene oxide followed by cross-linking. Phosphorus oxychloride is disclosed as a cross-linking agent. Treatment of corn starch with hypochlorite is disclosed in U.S. Patent No. 2,070,776 to Bochskandl, U.S. Patent No. 2,951,776 to Scallet et al. and U.S. Patent No. 2,989,521 to Serti et al. The Serti et al. patent describes a process whereby starch is first cross-linked with epichlorohydrin followed by treatment with sodium hypochlorite. These patents do not disclose the processing conditions, or the products of the present invention and none of them relate to the preparation of modified starches for medical uses. The JP-B-7 106 377 discloses a treatment method for modified starch characterized by the fact that starch in an aqueous suspension is treated with 0.1-1.0% of an oxidizing agent and 0.1-1.0%, based on the starch, of sodium trimetaphosphate in the presence of Na⁺ ion as a catalyst and at a pH ranging from 8-12. U.S. Patent No. 2,938,901 discloses a process for making an inert dusting powder which comprises treating starch with metaphosphates or polymetaphosphates in an amount of 0.01 to 3.0 percent based on starch. A medical dusting powder comprising a partially etherified starch powder and 0.05 to 10 percent by weight of magnesium oxide is disclosed in U.S. Patent No. 2,626,257. SUMMARY OF THE INVENTIONThe absorbable dusting powder composition of the invention is made by modifying starch, preferably corn starch, in two steps. In the first step, the starch is treated with a hypochlorite to remove most of the protein and oxidize some of the hydroxyl groups. This step also causes whitening of the product. It has been found that protein from plant sources can cause allergenic response in humans. To reduce any possible allergenic reaction from the protein in starch, treatment, using hypochlorite, is important in the development of an absorbable dusting powder. In the second step, the hypochlorite modified starch is partially cross-linked with POCl₃ to allow better assimilation while meeting USP Standards. A sufficiently low level of cross-linking with POCl₃ prevents gelatinization during heat-pressure based sterilization. The low levels of cross-linking also increase the opportunity for assimilation by normal physiological functions. The USP requires that sedimentation, a measure which depends on the degree of cross-linking, not exceed a value of 75 milliliters (which, for the product of the present invention, is approximately equivalent to bound phosphorus levels of about 400 parts per million (ppm) as explained later in this specification). Magnesium oxide (MgO) can be added to the hypochlorite-modified cross-linked starch if desired. Magnesium oxide is commonly used to increase the flowability of dry starch products. When the starch materials formulated with MgO are placed in water, the MgO becomes magnesium hydroxide, an alkaline substance. The USP has limits on the maximum quantities of magnesium oxide that can be used as well as a maximum pH specification that would be indicative of the generation of magnesium hydroxide in solution. DETAILED DESCRIPTION OF THE INVENTIONThe starting material starch used in accordance with the present invention can be derived from various cereal and root materials including corn, milo, wheat, rice, arrowroot, beet, potato, tapioca, waxy corn and waxy milo. Granular corn starch which is made in the corn wet-milling process is preferred because it is readily available, inexpensive and relatively pure as it is produced so that it does not have to be heavily refined after it comes from a corn-wet milling plant. Corn starch is a carbohydrate polymer derived from corn of various types and composed of about 25% amylose and about 75% amylopectin. It is generally in the form of a fine white powder having a granule size from about 5 to about 25 microns with the average granule size being about 13.9 microns. Bulk density ranges from about 0.61 to 0.75 g/cm³ (38 to 47 pounds per cubic foot) depending on the drying technique used. Flash dried and spray dried starches have bulk densities at the low end of the range and belt dried starches have bulk densities at the high end. Moisture content of corn starch is generally about 12%, but varies with ambient relative humidity. The gelatinization temperature, as defined by the loss of birefringence, is from about 68 to 72° C. The starting material starch can be unmodified or modified. Suitable modified starches include oxidized starches such as those prepared with hypochlorite or peroxide. The hypochlorite used in accordance with the invention may be a hypochlorite of sodium, potassium, calcium or magnesium. Sodium hypochlorite (NaOCl) is preferred because it is more readily commercially available. The phosphorus oxychloride (POCl₃) used in accordance with the invention is a technical grade compound which generally has a specification of 99.5% purity. Phosphorus oxychloride, which is also known as phosphorus oxytrichloride or phosphoryl chloride, is a colorless to pale yellow fuming liquid. It reacts exothermically with water to produce phosphoric and hydrochloric acids. If magnesium oxide is used in accordance with the invention, it should meet the requirements of USP Standards. The process of the invention can be carried out in a continuous or batchwise manner. The first process step comprises treating a slurried starting material starch with a hypochlorite to remove most of the protein and oxidize some of the hydroxyl groups. The slurried starting material starch should have a dry substance (d.s.) from 10% to 45%. The hypochlorite used can have a concentration from 5% to 25% by weight (w/w) chlorine. If necessary, an acid or alkali is added with the hypochlorite to maintain the pH of the reaction mixture at from 5 to 10. Suitable reagents for this purpose are hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide and potassium hydroxide. The starch is preferably reacted with hypochlorite at a temperature from about 38°C (100°F) to about 66°C (150°F) for a period of time sufficient to remove the protein to a level of less than about 0.15% w/w, with levels of about 0.05% w/w or less being particularly preferred, and oxidize from 0.5% w/w to 0.05% w/w of the hydroxyl groups. Typical reaction times are from 15 minutes to 2 hours. The degree of oxidation is determined by measuring the carboxyl content of the starch using standard analytical methods such as those set forth in Whistler et al., STARCH: Chemistry and Technology, Vol II (Academic Press 1967) Chapter XXV entitled Characterization and Analysis of Starches pp. 620-621; and Bernetti et al., Modern Methods of Analysis of Food Starches, Cereal Foods World, Vol. 35, No. 11, November 1990 (American Association of Cereal Chemists Inc. 1990) p. 1102. Following the reaction with hypochlorite, any free chlorine present in the reaction slurry should be neutralized; otherwise the reaction can continue, even in the dry form, although at a reduced rate. Neutralization, if needed, can be accomplished by admixing a neutralizing compound such as sodium bisulfite, sodium sulfite, potassium bisulfite, potassium sulfite or sulfur dioxide gas in a sufficient quantity to achieve a value of no detectable chlorine as determined by suitable analytical methods for residual oxidants such as that set forth in the USP Standards for starch, page 1986 [9005-25-8] under Oxidizing Substances . At this stage, the reaction slurry can either be directed to the next reaction step, or dewatered and the hypochlorite treated starch can be dried by conventional means and saved for subsequent processing. If the material is to be saved, reaction slurry pH is adjusted to from 5 to 8 before dewatering and drying. Suitable pH adjustment agents include sodium hydroxide, potassium hydroxide; hydrochloric, sulfuric or phosphoric acid; or any other acid or base that will yield non-toxic soluble salts. Suitable dewatering techniques include centrifugation and filtration. Drying can be carried out in a flash dryer, ring dryer, spray dryer, belt dryer or the like. The reaction slurry from the hypochlorite treatment stage is adjusted by the addition or removal of water, if necessary, to a d.s. from 10% to 45%. If dried hypochlorite treated starch is used, it is reslurried with the addition of water to a d.s. within the same range and mixed to prepare a uniform dispersion. Slurry temperature at this stage is preferably maintained at from 38°C 100°F to 66°C (150°F). A salt can be added at a level from 1% to 5% dry basis (d.b.) to the slurry as a gelation suppressant to reduce the tendency of starch granules to swell in the presence of base or alkali and to retard hydrolysis of the POCL₃ reagent. Commonly used salts include sodium chloride and sodium sulfate. Then the pH is adjusted by adding caustic to attain a slurry pH from 11.5 to 12.5. Suitable caustic agents include sodium hydroxide and potassium hydroxide. Phosphorus oxychloride is then added at a concentration from 0.05% to 1.1% w/w, preferably from 0.5% to 1.0% w/w, based on dry substance, to cross-link the starch. Typical reaction times are from 15 to 45 minutes. At higher slurry temperatures shorter times might be used and longer times may be suitable for lower slurry temperatures. Higher concentrations will result in more cross-linking and lower concentrations will result in less cross-linking. The degree of cross-linking of the product of the invention can be expressed as that which will yield a USP sedimentation value in milliliters (ml.) of 45 to 95, preferably 70-95, and most preferably from 70-75. (The most preferred range is based on present USP standards. However, compositions having higher sedimentation values may be more desirable since they are more easily assimilated by the body.) Excessive cross-linking, yielding a sedimentation value of less than bout 45 ml. is detrimental to physiological assimilation which becomes difficult or reduced at such levels. The cross-linked product is then washed and neutralized. Washing can be carried out either before or after neutralizing, but it is preferred to neutralize first because it reduces the presence of ash before washing. (Neutralization is necessary because it converts hydroxides to salts and salts are easier to remove.) Neutralization is accomplished by adding acid to bring the slurry to a pH of from 6 to 8. Suitable neutralizing acids include hydrochloric, sulfuric and phosphoric acids. Hydrochloric acid is preferred because it is readily available and essentially all of the resulting salts are soluble. Washing is necessary to remove residual inorganic and organic components and is accomplished by dewatering and reslurrying in one or more cycles until acceptable levels (preferably the lowest possible levels) of such residual components are reached. Dewatering can be carried out by means of a filter or centrifuge. Reslurrying following dewatering should be to 10 to 20% w/w solids. Slurry washing can also be accomplished using successive stages of hydroclones. The washed, neutralized slurry is then dried to a moisture content from 8% to 14% using a spray dryer, flash dryer, ring dryer, belt dryer or the like. The dried modified starch product is a free flowing white powder and is characterized by a protein content of less than about 0.15%, preferably about 0.05% or less, hydroxyl groups oxidized to a level of from 0.05% w/w to 0.5% w/w and a degree of cross-linking of hydroxyl groups characterized by having a USP sedimentation value of 45 to 95 ml. The modified starch composition can be used as a medical dusting powder for various applications including surgical gloves, catheters, tubing, drains and the like. It can be admixed with magnesium oxide if desired or if necessary to meet regulatory standards. The magnesium oxide can be added in an amount less than about 2% w/w dry substance and preferably from 0.5% to 2% w/w dry substance, with the maximum being based on USP specifications. When magnesium oxide is added, the objective is to obtain an end product having USP sedimentation values within the range of 45 to 95 ml., preferably 70-95 ml. and most preferably 70-75 ml. EXAMPLESSix samples of absorbable dusting powder were prepared. The final processing steps were conducted in a batch process using a 378 l (100 gallon) tank provided with an agitator. A high level of agitation was attained by adjusting a portable mixer so that the impeller was near the liquid surface. Agitation was continuous during all of the process steps from preparation of the starch slurry through completion of the cross-linking reaction. Each batch was made in the same way except for variations in concentrations and quantities as indicated below. Reaction Sequence45 kg (One hundred pounds) of BUFFALO (registered trademark) food grade granular starch available from Corn Products, Box 345, Summit-Argo, Illinois 60501 USA, is treated with sodium hypochlorite in a continuous process. The starch is slurried at 41% d.s. and combined with sodium hypochlorite having a concentration of 15% w/w chlorine and 31% w/w hydrochloric acid. The starch slurry is added to a reaction hold tank at a rate of 10.2 liters per minute, sodium hypochlorite is added at a rate of 14.5 liters per hour and hydrochloric acid is added at a rate of 0.69 liters per hour. The reaction mixture in the reaction hold tank is maintained at a temperature of 47°C. (117°F.) and a pH of 6.4 ± 0.3. Residence time in the reaction hold tank is 30 minutes. Sodium bisulfite (having a concentration of 15% w/w) is admixed with the product leaving the reaction hold tank to neutralize free chlorine. The addition takes place in a neutralization pipeline on the way into a neutralization tank. The flow of sodium bisulfite is adjusted as necessary to achieve no detectable free chlorine. Soda ash (having a concentration of 5% w/w) is added to the product leaving the neutralization tank. The addition takes place in a neutralization pipeline on the way to a basket centrifuge for dewatering. The flow rate of soda ash is adjusted as necessary to achieve a slurry pH of 5.0-5.5. The slurry is dewatered in the basket centrifuge and the dewatered hypochlorite-treated starch is dried in a flash dryer to a moisture content of 12% w/w. Alternatively, 45 kg (one hundred pounds) of oxidized starch having a protein content of about 0.15% d.s. is treated with hypochlorite in the same manner as set forth above except that sodium hypochlorite containing about 4% w/w free sodium hydroxide is added at a comparable rate and no hydrochloric acid is added. For each reaction batch, 170 l (45 gallons) of water were added to a 378 l (100 gallon) tank and heated to a temperature of about 110°F. (43°C.) For each of five samples, 136 kg (300 pounds) of BUFFALO starch (not hypochlorite-treated) was added to prepare starch slurries having 40% starch solids while maintaining the temperature at about 43°C (110° F). For the sixth sample, 45 kg (100 pounds) of the hypochlorite-treated BUFFALO starch was added to 114 l (30 gallons) of water to prepare a starch slurry having 20% starch solids. There was no other adjustment or control of temperature during subsequent processing steps. Each starch slurry was mixed for from 15 to 30 minutes before further processing. The objective of the mixing was to prepare a uniform dispersion. Sodium chloride (NaCl) was added to each starch slurry as a dry solid at a level of 3% based on starch dry substance. About 15 minutes after NaCl addition, sodium hydroxide (NaOH) was added as a 4% by weight solution. (The 4% NaOH solution was prepared by adding 50% by weight NaOH to dilution water.) NaOH addition was gradual over a period of about 20 minutes until a concentration of 2.05% by weight NaOH based on starch dry substance was attained. The NaOH addition point was into an area of high agitation on the liquid surface in the reaction tank. Slurry pH after NaOH addition was from about 12.0 to about 12.4. About 10 minutes after NaOH addition was completed, POCl₃ was measured in a graduated cylinder before addition. Of the six samples prepared, two were at a POCl₃ concentration of 0.6% by weight based on starch dry substance, two at 0.8% and two at 1.0%. The concentrations were varied to achieve different levels of cross-linking. POCl₃ was added gradually over a period of 30-60 seconds. Vapors were controlled with a vat hose connected to an exhaust fan. The cross-linking reaction was considered completed 10 minutes after POCl₃ addition. Reaction slurry pH following cross-linking was from 11.3 to 11.9. Washing and NeutralizationSome of the reaction slurries were separated into two fractions with about one-third being neutralized before washing. The remaining two-thirds were neutralized after washing. Neutralization was accomplished by adding 1% w/w hydrochloric acid to the slurries to bring the pH to about 7. The cross-linked reaction product was washed in three steps using a 91 cm (36 inch) diameter gravity nutsche filter. (A nutsche filter is a tank equipped with a false bottom, perforated or porous, that may support a filter medium or may itself act as the septum.) Two different tightly woven filter cloths were used in separate trials. One was a white polyamide-nylon fabric made from a monofilament source having a mesh of -3-53/21 xx and a width of 40-42 inches. This cloth is sold under the trademark MITEX by Tetko Incorporated, 333 S. Highland Avenue, Briarcliff Manor, New York 10523 USA. The other was a gray cotton fabric made from a twisted multifilament thread and sold under the Style Number EMPH 101 by TestFabrics Inc., 200 Blackford Avenue, Middlesex, NJ 08846 USA. Both filter cloths gave satisfactory results. A vacuum generated by a vacuum pump at a level of 380 mm (15 inches) mercury (Hg) was used. Each filtration cycle was conducted for 5-15 minutes resulting in filter cakes 2,5-7,5 cm (1-3 inches) thick having a moisture content of about 50%. The filter cakes were reslurried to 35-40% by weight solids between each step and after the last filtration step. DryingThe washed, neutralized slurries were each separately spray dried in a DeLaval spray dryer (DeLaval, Inc., Lawrenceville, New Jersey USA). Dryer inlet air at a temperature of 153°C (300°F) 10°C (50°F) wet bulb) was obtained from a gas furnace. Supply slurry was atomized through a high pressure nozzle at 18,000 kN/m² gauge (2600 p.s.i.g.) at a rate of 56,8 l/h (15 gallons/hour). Outlet air temperature was controlled at about 66°C (150°F). for a target product moisture of 10%. The drying rate was about 23 kg (50 pounds) of product per hour. The spray dried product was free flowing with low dust generation when handled and had a somewhat granular texture. Microscopic examination revealed roughly spherical agglomerates ranging in size from a few to several hundred individual starch granules. In the presence of water, the agglomerates immediately and totally dispersed. Product AnalysesAnalytical results are summarized in Tables I and II below. Sample POCl₃ dose % moist. pH Ash, % d.b.Sedimentation 1A0.66.78.91.652 1B0.66.89.31.051 2A0.87.79.21.847 2G0.89.99.30.759 3A1.08.38.81.545 3B1.010.09.31.1 50 The POCl₃ dose was a percentage based on total starch, dry substance. The A samples and the G sample were washed before the neutralization step and the B samples were washed after neutralization. The A and B samples were made using the BUFFALO starch starting material and the G sample was made using the hypochlorite-treated BUFFALO starch starting material. Sample Na, ppm d.b. Protein, % d.b. Solubles, % d.b. Bact. Mold/Yeast 1A69000.211.635005 1B27000.341.05200180 2A70000.201.9480070 2G28000.051.3780040 3A43000.261.235010 3B15000.290.9---- Microbial analytical values for bacteria (Bact.) and mold and yeast are in colony forming units per gram (cfu/g). Sample Formulation With MgOEach of the six samples was formulated in the laboratory with 0.25, 0.50 and 0.75 percent magnesium oxide to determine the effect on pH and sedimentation volume shown in Table III. A magnesium level of about 0.5% was enough to reach the minimum 10.0 pH for all of the samples and still be within the sedimentation specification. Sample MgO, % on d.s. pH U.S.P. Sedimentation, ml 1A08.952 0.259.6568 0.509.9570 0.7510.070 1B09.351 0.259.958 0.5010.0562 0.7510.165 2A09.247 0.259.960 0.5010.0563 0.7510.270 2G09.359 0.2510.273 0.5010.2574 0.7510.3576 3A08.845 0.2510.0560 0.5010.262 0.7510.364 3B09.350 0.2510.0564 0.5010.2566 0.7510.368	Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, IT, LI, NL, SEA modified starch composition comprising a protein content of less than about 0.15% by weight, from 0.5 to 0.05% by weight carboxyl groups, obtainable by crosslinking with 0.05% to 1.1% w/w POCl₃ and having a USP sedimentation value ( USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary ) from 45 to 95 milliliters. The composition of claim 1 further comprising magnesium oxide in an amount less than about 2% by weight dry substance. The use of the composition of claim 1 as a medical lubricant. A process for preparing a modified starch composition comprising treating a starch with a hypochlorite to remove protein to a level less than about 0.15% by weight and oxidize from 0.5 to 0.05% by weight of the hydroxyl groups, if present, neutralizing any free chlorine by admixing a chlorine neutralizing compound in a sufficient quantity, and then partially cross-linking the hypochlorite treated starch with 0.05% to 1.1% w/w phosphorous oxychloride to obtain a composition having a USP sedimentation value ( USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary ) from 45 to 95 milliliters. The process of claim 4 wherein the hypochlorite is sodium hypochlorite. The process of claim 4 wherein a starch slurry having a dry substance from 10% to 45% is first reacted with a hypochlorite at a pH from 5 to 10 and a temperature from 38 (100) to 66°C (150°F) for a period of time sufficient to reduce the protein content of the starch to a level of less than about 0.15% by weight and oxidize from 0.5 to 0.05% by weight of the hydroxyl groups, followed by, if present, neutralizing any free chlorine by admixing a chlorine neutralizing compound in a sufficient quantity and followed by reacting with 0.05% to 1.1% w/w phosphorus oxychloride at a pH from 11.5 to 12.5 and a temperature from 38 (100) to 66°C (150°F) for a period of time sufficient to obtain a composition having a USP sedimentation value ( USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary ) from 45 to 95 milliliters. Claims for the following Contracting State : ESA process for preparing a modified starch composition comprising treating a starch with a hypochlorite to remove protein to a level less than about 0.15% by weight and oxidize from 0.5 to 0.05% by weight of the hydroxyl groups, if present, neutralizing any free chlorine by admixing a chlorine neutralizing compound in a sufficient quantity, and then partially cross-linking the hypochlorite treated starch with 0.05% to 1.1% w/w phosphorous oxychloride to obtain a composition having a USP sedimentation value ( USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary ) from 45 to 95 milliliters. The process of claim 1 further comprising admixing magnesium oxide in an amount less than about 2% by weight dry substance. The process of claim 1 wherein the hypochlorite is sodium hypochlorite. The process of claim 1 wherein a starch slurry having a dry substance from 10% to 45% is first reacted with a hypochlorite at a pH from 5 to 10 and a temperature from 38 (100) to 66°C (150°F) for a period of time sufficient to reduce the protein content of the starch to a level of less than about 0.15% by weight and oxidize from 0.5 to 0.05% by weight of the hydroxyl groups, followed by, if present, neutralizing any free chlorine by admixing a chlorine neutralizing compound in a sufficient quantity and followed by reacting with 0.05% to 1.1% w/w phosphorus oxychloride at a pH from 11.5 to 12.5 and a temperature from 38 (100) to 66°C (150°F) for a period of time sufficient to obtain a composition having a USP sedimentation value ( USP XXII, NF XVII, The United States Pharmacopeia, The National Formulary ) from 45 to 95 milliliters. The use of the composition of claim 1 as a medical lubricant.	CPC INTERNATIONAL INC; CPC INTERNATIONAL INC.	FITT LARRY E; MCNARY HARRY THOMAS; FITT, LARRY E.; MCNARY, HARRY THOMAS
EP-0489425-B1	489,425	EP	B1	EN	19,960,904	1,992	20,100,220	new	C08F2	null	C08F251, C08F2	C08F 251/02, C08F 2/20	Vinyl polymerization particle size control	Particle Size Distribution (PSD) of polymer produced from styrene, methylmethacrylate, vinyl chloride, diethylaminoethylmethacrylate and butyl methacrylate vinyl monomers is controlled above 60% with less than 0.1% latex production using tri-calcium phosphate (TCP) in combination with a thickening agent which is one or more: (a) hydroxyethylcellulose molecule weight 300,000 to 1,000,000; (b) hydrophobically modified hydroxyethylcellulose molecular weight 100,000 to 800,000; (c) carboxymethylmethylcellulose, carboxymethylmethylhydroxyethylcellulose or carboxymethylmethylhydroxypropylcellulose molecular weight 20,000 to 140,000.	The invention relates to control of particle size for polymers prepared from vinyl monomers. In particular, a cellulose ether allows preparation of a homogenous particle size distribution of the polymer. Suspension polymerization is a technique used to produce micron size and larger particles, whereas emulsion polymerization produces latices having a particle size less than 1.0 micron. In suspension polymerization a non-water soluble initiator is dissolved in the monomer, whereas in emulsion polymerization a water soluble initiator forms an initiator radical in the aqueous phase. Differences between suspension polymerization and emulsion polymerization are discussed in U.S. patents 4,229,569; 4,093,776 and 4,552,939 as well as in technical encyclopedias. It is known to use cellulose ethers and other polysaccharide polymer thickeners to control vinyl monomer polymerization. U.S. patent 3,786,115 describes a process for styrene polymerization in the presence of 0.01 to 1% hydroxyethylcellulose, 0.01 to 3% substantially water insoluble inorganic phosphate and/or carbonate and 0.001 to 0.02% anionic surface active agent. EPO publication 0 068 298 discloses styrene suspension polymerization employing calcium or magnesium phosphate in a water phase. U.S. patent 4,352,916 discloses latex formation from vinyl monomers in the presence of a hydrophobically modified hydroxyethylcellulose wherein the vinyl monomer is selected from styrene, methylmethacrylate, vinyl chloride, diethylamino ethylmethacrylate and butylmethlacrylate. U.S. patent 4,609,512 discloses particle size control with an aqueous phase including such salts as calcium chloride, iron (III) chloride, copper nitrate, zinc sulfate, calcium chloride, cobalt (III) chloride and magnesium chloride. U.S. patent 4,833,198 discloses the preparation of a laurylmethacrylate/acrylic acid copolymer and use of copolymer in combination with fumed silicon dioxide as a suspension agent for vinyl polymerization. U.S. patent 4,868,238 discloses suspension polymerization of a vinyl monomer in the presence of 0.01 to 2.0% carboxymethyl hydrophobically modified hydroxyethylcellulose and optionally an electrolyte or polyelectrolyte. U.S. Patent 4,910,273 discloses a partially saponified polyvinyl alcohol to serve as a suspension stabilizer for vinyl chloride polymerization. Yet in spite of what was known in the art, a need still remained for a means to provide polymer particles with a more homogeneous particle size distribution. It is in meeting this need that the present invention provides an advance in the state of the art of vinyl monomer polymerization. A process for controlling particle size of polymers prepared from vinyl monomers in the presence of a thickening agent of a cellulose ether derivative is characterized in that the cellulose ether derivative is one or more of: (a) hydroxyethylcellulose with a molecular weight of 300,000 to 1,000,000 and a molar substitution (M.S.) of 1.5 to 3.5; (b) hydrophobically modified hydroxyethylcellulose with a molecular weight of 100,000 to 800,000 and an M.S. of 1.5 to 4.1 with a hydrophobic modification chain of C4 to C22 in an amount of 0.1 to 1.0 percent by weight based on the total weight of the hydrophobically modified hydroxyethylcellulose, which is used in an amount of 0.01 to 0.6% by weight; (c) carboxymethylmethylcellulose, carboxymethylmethylhydroxyethylcellulose or carboxymethylmethylhydroxypropylcellulose with a molecular weight of 20,000 to 400,000 with a degree of carboxymethyl substitution of from 0.05 to 1.0 which is used in an amount of 0.01-0.50% by weight based on the weight of the vinyl monomer; such that a polymer prepared from the vinyl monomer has a homogeneity of particle size distribution (PSD) which is 60% or higher and the weight percentage of latex is below 0.1% by weight based on the starting weight of vinyl monomer selected from the group of styrene, methylmethacrylate, vinyl chloride, diethylaminoethylmethacrylate and butyl methacrylate. It is preferred that the thickening agent be used in combination with tri-calcium phosphate (TCP). It has been discovered that improved particle homogeneity can be obtained without the use of metal salts via the careful selection of suitable cellulose ether derivatives. It was a surprising result to find that out of all available polysaccharide derivatives there were only a few cellulose ethers derivatives with limited molecular weight range and type and degree of substitution which were effective in the process of the invention. Effective amounts of hydroxyethylcellulose, carboxymethylmethylcellulose, carboxymethylmethylhydroxyethylcellulose and carboxymethylmethylhydroxypropylcellulose in a polymerization reaction range from 0.01 to 0.50% by weight based on the weight of vinyl monomer, whereas in the case of hydrophobically modified hydroxyethylcellulose the effective amount ranges from 0.01 to 0.60% by weight. A preferred range is 0.05 to 0.30% by weight. All of these materials are available from the Aqualon Company. Preferably, the hydrophobically modified hydroxyethylcellulose is modified with hexadecyl, butyl or decyl in an amount of 0.2 to 0.7% by weight based on the total weight of the hydrophobically modified hydroxyethylcellulose. Carboxymethyl degree of substitution (D.S.) should be from 0.05 to 1.0, preferably from 0.2 to 0.6. Hydroxypropyl substitution should be from 2 to 12% by weight and hydroxyethyl substitution from 1 to 15% by weight. The carboxymethylcellulose, carboxymethylmethylhydroxypropylcellulose or carboxymethylmethylhydroxyethylcellulose has a preferred degree of carboxymethyl substitution of 0.2 to 0.8 and a methoxyl substitution of 20 to 30%. Suspension polymerizations were run to test the effectiveness of the suspending agent using variations of the following recipe: Vinyl monomer300 - 610g Deionized water740 - 1050 g Initiator0.6 - 2.0 g Stabilizer0.1 - 3.0 g Tri-calcium phosphate0 - 0.25 Reaction temperature75°C Reaction time5 - 8 hours Stirrer speed600 rpm In each case the polymerization was run at atmospheric conditions under a nitrogen blanket. After cooling to room temperature the suspension was filtered through a Büchner funnel and washed with deionized water, methyl alcohol and finally with deionized water. The following examples illustrate the practice of the invention which has industrial applicability for vinyl polymerization. Example 1Styrene Polymerized with High Molecular Weight HECThe following formulation was used with hydroxyethylcellulose (HEC) available from the Aqualon Company to give the results shown in Table 1. Styrene610 g Deionized water740 g Initiator2 g StabilizerVaried towards average PS-particle size of 400 µm Reaction temperature90°C Reaction time8 hours Stirrer speed600 rpm Example Molecular Weight of HEC Use Level HEC (% w/w) PSD (%) Emulsion Polystyrene (% w/w) Control290000 (250 G)0.28640.2 Ex. 1A690000 (250 M)0.20660.1 Ex. 1B1000000 (250 HH)0.18700.1 The above examples 1A and 1B demonstrate the positive effect of these high MW types over the standard type Natrosol® 250G hydroxyethylcellulose with respect to stabilizing efficiency and homogeneity of the particle size distribution. Example 2Methylmethacrylate Polymerized With High Molecular Weight HECThe following formulation was used with hydroxyethylcellulose (HEC) available from the Aqualon Company as shown in Table 2. Methylmethacrylate300 g Deionized water1050 g Initiator0.6 g StabilizerVaried towards average PMMA -particle size of 400 µm Reaction temperature75°C Reaction time5 hours Stirrer speed600 rpm Example Molecular Weight of HEC Use Level HEC (% w/w) PSD (%) Control290000 (250 G)0.1863 Ex. 2690000 (250 M)0.1470 From above table we can draw the conclusion that in the methylmethacrylate system the same advantages were observed as in Example 1 with styrene polymerization. Example 3Effect of Hydrophobic Modification and Molecular Weight of HMHEC and its combination With a Water Insoluble Salt Like Tri-Calcium PhosphateUsing the formulation of Example 1, a positive effect was observed for hydrophobically modified hydroxyethylcellulose (HMHEC) over non-modified HEC when combining these products with a water insoluble salt like tri-calciumphosphate (TCP). Moreover particle size control of the polystyrene beads could be accomplished by controlling the hydrophobic modification in HMHEC with respect to type and amount in combination with the molecular weight of the HEC backbone. Table 3 contain comparative results. HMHEC VERSUS HEC IN COMBINATION WITH TCP Hydrophobe TCP (% w/w) WSP (% w/w) PSD (%) Type w/w (%) Control Natrosol® 250G HEC---0.2864 Example 3A HMHECHexadecyl0.4-0.6-0.2573 Control Natrosol® 250G HEC--0.250.3251 Example 3B HMHECHexadecyl0.4-0.60.250.2375 The above table demonstrates the positive influence of hexadecyl modification on particle size control and stabilizing efficiency. Example 4Example 3 was varied by using different hydrophobic alkyl chains on the hydrophobically modified HEC. Table 4 gives comparative results. THE EFFECT OF THE LENGTH OF THE HYDROPHOBIC ALKYL CHAIN Hydrophobe WSP (% w/w) TCP (% w/w) PSD (%) Type w/w (%) Control Natrosol® 250G --0.280.2551 Example 4AButyl0.4-0.60.270.2566 Example 4BDecyl0.4-0.60.250.2565 Example 4CHexadecyl0.4-0.60.230.2575 Despite the fact that a length of the alkyl chain longer than C16 has not been tested yet, a clear tendency can be observed, i.e., an improvement in stabilizing efficiency as well as particle size control resulting in a more homogeneous particle size distribution. Example 5Example 3 was varied by using varying amounts of hexadecyl modification. Table 5 gives comparative results. THE EFFECT OF VARYING HEXADECYL MODIFICATION Hydrophobe TCP (% w/w) WSP (% w/w) PSD (%) Type w/w (%) Control Natrosol® 250G--0.280.2551 Example 5AHexadecyl0.2-0.40.180.2562 Example 5BHexadecyl0.4-0.60.230.2575 Example 5CHexadecyl0.6-1.00.220.2572 As can be observed from the above table, an optimum hydrophobe level exists in the order of 0.5% w/w with respect to particle size distribution. Example 6Example 3 was varied by using different molecular weight HEC backbone with equivalent hexadecyl substitution. Table 6 gives comparative results. EFFECT OF MOLECULAR WEIGHT OF HEC BACKBONE Hydrophobe Molecular Weight WSP (% w/w) TCP (% w/w) PSD (%) Type w/w (%) Reference Example 6AHexadecyl0.4-0.6900000.180.2562 Example 6BHexadecyl0.4-0.62900000.230.2575 Example 6CHexadecyl0.4-0.66900000.220.2572 The experimental data shows that an optimum molecular weight exists for the HMHEC for an effective particle size control. The examples 4, 5 and 6 demonstrate how the suspension polymerized polystyrene beads can be controlled by means of molecular weight of HEC backbone, type and amount of hydrophobic modification in combination with an inorganic pickering stabilizer like TCP. On top the formation of emulsion polystyrene appeared to be very low: <0.1% w/w on styrene monomer. Example 7The methylmethacrylate formulation of Example 2 was used with a hexadecyl hydrophobe HEC. Comparative results are shown in Table 7. Hydrophobe Molecular Weight WSP (% w/w) TCP (% w/w) PSD (%) Type w/w (%) Control250G0.4-0.62900000.320.2551 Example 7Hexadecyl0.4-0.62900000.080.2570 Example 7 shows that the hydrophobically modified HEC of Example 6 is also an effective stabilizer in the S-polymerization of methylmethacrylate. Example 8Carboxymethylated cellulose derivatives were evaluated in combination with tri-calcium phosphate for effective stabilization in suspension polymerization. Table 8 gives comparative results where all polymers are available from Aqualon Company. COMBINATIONS OF CARBOXYMETHYLATED CELLULOSE DERIVATIVES WITH TRI-CALCIUM PHOSPHATE WSP (% w/w) TCP (% w/w) Particle Size (microns) PSD (%) ControlBlanose™ 7M31D0.25-Coagulum ControlBlanose™ 7M31D0.250.25Coagulum Ex. 8ABlanose™ 7M31D/Natrosol® 250G0.25/0.10.2533563 Ex. 8BCMHEC 420G0.250.2556350 Ex. 8CCMMHEC0.2540048 Ex. 8DCMMHEC 0.180.2540062 Ex. 8ECMMHPC 0.14-40026 Ex. 8FCMMHPC 0.110.2540078 The above samples show several combinations of carboxymethylated cellulose derivatives with TCP. From these examples it was shown that a combination of carboxymethylated MHEC and TCP as well as carboxymethylated with TCP gave excellent particle size control with narrow PSD's. These combinations performed much better than these cellulose derivatives alone.	A process for controlling particle size of polymers, prepared by a suspension polymerization process, from vinyl monomers in the presence of an initiator and a thickening agent, characterized in that the thickening agent is a cellulose ether derivative of one or more of: (a) hydroxyethylcellulose with a molecular weight of 300,000 to 1,000,000 and a molar substitution (M.S.) of 1.5 to 3.5 which is used in an amount of 0.01 to 0.50% by weight based on the weight of vinyl monomer; (b) hydrophobically modified hydroxyethylcellulose with a molecular weight of 100,000 to 800,000 and an M.S. of 1.5 to 4.1 with a hydrophobic modification chain of C4 to C22 in an amount of 0.1 to 1.0 percent by weight based on the total weight of the hydrophobically modified hydroxyethylcellulose which is used in an amount of 0.01 to 0.6% by weight; (c) carboxymethylmethylcellulose, carboxymethylmethylhydroxyethylcellulose or carboxymethylmethylhydroxypropylcellulose with a molecular weight of 20,000 to 400,000 with a degree of carboxymethyl substitution of from 0.05 to 1.0 which is used in an amount of 0.01 to 0.50% by weight based on the weight of vinyl monomer; such that a polymer prepared from the vinyl monomer has a homogeneity of particle size distribution (PSD) with 60% or higher and the weight percentage of latex is below 0.1% by weight based on the starting weight of the vinyl monomer selected from the group of styrene, methylmethacrylate, vinyl chloride, diethylaminoethylmethacrylate and butylmethacrylate. The process of claim 1 where the hydroxyethylcellulose has a molecular weight above 500,000 and an M.S. of 2.0 to 3.0. The process of claim 2 where tri-calcium phosphate (TCP) is used in combination with hydroxyethylcellulose. The process of claim 1 where the hydrophobically modified hydroxyethylcellulose is modified with hexadecyl, butyl or decyl. The process of claim 4 where the modification is in an amount of 0.2 to 0.7 percent by weight based on the total weight of the hydrophobically modified hydroxyethylcellulose. The process of claim 5 where the hydrophobically modified hydroxyethylcellulose is used in combination with TCP. The process of claim 1 where carboxymethylmethylcellulose, carboxymethylmethylhydroxyethylcellulose or carboxymethylmethylhydroxypropylcellulose have a degree of carboxymethyl substitution of 0.2 to 0.6. The process of claim 7 where the thickening agent is used in combination with TCP. The process of claim 1 where carboxymethylcellulose has a degree of carboxymethyl substitution of 0.2 to 0.8 and a methoxyl substitution of 20 to 30%. The process of claim 1 where carboxymethylmethylhydroxypropylcellulose has a degree of carboxymethyl substitution of 0.2 to 0.8 and a methoxyl substitution of 20 to 30%. The process of claim 1 where carboxymethylmethylhydroxyethylcellulose has a degree of carboxymethyl substitution of 0.2 to 0.8 and a methoxyl substitution of 20 to 30%.	AQUALON CO; AQUALON COMPANY	KROON GIJSBERT; KROON, GIJSBERT
EP-0489426-B1	489,426	EP	B1	EN	19,970,820	1,992	20,100,220	new	G03F7	null	G03F7, H01L21	G03F 7/20T16, G03F 7/20B	Projection exposure method	For projecting a photomask (5) pattern on a wafer (10) using a projection optical system (1-4,6) having a short wavelength light source (1) and a high numerical aperture, a method for projection exposure is proposed, by which a focal margin may be improved to achieve stable resolution and improved throughput. It is assumed for example that three-stage sequential light exposure is performed by setting an image plane at three positions, namely at a center focal position which is a mean height position of highs and lows of the water surface step difference and plus and minus focal positions offset a predetermined amount on each side of the center focal position. If light exposure is performed at each of these positions with an exposure light volume equal to one-third of the total exposure light volume, the focus margin becomes smaller than that in the case of the two-stage light exposure. By using a relatively small exposure light volume at the center focal position according to the present invention, the focal margin may be enlarged, although the synthesized light intensity contrast becomes minimum at the center focal position. The same effect may also be achieved by continuous light exposure with the constant exposure light volume using a relatively high speed of movement of the image plane at the center focal position for improving the throughput.	BACKGROUND OF THE INVENTIONField of the InventionThis invention relates to a method according to the preamble of claim 1 for projection exposure applied to photolithography for preparation of semiconductor devices. More particularly, it relates to a method for exposure projection which allows for uniform resolution over an entire wafer surface. Description of Related ArtIn the field of semiconductor integrated circuits, submicron size processing has already been realized in mass-producing plants, while researches are currently conducted on half-micron size processing and even on quarter-micron size processing which is thought to be indispensable in 64 Mbit level DRAMs. The technology which has played a key role in the progress of ultra-fine processing is photolithography. The progress so far achieved in ultra-fine processing owes much to reduction in exposure wavelengths of the exposure light and an increase in the numerical aperture (NA) of optical lenses of a stepper. However, the reduction in the exposure light wavelengths and the increase in the numerical aperture are not desirable from the viewpoint of increasing the depth of focus, because the depth of focus is proportionate to the wavelength of exposure light and inversely proportionate to the second power of numerical aperture. On the other hand, the surface step difference of a semiconductor wafer as a member to be exposed tends to be increased recently with increase in the density of semiconductor integrated circuits. The reason therefore is that, for the sake of maintenance of circuit performance and reliability under the current tendency towards a three-dimensional device construction, reduction in the three-dimensional design rule is not progressing smoothly as compared to that in the two-dimensional design rule. If the surface of a semiconductor wafer presenting larger step differences is coated with a photoresist material to form a photoresist layer, larger step differences or fluctuations in film thicknesses are similarly produced in the so-formed photoresist layer. As to the step differences produced over finer patterns, the wafer surface was smoothed by a multilayer resist method. However, a step difference produced over a wider area, such as a step produced between memory cells and peripheral circuits, can not be compensated with the multilayer resist method. If such wafer is to be exposed to light, the position of an image plane can not but be selected to be a mid position between highs and lows of the step difference. In addition, the image plane can not be a completely flat plane due to distortion of the image plane of a projecting lens, while the wafer surface can not be completely normal to an optical axis of the projecting optical system. Under these circumstances, and also as a result of increased light absorption of the photoresist material caused by use of shorter wavelengths, difficulties are raised in achieving uniform resolution on an entire wafer surface. Thus the requirements for resolution and those for depth of focus are essentially contradictory to each other. For combatting this problem, researches are being conducted for developing techniques for achieving high contrast and hence high resolution through special artifices and methods for using an exposure device on the premise that the numerical aperture is suppressed to a predetermined level and a practically useful level of depth of focus is maintained. Among these techniques is a so-called FLEX method, according to which, as disclosed in JP Patent KOKAI (Unexamined) Publication No.58/17446 (1983), a number of light exposure operations is carried out while the image plane is shifted through the same photomask for effectively maintaining optical image contrast extended along the optical axis. For shifting the image plane, at least one of the photomask, semiconductor wafer or the projecting optical system is wobbled along the optical axis, as disclosed in the above mentioned Publication, or shifted stepwise or continuously each time light exposure is performed, as disclosed in JP Patent KOKAI Publication No.63/64037 (1988). The simplest FLEX method is a two-stage method having two different points on the optical axis as positions for the image plane. Referring to Fig.1, an example in which the image plane is shifted along the optical axis (Z axis) by vertically driving a wafer-setting Z stage is hereinafter explained. In this figure, the stage position (in µm) along the Z axis is plotted on the horizontal axis. This stage position is defined as an offset (focal offset) from a reference point which is the position of the image plane set at a mean height position between the highs and lows of the step difference of the wafer (center focal position) as a point of origin. The direction proceeding towards a light source and that away from the light source are termed the minus (-) direction and the (+) direction, respectively, while the position of the image plane in which the wafer is shifted in the (-) direction and that in which the wafer is shifted in the (+) diction are termed the minus (-) focal position and the plus (+) focal position, respectively. The contrast in light intensities is plotted on the vertical axis. Two solid lines e and f represent contrasts in light intensities when projection light exposure is performed with the same volume of light exposure with the image plane having been shifted -1.0 pm and +1.0 µm from the point of origin, respectively. A broken line g represents contrasts of light intensities obtained by synthesizing the curves e and f. Although the light intensity contrast strictly is not in linearly correlated with the volume of light exposure, it is assumed herein to correspond approximately to the volume of light exposure for convenience. In order for the pattern to be dissolved satisfactorily on the entire surface of the wafer, a light intensity contrast higher than a predetermined level need to be maintained within a predetermined extent along the optical axis as determined by the step difference of a wafer surface, distortion of an imaging surface of a projecting lens, tilt of the wafer or the like. If it is assumed that an appropriate extent of the light intensity contrast corresponding to a practically sufficient resolution is 0.5 to 0.8 and the range along the Z axis with which such range of the light intensity contrast is achieved is defined as a focal margin, the focal margin as viewed on the synthesized light intensity contrast shown by the broken line g is approximately 1.2 µm along the (-) and (+) directions, or 2.4 µm in sum, as shown by ranges B1 and B2. However, the synthesized light intensity contrast becomes lower than 0.5 in the vicinity of the center focul position so that stable resolution can not be achieved. The result is that inconveniences such as fluctuations in contact hole diameters, for example, are produced. On the other hand, a three-stage method has also been proposed, in which light exposure at the center focal position is additionally performed in the above mentioned two-stage method. This alternative method is hereinafter explained by referring to Fig.2. In an example, shown in Fig.2, light exposure is performed not only at the focal offsets at +1.0 µm, but also at the center focal position. Thus, in Fig.2, three solid lines h, i and j represent light intensity contrast curves when projection light exposure is performed with the same volume of light exposure with the focal offsets of -1.0 µm, 0 µm and +1.0 µm, respectively. A broken line k represents a light intensity contrast curve obtained by synthesis of three curves h, i and j. It is noted that, since the total volume of light exposure is the same as that with the above mentioned two-stage method, the volume of light exposure for one light exposure operation is less than that in the case of the two-stage method. With this technique, the focal margin as seen on the synthesized light intensity contrast curve shown by the broken line k is obtained as a continuous range which, as shown by a range C in Fig.2, in contrast to the two-stage method, meaning that instability in the vicinity of the center focal position has now been eliminated. However, the focus margin with the above mentioned three stage method is about 2.2 µm, as shown in Fig.2, which is less than that obtained with the two-stage method shown in Fig.1. Thus the merit proper to the three-stage method may not be said to be functioning satisfactorily. Object and Summary of the inventionIt is therefore an object of the present invention to provide a projection exposure method comprising setting the image plane in three or more stages in effecting light exposure, whereby not only the focal margin may be enlarged but also the throughput may be improved. To solve this object the present invention provides a method as specified in claim 1. The dependent claims describe particular embodiments of the invention. The reason the focal margin is decreased with the conventional three-stage method as compared with that with the two-stage method is that, as a result of dividing the total volume of light exposure into three equal parts, the light intensity contrast is decreased in its entirety, above all, it is decreased most acutely at both ends of the range of shifting of the image plane. The present inventor has directed attention to the fact that the light intensity contrast is improved in the vicinity of the center focal position in the case of the curve for the synthesized light intensity contrast shown by broken line k in Fig.2, and arrived at a notion that, if the volume of light exposure in this region is partially distributed to the minus focal and plus focal sides, the focal margin may be enlarged in its entirety, even although the profile of the curve should be decreased to a minimum value near the center focal position. It is on the basis of this concept that, in effecting light exposure by setting three or more positions for the image plane in accordance with the present invention, the volume of light exposure is reduced relatively in the vicinity of the center of the setting range of the image plane. However, with sequential light exposure in which it is necessary to perform stage movement and stop, shutter opening and closure and increase or decrease of the light exposure power, throughput can not be improved beyond a certain threshold value. In this consideration, the present invention further proposes a method comprising moving at least one of the projecting optical system, photomask and the wafer along the optical axis with a speed distribution depending on the position of the image plane along the optical axis. With the proposed method, the volume of light exposure is decreased and increased in regions of higher and lower speeds, respectively, even if the volume of light exposure is constant and the shutter is perpetually in the open condition. If it is desired to decrease the volume of light exposure in the vicinity of the center focal position, it suffices to increase the speed of one of the optical system, photomask and the wafer in the vicinity of the center focal position. As a result, the number of parameters to be controlled is decreased and the throughput markedly improved as compared with those with the conventional multi-stage light exposure system. It will be seen from above that, in accordance with the present invention, the focal margin may be enlarged by relatively decreasing the volume of light exposure in the vicinity of the center focal position. On the other hand, throughput my also be improved by an ingenuous artifice of gradating the speeds of movement along the Z axis of the unit(s) capable of moving the image plane. Thus the present invention has a significant practical merit under the situation of the decreased depth of focus as a consequence of the use of shorter wavelengths of the exposure light and the higher numerical aperture. BRIEF DESCRIPTION OF THE DRAWINGSFig.1 is a graph showing light intensity contrast curves with the conventional two-stage method. Fig.2 is a graph showing light intensity contrast curves with the conventional three-stage method. Fig.3 is a schematic view showing an example of construction of a projection light exposure device employed for practicing the invention. Figs.4a to 4c are schematic cross-sectional views showing an example of position setting of an image plane in case the present invention is applied to a three-stage method, wherein Fig.4a shows the minus focal position, Fig.4b shows the center focal position and Fig.4c shows the plus focal position. Fig.5 is a graph showing light intensity contrast curves obtained on application of the present invention to a three-stage method. Fig.6 is a graph showing a pattern of gradation of the speed of movement of the Z stage on application of the present invention. DETAILED DESCRIPTION OF THE INVENTIONReferring to the drawings, certain preferred embodiments of the present invention will be explained in detail. Example 1In the present example, the present invention is applied to a three-stage method, and the image plane is moved by raising and lowering the wafer. Fig.3 shows a schematic structure of a projection optical system and a control system of a projection exposure device employed in the present example. With the projection optical system, the light radiated from a light source 1 is reflected and converged by a reflective mirror 2 to fall via an aperture 3 on a collimator lens 4 whereby it is collimated and then transmitted through a photomask 5 so as to be projected by an imaging lens 6 on a wafer 10 placed on a wafer stage 7. The wafer stage 7 is composed of an XY stage 8 for shifting the wafer 10 in its in-plane direction or XY direction and a Z stage 9 for shifting the wafer along the optical axis or Z axis. The wafer 10 may be moved to a designated position three-dimensionally by the combination of the movements of the stages 8 and 9. The control system is made up of a shutter control system 17 for controlling the timing of light exposure, an XY control system 14 for driving the XY stage 8 to a designated position, an XY sensor 11 for detecting the relative position of the wafer 10 in the XY plane, a Z control system 13 for driving the Z stage 9 to its designated position, a Z sensor 12 for detecting the relative position of the wafer 10 in the Z axis direction, a computer 16 for collectively controlling the light exposure device in its entirety and a bus line for interconnecting the control systems 13, 14 and 17 with the computer 16. In this computer, the light exposure position in the XY plane on the wafer 10, the number of the image planes set for the respective light exposure positions in the XY plane, the amount of movement of the Z stage 9 and the volume of light exposure for the image plane in each of the light exposure positions etc. are stored previously. The control systems 13, 14 and 17 receive various signals generated on the basis of the information stored in the computer 16 over bus line 15 to perform prescribed control operations. In Figs.4a to 4c, the manner in which the image plane is moved for light exposure in accordance with the three-stage method is shown schematically. In these figures, light exposure is performed while the image plane is moved within an extent of +1 µm with respect to the wafer 10 comprised of a photoresist layer 21 formed on a substrate 20 formed of a predetermined layer of material. It is noted that warping of the wafer 10, surface step differences of the photoresist layer 21 or distortions of the image plane caused by aberrations of the projection optical system, generated in a region, not shown, are substantially contained within this extent of movement of 2 µm. The coordinate system data entered in the figures are intended for aiding in the understanding of the movement of the image plane along the z axis (focal offsetting). Thus the origin 0 denotes a mid point of the extent of the movement, the minus (-) direction is the direction of approaching the imaging lens 6 and the plus (+) direction denotes the direction of moving away from the imaging lens 6. Fig.4a shows the minus focal position with the focal offset of -1.0 µm, Fig.4b shows the center focal position with the focal offset of 0 µm and Fig.4c shows the plus focal position with the focal offset of +1.0 µm. The following is the sequence of effecting light exposure by the three-stage method using the above described projection light exposure device. The method described below is a method for light exposure known as a step-and-repeat system. After the XY control system 14 has moved the XY stage 8 to a predetermined position under the commands from the computer 16, the Z control system 13 actuates the Z stage 9 to uplift the wafer 10 to a position corresponding to -1.0 µm of the focal offset, as shown in Fig.4a. The relative position of the wafer 10 is fed back to the XY control system 14 and the Z control system 13 by means of the XY sensor 11 and the Z sensor 12 so as to be corrected automatically if necessary. A shutter, not shown, is opened under the commands of the shutter control system 17 to effect light exposure with a predetermined exposure light volume. After the end of light exposure, the shutter is closed and the Z stage 9 is actuated for lowering the wafer 10 to the center focal position shown in Fig.4b where light exposure is again performed by the same sequence of operations as described above. After the end of the second light exposure, the wafer 10 is further lowered to a position corresponding to the focal offset of +1,0 µm, as shown in Fig.4c, where light exposure is again performed by the same sequence of operations. It is noted that, at the time of light exposure near the center focal position, among the above described three light exposure operations, the exposure light volume is decreased as compared to that at the time of the light exposure at the plus and minus focal offset positions. This is shown by light intensity contrast curves shown in Fig.5, in which three solid lines a, b and c represent the light intensity contrast curves corresponding to the focal offsets of -1.0 µm, 0 µm and +1.0 µm, respectively. It is noted that the volume of light exposure at the focul offsets of ±1.0 µm is selected to be slightly smaller than that with the two-stage method shown in Fig. 1, with the decreased volume of exposure light being distributed and supplemented to the exposure light volume at the center focal position. A light intensity contrast curve shown by a broken line d is obtained by synthesizing these three curves together. By such light exposure, a continuous focal margin extending about 2.8 µm is achieved, as shown at a range A in Fig.5, due to the fact that the drop of the light intensity contrast in the vicinity of both ends of the extent of the Z stage movement as shown in Fig.2 is suppressed, while that in the vicinity of the center focal position as shown in Fig.1 is reduced. It is noted that, although the three-stage light exposure is started in the above explanation from the minus focus side, it may also be started from the plus focus side without any inconvenience. It is also noted that, although the image plane is set in the above embodiment at three prescribed positions on the XY plane, the present invention is not limited to this embodiment, but may be applied to cases of setting the image plane at four or more positions. In these cases, it becomes necessary to optimize the distribution of the exposure light volume depending on the number of the setting positions of the image plane. To this end, it suffices to decrease the exposure light volume at the center focal position relatively for odd-numbered setting positions for the image plane and at least two positions on both sides of the center focal position for even-numbered setting positions for the image plane. Example 2In the present example, the efficiency of the light exposure operation is improved further as compared to that achieved with the preceding example 1. The construction of the wafer 10 and the projection light exposure device employed in the present example 1 as well as the extent of movement of the image plane is the same as that described in example. However, the operation of light exposure is not performed herein by the above mentioned step-and-repeat system, but, with the shutter in the perpetually opened state, the speed of movement of the Z stage is changed in accordance with a pattern shown for example in Fig.6. That is, the speed of movement of the Z stage was set so that it is rather small in the vicinity of ±1.0 µm offsets and increased as the Z stage approaches to the center focal position, becoming maximum at the center focal position. In this case, the above mentioned pattern of speed change or gradation need to be stored in the computer 16 instead of the number of setting positions of the image plane. Under such setting, if the exposure light power is constant, the volume of light exposure is proportionate to the light exposure time, which in turn is inversely proportionate to the stage shifting speed. Thus the volume of light exposure becomes maximum and minimum in the vicinity of the center focal position ±1.0 µm and in the vicinity of the center focal position, respectively, so that a pattern of changes or gradations of the exposure light volume approximately similar to that of Fig.5 is achieved. The changes or gradations of the exposure light volume may naturally be combined in any desired manner with those of the shifting speed of the Z stage 9. With the present method, the image plane may be moved continuously without intermediate stopping, while only one light exposure operation at one of the light exposure positions on the XY plane suffices. The result is that the time consumed in the movement and stopping of the Z stage 9 or shutter opening and closure may be saved so that throughput may be improved significantly.	A method for projection exposure of projecting a photomask (5) pattern on a wafer (10) by a projection optical system (1-4,6) comprising setting an image plane of said pattern on said wafer (10) at three or more positions along the optical axis of said optical system (1-4,6) within a predetermined extent, and carrying out light exposure operations sequentially at these positions, characterized in that the exposure light volume at or near the mid point of said extent is smaller than that at both ends of said extent. The method as claimed in claim 1 wherein setting of said image plane is performed by driving said projection optical system (1-4,6). The method as claimed in claim 1 wherein setting of said image plane is performed by driving said photomask (5). The method as claimed in claim 1 wherein setting of said image plane is performed by driving (see 8) said wafer (10).	SONY CORP; SONY CORPORATION	KITAGAWA TETSUYA; KITAGAWA, TETSUYA
EP-0489428-B1	489,428	EP	B1	EN	19,950,726	1,992	20,100,220	new	B05D3	C04B41, C23C18	C09D183, B05D3, C04B41, C23C18	C09D 183/16, B05D 3/04, C04B 41/50R58H, C04B 41/87, C04B 41/52, C23C 18/12, C04B 41/89	Formation of heat-resistant dielectric coatings	Heat resistant, dielectric coatings are formed by applying a heat resistant coating composition comprising an organic silicon polymer, a silazane compound, and an inorganic filler to a substrate, and baking the coating in ammoniacal atmosphere at 200 to 1000°C. Similarly, heat resistant, dielectric coatings are formed by applying the same composition as above to a substrate, baking a first coating layer in air, applying an organic silicon polymer base coating composition to the first coating layer, and baking a second coating layer in ammonical atmosphere.	This invention relates to a method for forming heat-resistant, dielectric coatings having improved adhesion, heat resistance, and electric insulation. Polyorganosiloxane base coating compositions are superior in heat resistance to coating compositions of organic polymers such as polyester and polyimide, but cannot withstand elevated temperatures of higher than 400°C for a long time. In the recent years, there is an increasing demand for coating compositions capable of preventing oxidation and corrosion of metallic and non-metallic substrates which are serviced at high temperatures in excess of 1000°C. It is also desired to develop coating compositions which form coatings maintaining electric insulation at high temperatures and having good adhesion. A variety of heat resistant coating compositions have been proposed in the art. (1) Japanese Patent Application Kokai (JP-A) No. 54768/1987 discloses a composition comprising a polytitanocarbosilane, a silicone resin, and an inorganic filler. (2) JP-A 235370/1987 discloses a composition comprising a polycarbosilane, a silicone resin, and an inorganic filler. (3) JP-A 92969/1990 discloses a heat resistant coating composition having an organometallic polymer and silicon dioxide blended therein. (4) Japanese Patent Publication No. 50658/1983 discloses a composition comprising a borosiloxane resin. These proposals, however, have some drawbacks. Heat resistant coating compositions (1) and (2) are unsatisfactory in adhesion to substrates at high temperatures, crack resistance of coatings, and high-temperature electric insulation. Heat resistant coating composition (3) suffers from separation and cracking of coatings at high temperatures and poor electric insulation. Heat resistant coating composition (4) is poor in water resistance and high-temperature electric insulation. The previously proposed approaches do not satisfy all the requirements of high-temperature adhesion, heat resistance, water resistance, and electric insulation. There is a need for developing a heat resistant coating composition capable of satisfying all such requirements. JP-A-2 092 534 discloses a method of forming a heat resistant dielectric coating onto a substrate. An undercoating is formed by applying a resin, such as a polycarbosilane resin or polysilazane resin which further contains an insulating inorganic filler. An upper layer is provided on the underlayer by coating and baking a finish coating containing a resin, such as a polycarbosilane resin or a polysilazane resin. JP-A-63-234 069 discloses a method of preparing a heat resistant coating by applying a suspension of a resin, such as a polycarbosilane resin or a polysilazane resin, an inorganic filler and a silicone resin and/or heat-resistant synthetic resin containing nitrogen-containing heterocyclic rings in the molecule in an organic solvent. Therefore, an object of the present invention is to provide a method for forming coatings which firmly adhere to metallic and non-metallic substrates, and have improved heat resistance, water resistance, solvent resistance, corrosion resistance and high-temperature electric insulation. The inventors have found that by applying a heat resistant coating composition comprising an organic silicon polymer, a silazane compound, and an inorganic filler to a conductive or non-conductive substrate, and baking the composition in ammonia gas or a mixture of ammonia and an inert gas, there are formed ceramic heat-resistant, dielectric coatings on the substrate featuring improved properties including heat resistance, electric insulation and close adhesion as well as high hardness, water resistance, chemical resistance and solvent resistance. Also the inventors have found that by forming a first coating layer on a substrate from a heat resistant coating composition comprising an organic silicon polymer, a silazane compound, and an inorganic filler, and then forming a second coating layer on the first coating layer from a coating composition comprising an organic silicon polymer, especially by baking the second coating layer in ammonia gas or a mixture of ammonia and an inert gas, there are formed composite coatings featuring improved properties including heat resistance, water resistance, close adhesion, solvent resistance, and electric insulation. Therefore, in a first form, the present invention provides a method for forming a heat resistant, dielectric coating comprising the steps of applying a heat resistant coating composition comprising an organic silicon polymer, a silazane compound selected from the group consisting of tetramethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane and mixtures thereof, and an inorganic filler to a substrate; and baking the coating in an atmosphere of ammonia gas or a mixture of ammonia gas and an inert gas. In a second form, the present invention provides a method for forming a heat resistant, dielectric coating comprising the steps of applying a heat resistant first coating composition comprising an organic silicon polymer, a silazane compound selected from the group consisting of tetramethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane and mixtures thereof, and an inorganic filler to a substrate; baking the first composition to form a first coating layer; applying a second coating composition comprising an organic silicon polymer to the first coating layer; and baking the second composition to form a second coating layer on the first coating layer, preferably in an atmosphere of ammonia gas or a mixture of ammonia and an inert gas. The present invention uses a heat resistant coating composition comprising an organic silicon polymer, said silazane compound, and an inorganic filler as essential binding components. A first essential component of the heat resistant coating composition according to the present invention is an organic silicone polymer which is preferably selected from polycarbosilanes and polysilazanes. The polycarbosilanes are known from JP-B 26527/1982 (or US 4,052,430, DE 2618246, FR 2308650 and GB 1551952), for example. Such polycarbosilanes may be synthesized, for example, by reacting dimethyldichlorosilane with metallic sodium and subjecting the resulting polysilanes to pyrolytic polymerization. The polysilazanes are known from the following patent publications and applications, all by Shin-Etu Chemical Co., Ltd. (1) JP-A 290730/1987 which corresponds to US 4,771,118 and 4,870,035, FR 2,599,745 and DE 3,719,343 A1 and discloses a process for manufacturing an organic silazane polymer which comprises reacting ammonia with a mixture of methyldichlorosilane, methyltrichlorosilane and dimethyldichlorosilane to obtain an ammonolysis product, and polymerizing the ammonolysis product in the presence of a basic catalyst capable of deprotonation to obtain an organic silazane polymer. Preferably, the mixing ratios of methyldichlorosilane, methyltrichlorosilane and dimethyldichlorosilane are in ranges of 55 to 80 mol %, 10 to 30 mol % and 5 to 25 mol %, respectively. (2) JP-A 117037/1988 and 193930/1988 which correspond to US 4,869,854, FR 2,606,777 and DE 3,736,914 A1 disclose a process for manufacturing an organic silazane polymer which comprises: reacting ammonia with a mixture consisting of at least one compound selected from the group consisting of organic silicon compounds of the formula (I); at least one compound selected from the group consisting of organic silicon compounds of the following formula (II); and at least one compound selected from the group consisting of organic silicon compounds of the following formula (III); in which R represents hydrogen, chlorine, bromine, methyl radical, ethyl radical, phenyl radical or vinyl radical; R₁ represents hydrogen or methyl radical, R₂ represents hydrogen, methyl radical, ethyl radical, phenyl radical or vinyl radical and X represents chlorine or bromine, to obtain an ammonolysis product, the mixing ratios of the organic silicon compounds shown by the above formulae (I), (II), and (III) being in ranges of 1 to 25 mol %, 1 to 25 mol %, and 50 to 80 mol %, respectively, and polymerizing the ammonolysis product in the presence of a bacic catalyst capable of deprotonation to obtain an organic silazane polymer. Preferably, the amounts of hydrogen, vinyl radical and alkyl or phenyl radical in R₂ of the organic silicon compounds of the formulae (II) and (III) are in ranges of 55 to 90 mol %, 0 to 30 mol % and 0 to 30 mol %, respectively. (3) JP-A 210133/1988 which corresponds to US 4,847,345, FR 8802317 and DE 3805796 A disclose a process for manufacturing an organic silazane polymer which comprises reacting an organic silicon compound of the following formula (I): in which R represents hydrogen, chlorine, bromine, methyl radical, ethyl radical, phenyl radical or vinyl radical, R₁ represents hydrogen or methyl radical and X represents chlorine or bromine, or a mixture of an organic silicon compound of the formula (I) above and an organic silicon compound of the following formula (II): in which R₂ and R₃ represent hydrogen, chlorine, bromine, methyl radical, ethyl radical, phenyl radical or vinyl radial and X represents chlorine or bromine with a disilazane of the following formula (III): in which R₄, R₅, R₆ represents hydrogen, methyl radical, ethyl radical, phenyl radical or vinyl radical in an anhydrous state at a temperature of from 25°C to 350°C while distilling off by-produced organic ingredients out of the system to obtain an organic silazane polymer. Preferably, the mixing ratio of the organic silicon compounds shown by the above formulae (I) and (II) is in the range of 50 to 100 mol %: 0 to 50 mol %. (4) JP-A 153730/1989 which discloses a method for preparing an organic silazane polymer comprising the steps of: reacting ammonia with a mixture of an organic silicon compound of the following formula (I): in which R represents methyl radical, ethyl radical or phenyl radical and X represents chlorine or bromine, and an organic silicon compound of the following formula (II): in which R represents methyl radical, ethyl radical or phenyl radical, R₁ represents hydrogen or vinyl radial and X represents chlorine or bromine, in a mixing ratio of the compounds (I) and (II) ranging from 20:80 to 90:10 (mol %) to obtain a silazane compound, and polymerizing the silazane compound in the presence of an alkali catalyst to obtain an organic silazane polymer.; (5) JP-A 50238/1991, 51315/1991 and 51316/1991 which correspond to US SN 07/554,129 and EP 409146 A2 disclose a method for preparing an organic silazane polymer, comprising the steps of: passing a silazane compound in vapor form through a hollow tube heated at a temperature in the range of from 400 to 700°C for activating the silazane compound, and thermally polymerizing the silazane compound in a liquid phase. Preferably the silazane compound has the following formula (I) or (II):(CH₃)₃Si-NH-Si(CH₃)₃ (I)(6) JP-A 81330/1991 which corresponds to US SN 07/571,132 and EP 417562 A2 disclose a method for preparing an polytitanocarbosilazane polymer comprising the step of reacting (A) an organic silicon compound of the general formula: wherein R is selected from the group consisting of hydrogen, chloro, bromo, methyl, ethyl, phenyl and vinyl radicals, R¹ is hydrogen or a methyl radical, and X is chloro or bromo, (B) an organic silicon compound of the general formula: wherein R² and R³ are independently selected from the group consisting of hydrogen, chloro, bromo, methyl, ethyl, phenyl and vinyl radicals, and X is chloro or bromo, (C) a titanium compound, and (D) a disilazane of the general formula: wherein R⁴, R⁵ and R⁶ are independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl and vinyl radicals. Preferably, the compounds of formulae (I) and (II) are mixed in a molar ratio (I)/(II) of from 10/90 to 40/60. The titanium compound is used in an amount of 1 to 10 mol % based on the total of the organic silicon compounds of formulae (I) and (II). The disilazane of formula (III) is used in at least equimolar amount to the total of components (A), (B), and (C). (7) JP-A 190933/1991 which corresponds to US SN 07/631,272 and EP 434031 A2 disclose a method for preparing an organic silazane polymer comprising the steps of: reacting an organic silicon compound of formula (I): wherein R is selected from the class consisting of hydrogen, chloro, bromo, methyl, ethyl, phenyl, and vinyl, R¹ is hydrogen or a methyl, and X is chloro or bromo, or a mixture of an organic silicon compound of formula (I) and an organic silicon compound of formula (II): wherein R² and R³ are independently selected from the class consisting of hydrogen, chloro, bromo, methyl, ethyl, phenyl and vinyl, and X is chloro or bromo, with a disilazane of formula (III): wherein R⁴, R⁵ and R⁶ are independently selected from the class consisting of hydrogen, methyl, ethyl, phenyl and vinyl, at a temperature of 25 to 350°C in an anhydrous atmosphere, and reacting the resulting organic silazane polymer with ammonia, thereby reducing the residual halogen in the polymer. (8) JP-A 190932/1991 which discloses a method of preparing a hafnium-containing silazane polymer comprising reacting (A) a halogenated organic silicon compound such as those described above, (B) a hafnium compound of the following formula (I):HfX₄ (I) in which X represents chlorine or bromine, and (C) a disilazane of the following formula (II) in which R₁, R₂ and R₃ are independently selected from hydrogen, methyl radical, ethyl radical, phenyl radical and vinyl radical. In the present invention, the polycarbosilanes and the polysilazanes are used as the organic silicone polymers as described above. Since the degree of polymerization of the organic silicone polymer largely affects coating performance, especially coating crack resistance, the polycarbosilanes should preferably have a number average molecular weight of about 500 to 5,000, more preferably from about 600 to about 2,000, most preferably from about 650 to about 1,200, and the polysilazanes preferably have a number average molecular weight of about 400 to about 3,000, more preferably from about 500 to about 2,000, most preferably from about 550 to about 1,200. Below the lower limit of number average molecular weight, the resulting composition would poorly adhere to substrates. Above the upper limit, cracks would occur in the resulting coatings which could be peeled off during subsequent baking. The organic silicone polymers may be used alone or in admixture of two or more. Preferably the composition contains about 5 to 50% by weight, more preferably about 15 to 30% by weight of the organic silicone polymer based on the total weight of the composition (organic silicone polymer plus silazane compound plus inorganic powder). Less than 5% by weight of the organic silicone polymer would sometimes be too small to provide the composition with satisfactory heat resistance, adhesion, and coating hardness whereas more than 50% would sometimes form coatings susceptible to cracking and peeling after baking. The organic silicone polymer component is generally converted into SiC, Si₃N₄ and the like by subsequent baking of coatings in an inert gas such as nitrogen and argon. If coatings are baked in air, then the organic silicone polymer component is converted into a ceramic material consisting essentially of SiC, Si₃N₄ and SiO₂, ensuring that the present composition form fully heat resistant coatings. A second essential component is a silazane compound which is selected from tetramethyldisilazane, hexamethylcyclotrisilazane, and octamethylcyclotetrasilazane alone or a mixture of two or more. Preferably the silazane compound is blended in an amount of about 5 to 40%, especially about 10 to 30% by weight of the total weight of the binding components (organic silicon polymer plus silazane compound plus inorganic filler). Less than about 5% of silazane compound would result in less desirable electric insulation whereas more than about 40% of silazane compound would adversely affect coating hardness and adhesion. A third essential component is an inorganic filler which is preferably selected from Al₂O₃, SiO₂, Fe₂O₃, TiO₂, MgO, ZrO₂-SiO₂, 3Al₂O₃·2SiO₂, ZnO-MgO, Si₃N₄, SiC, and BN alone or a mixture of two or more. The inorganic filler preferably has a mean particle size of about 0.1 to 30 µm, especially about 1 to 5 µm although the particle size is not critical. Preferably the inorganic filler is blended in an amount of about 10 to 70%, especially about 30 to 60% by weight of the total weight of the binding components. Less than about 10% of filler would incur difficulty of application and pinholes in the coatings whereas more than about 70% of filler would result in low coating adhesion. The heat resistant coating composition is applied by dissolving and dispersing the organic silicon polymer, silazane compound, and inorganic filler in an organic solvent such as hexane, benzene, toluene, xylene, and N-methylpyrrolidone. The concentration may range from 50 to 500 parts by weight of organic solvent per 100 parts of the binding components. In the first form of the invention, the above-defined coating composition is first applied to substrates. The type of substrate is not critical and either metallic or non-metallic substrates may be used. Preferably, the substrates are pre-treated on their surface by conventional techniques, for example, by polishing with sand paper followed by removal of oily values. Any desired technique may be used to apply the coating composition to substrates. Exemplary are brush coating, spray coating, flow coating, dipping, and roll coating. It is preferred to coat the composition to a (wet) thickness of about 20 to 150 µm, especially about 30 to 100 µm. Coatings of less than about 20 µm thick are likely to induce pinholes which are detrimental to corrosion resistance whereas more than 150-µm thick coatings would partially peel off at the end of baking. Next, the thus applied coatings are baked after conventional treatment, for example, drying at room temperature. Baking is carried out in an atmosphere of ammonia gas or a mixture of ammonia and an inert gas. Conventional methods carry out baking in air, which fails to achieve coatings having high electric insulation at high temperatures for the following reason. When coating compositions containing polycarbosilane and polysilazane are baked in air, these components are converted into ceramics of SiO₂ type which have poor electric insulation at high temperatures. This can be avoided by baking the coating composition in an atmosphere of either ammonia gas or a mixture of ammonia and an inert gas. Then polycarbosilane and polysilazane components are converted into nitride, Si₃N₄ which insures high electric insulation at high temperatures. Ammonia gas is preferably present in the baking atmosphere at a concentration of about 10 to 100%, especially about 50 to 100%. Baking conditions may be properly controlled. Desirable is a two-step baking procedure including preliminary drying at room temperature to 300°C, especially 150 to 250°C for about 5 to 120 minutes, especially about 15 to 60 minutes, and baking at 200 to 1,000°C, especially 400 to 800°C for about 10 to 120 minutes, especially about 30 to 60 minutes. In the second form of the invention, the above-defined coating composition is first applied to substrates and baked to form a first coating layer, and thereafter, a coating composition containing an organic silicon polymer is applied and baked to form a second coating layer on the first coating layer. With respect to the formation of the first coating layer, the method of applying the heat resistant coating composition to substrates and the coating thickness are the same as in the first form. However, baking is preferably carried out in air at a temperature of about 200°C or higher for about 15 to 60 minutes. Temperature of lower than 200°C would result in a first coating layer having low strength or hardness. Desirable is a two-step baking procedure including preliminary baking at lower than 250°C for about 15 to 30 minutes, and baking at 400 to 700°C for about 15 to 60 minutes. If necessary, baking is carried out in an inert gas atmosphere or another atmosphere. In this way, there is formed the first coating layer. Since the first coating layer alone cannot provide satisfactory electric insulation at high temperatures, an organic silicon polymer base coating is formed on the first coating layer according to the second form of the invention in order to provide a second coating layer having satisfactory electric insulation at high temperatures. The second coating layer may be formed by applying an organic silicon polymer, preferably a solution of organic silicon polymer in organic solvent, to the first coating layer. The organic silicon polymer used herein may be polycarbosilane or polysilazane as previously defined. The degree of polymerization of the organic silicon polymers is selected from the standpoint of crack resistance of the resulting coatings. For example, polycarbosilanes preferably have a number average molecular weight of about 500 to 5,000, more preferably 600 to 2,000, especially 650 to 1,200. Polysilazanes preferably have a number average molecular weight of about 400 to 3,000, more preferably 500 to 2,000, especially 550 to 1,200. These organic silicon polymers are often used by dissolving them in organic solvents such as hexane, toluene, benzene, and xylene. The amount of solvent used varies with the type of organic silicon polymer and the thickness of coatings although the polymer is often diluted with the solvent to a concentration of 10 to 70%, especially 30 to 60% by weight. Dipping, spray coating and other conventional coating techniques may be employed. Preferably, the organic silicon polymer base coating is about 5 to 150 µm, especially about 10 to 50 µm thick. After application, the coatings are dried and then baked, preferably in an atmosphere of ammonia gas or a mixture of ammonia and an inert gas as in the previous embodiment. Baking in ammonia gas causes polycarbosilane and polysilazane to convert into Si₃N₄ type materials which ensure that the resultant coatings experience no lowering of electric insulation at high temperatures. Baking in another atmosphere is less desirable. For example, baking in inert gas causes polycarbosilane to convert into SiC plus excess carbon and polysilazane to convert into a SiC and Si₃N₄ mixed system, both failing to achieve electric insulation at high temperatures. Baking in air results in coatings of SiO₂ material which provide less satisfactory electric insulation at high temperatures and sometimes low adhesion and low hardness. The baking temperature ranges from about 400 to 800°C, preferably from about 600 to 700°C. Nitriding does not take place below about 400°C so that only coatings of lower hardness are obtained whereas metallic substrates would be attacked by ammonia gas above 800°C. According to the method of the invention, there can be formed coatings which firmly adhere to metallic or non-metallic substrates, have high heat resistance, that is, withstand temperatures of higher than about 400°C, and exhibit excellent other properties including hardness, high-temperature electric insulation, water resistance, chemical resistance, and solvent resistance. The invention thus find great utility in applications of providing corrosion resistant, oxidation resistant coatings on metallic substrates and heat resistant, dielectric coatings on conductors. EXAMPLEExamples of the present invention are given below by way of illustration and not by way of limitation. The organic silicon polymers used in Examples were synthesized by the following procedures. The first two examples are illustrative of the synthesis of polycarbosilanes. Reference Example 1A 5-liter, three-necked flask was charged with 2.5 liters of dry xylene and 400 grams of metallic sodium and heated to the boiling point of xylene in a nitrogen gas stream whereby metallic sodium was dissolved and dispersed. To the flask, 1 liter of dimethyldichlorosilane was added dropwise over one hour. At the end of addition, the reaction mixture was heated under reflux until the reaction was completed. The resulting precipitate was removed by filtration from the reaction mixture, which was washed with methanol and then with water, yielding 400 grams of polysilane in white powder form. Then an autoclave equipped with a gas inlet tube, agitator, condenser, and distillation tube was charged with 400 grams of polysilane, which was subjected to polymerization under a pressure of 0.49 MPa·G (5 kg/cm²G) at 450°C. There was obtained a polycarbosilane, designated Polymer A, having a number average molecular weight of 1250. Reference Example 2Reference Example 1 was repeated except that autoclave polymerization was under a pressure of 0.49 MPa·G (5 kg/cm²G) at 430°C. There was obtained a polycarbosilane, designated Polymer B, having a number average molecular weight of 900. The following two examples are illustrative of the synthesis of polysilazanes. Reference Example 3A dry 1-liter, four-necked flask equipped with a stirrer, thermometer, ammonia inlet tube, and deeply cooled condenser was charged with 850 ml of hexane and then with a mixture of 40.3 grams of methyldichlorosilane, 7.5 grams of methyltrichlorosilane, and 12.9 grams of dimethyldichlorosilane, and cooled to -20°C. Excess ammonia gas was admitted into the solution for 4 hours at a flow rate of 12 liter/hour for reaction. Thereafter, the reaction mixture was warmed to room temperature while the condenser was replaced by an ambient cooling condenser so that unreacted ammonia could escape from the reactor. By removing the ammonium chloride by-product by filtration and stripping off the hexane solvent, there was obtained 27.3 grams of liquid silazane. Next, a 300-ml flask equipped with a stirrer, thermometer, dropping funnel, and gas inlet tube was charged with 0.2 grams of potassium hydride and 125 ml of tetrahydrofuran. To the flask was added 27.3 grams of the liquid silazane in 75 ml of tetrahydrofuran at room temperature through the dropping funnel. Evolution of a large volume of gas was observed during the addition. The temperature was raised to 60°C, at which reaction was continued for 2 hours until completion. Then the reaction solution was cooled down. Addition of 2.5 grams of methyl iodide resulted in a white precipitate of KI. After the majority of tetrahydrofuran was removed, 80 ml of hexane was added to the residual white slurry. The mixture was filtered and the hexane was removed from the filtrate in a vacuum of 133.3 Pa (1 mmHg) at 70°C, yielding 25.3 grams of a solid silazane polymer, designated Polymer C, having a number average molecular weight of 1200. Reference Example 4A dry 2-liter, four-necked flask equipped with a stirrer, thermometer, gas inlet tube, and condenser was charged with 1.5 liters of toluene and then with a mixture of 149.5 grams (1 mol) of methyltrichlorosilane and 261 grams (2.4 mol) of trimethylchlorosilane. Ammonia gas was admitted into the solution at room temperature for 3 hours at a flow rate of 90 liter/min. (total NH₃ added 12 mol). With stirring, the reaction mixture was aged for one hour at room temperature until the reaction was complete. The ammonium chloride by-product was removed by filtration and washed with 2 liters of toluene. The toluene was stripped from the combined filtrate at 120°C and 4,000 Pa (30 Torr), yielding 89 grams of a colorless clear silazane compound having a molecular weight of 436. Next, a 300-ml flask equipped with a stirrer, thermometer, and condenser was charged with 89 grams of the silazane compound. The reactor was purged with nitrogen gas stream and slowly heated. A low molecular weight fraction distilled out at a temperature of 270°C. The temperature was further raised to 300°C at which the reactor was held for two hours. On cooling the flask, there was yielded 55 grams of a pale yellow solid, designated Polymer D, having a number average molecular weight of 1070. Examples 1-7 and Comparative Examples 1-2Coating compositions were prepared in accordance with the formulation shown in Table 1. To stainless steel pieces of 50 mm × 50 mm × 3 mm which had been polished with #240 sand paper, degreased and cleaned, the coating compositions were applied to a thickness of 70 µm by means of a bar coater and then dried at room temperature. The coatings were subjected to preliminary drying at 250°C for 30 minutes in air and then baked at the temperature in the atmosphere both reported in Table 1. The thus coated steel plates were examined by the following performance tests. The results are also shown in Table 1. (1) Coating hardnessThe coating was scratched by the pencil scratch test according to JIS K-5400 to determine pencil hardness. (2) AdhesionAdhesion was examined in accordance with JIS K-5400 by scribing the test piece on the coating surface at intervals of 1 mm, applying adhesive tape thereto, lifting off the tape, and counting the number of coating sections left adhered. (3) Electric insulationElectric insulation was measured with direct current at 500 V in accordance with JIS C - 1303. (4) Heat resistanceHeat resistance was examined by heating the test piece in air at 700°C for 1,000 hours, allowing it to cool down, and observing whether or not the coating was cracked or separated. (5) Water resistanceWater resistance was examined by immersing the test piece in hot water at 80°C for 1,000 hours and observing whether or not the coating was cracked or separated. (6) Alkali resistanceAlkali resistance was examined by immersing the test piece in 10% NaOH aqueous solution for 1,000 hours and observing the coating for cracking or separation. (7) Corrosion resistanceCorrosion resistance was examined by immersing the test piece in 10% HCl aqueous solution for 1,000 hours and observing the coating for cracking or separation. (8) Solvent resistanceSolvent resistance was examined by immersing the test piece in xylene for 1,000 hours and observing the coating for cracking or separation. As seen from Table 1, the coatings obtained by applying and baking the heat resistant coating compositions of Examples 1-7 are excellent in various properties including substrate adhesion, hardness, insulation, heat resistance, water resistance, and chemical resistance. Examples 8-14 and Comparative Examples 3-4Coating compositions for the first layer were prepared in accordance with the formulation shown in Table 2. To stainless steel pieces of 50 mm × 50 mm × 3 mm which had been polished with #240 sand paper, degreased and cleaned, the first coating compositions were applied to a thickness of 70 µm by means of a bar coater and then dried at room temperature. The first coatings were baked at the temperature in the atmosphere both reported in Table 2. Then, coating compositions of the second layer were prepared in accordance with the formulation shown in Table 2. The second coating compositions were applied to a thickness of 10 µm by means of a bar coater, dried, and then baked at the temperature in the atmosphere both reported in Table 2. The double coated steel plates were examined by the same performance tests as before. The results are shown in Table 2. As seem from Table 2, the coatings obtained by applying and baking the coating compositions twice as in Examples 8-14 are excellent in various properties including substrate adhesion, hardness, insulation, heat resistance, water resistance, and chemical resistance.	A method for forming a heat resistant, dielectric coating comprising the steps of applying a heat resistant coating composition comprising an organic silicon polymer, a silazane compound selected from the group consisting of tetramethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane and mixtures thereof, and an inorganic filler to a substrate, and baking the coating in an atmosphere of ammonia gas or a mixture of ammonia gas and an inert gas. The method of claim 1 wherein said coating composition contains about 5 to about 40 % by weight of said silazane compound and about 10 to about 70 % by weight of said inorganic filler, the remainder being said organic silicon polymer. The method of claim 1 wherein the baking step is at a temperature of 200 to 1000°C. A method for forming a heat resistant, dielectric coating comprising the steps of applying a first coating composition comprising an organic silicon polymer, a silazane compound selected from the group consisting of tetramethyldisilazane hexamethylcyclotrisilazane octamethylcyclotetrasilazane and mixtures thereof, and an inorganic filler to a substrate, baking the first composition to form a first coating layer, applying a second coating composition comprising an organic silicon polymer to the first coating layer, and baking the second composition to form a second coating layer on the first coating layer. The method of claim 4 wherein the step of baking the second composition is carried out in an atmosphere of ammonia gas or a mixture of ammonia gas and an inert gas. The method of claim 4 wherein said coating composition contains about 5 to about 40% by weight of said silazane compound and about 10 to about 70 % by weight of said inorganic filler, the remainder being said organic silicon polymer. The method of claim 4 wherein the step of baking the first composition is carried out in air at a temperature of at least about 200°C. The method of claim 4 wherein the step of baking the second composition is carried out at a temperature of 400 to 800°C.	SHINETSU CHEMICAL CO; SHIN-ETSU CHEMICAL CO., LTD.	ISHIHARA TOSHINOBU; ITO KEN ICHI; TAKEDA YOSHIHUMI; ISHIHARA, TOSHINOBU; ITO, KEN'ICHI; TAKEDA, YOSHIHUMI
EP-0489429-B1	489,429	EP	B1	EN	19,960,619	1,992	20,100,220	new	H05K3	null	C08G73, H01B3, C08J7, H05K3, C09J179, B32B15, H05K1	C08G 73/10N1, C08J 7/04L79+L79/08, C09J 179/08, H05K 3/28B, T05K3:38D, B32B 15/08, T05K1:00C, C08G 73/10L, H01B 3/30C4	Method of producing flexible printed-circuit board covered with cover layer	A flexible printed-circuit board covered with a cover layer is produced by bonding (a) a flexible printed-circuit board that comprises a flexible base having a surface bearing a circuit and (b) a polyimide film having a surface treated to increase adhering property and another surface not treated to increase adhering property, each of the surfaces being coated with an adhesive layer, with the adhesive layer on the surface treated to increase adhering property interposed between the polyimide film and the surface bearing the circuit, and then peeling off the adhesive layer coating the polyimide film on the surface not treated to increase adhering property.	BACKGROUND OF THE INVENTION(a) Field of the InventionThe present invention relates to a method of producing a flexible printed-circuit board covered with a cover layer, wherein a covering film prevented effectively from curling is used so that it and the flexible printed-circuit board can be located together easily, and the applied cover lay is excellent in heat resistance, flexibility and dimensional stability. (b) Description of the Related ArtCover layer films are for protecting circuits made on flexible printed-circuit boards, and, generally, they are prepared by coating one surface of a base film, such as a polyimide film, with an adhesive, such as an acrylic adhesive or an epoxy adhesive, and are applied to a flexible printed-circuit board by bonding the surface coated with the adhesive to a surface of the flexible printed-circuit board bearing a circuit using heat and pressure. For the purpose of producing flexible printed-circuit boards of improved high efficiency, the use of conventional copper-clad laminates having a three-layer structure of copper foil/epoxy or acrylic adhesive/polyimide film has recently become replaced by the use of those having a two-layer structure of copper foil/polyimide film. However, using the above-described conventional cover layer films has ruined the advantages of copper-clad laminates of two-layer structure, since, after covering with the cover layer, the properties of the flexible printed-circuit boards, including heat resistance, are dominated by the acrylic or epoxy adhesives used for bonding the cover layer films. In order to overcome such a problem, the use of polyimide adhesives was proposed as disclosed in Japanese Patent Application Kokai Koho (Laid-open) No. 3-205474. According to this document, which corresponds to EP-A-0 389 951, the surface of the film bonded to the circuit is plasma treated to improve adherence. However, the use of polyimide adhesives in preparation of cover layer films for flexible printed-circuit boards also encountered a problem that the cover layer films curled when dried after coating, thereby interfering with proper location of them and flexible printed-circuit boards. The causes for the problem include the following (1) and (2). (1) Polyimide adhesives contract severely when dried after application thereof on a base film, since polyimides for adhesives are generally poor in the solubility in solvents as compared with acrylic or epoxy compounds for adhesives so that a large amount of solvents is required for the preparation of polyimide adhesives, with the concentration of the polyimide adhesive components in the polyimide adhesives lowered. (2) In production of two-layer flexible printed-circuit boards, for the purpose of preventing curling thereof, polyimides of low thermal expansion are generally used as base materials in order to make the circuit and the polyimide base similar in linear thermal expansion coefficient. While low thermal expansion is also required of the base films of cover lays, cover lay films themselves are apt to curl due to the difference in linear thermal expansion between the base film and adhesive layer thereof since polyimides for adhesives do not have low thermal expansion. SUMMARY OF THE INVENTION An object of the present invention is to provide a method of producing a flexible printed-circuit board covered with a cover lay, wherein a polyimide adhesive is used as the adhesive of a cover lay film, and the cover lay film is excellent in heat resistance and is prevented effectively from curling. As the results of the inventors' research for preventing cover lay films for flexible printed-circuit boards from curling due to the use of polyimide adhesives, they found that such curling of cover lay films could be prevented by using the generally poor adherence between polyimide/polyimide and by coating both surfaces of a base film with an adhesive to form a sandwich, only one of the surfaces that is to be bonded to the conductor-circuit-bearing surface of a flexible printed-circuit board being treated to improve adhering property prior to the application of the adhesive. The adhesive applied to the other surface that is not treated to improve adhesive property or is subjected to a release treatment prior to the application is peeled off from the base film after the cover lay film is bonded to the flexible printed-circuit board by heating and pressing the sandwich. That is, the present invention provides a method of producing a flexible printed-circuit board covered with a cover lay comprising: assembling (a) a flexible printed-circuit board that comprises a flexible base having a surface bearing a circuit; and (b) a polyimide film having a surface treated to increase adhering property and another surface not treated to increase adhering property, each of the surfaces being coated with an adhesive layer by applying a polyimide adhesive to each of the surface and drying the applied polyimide adhesive by heating, thereby forming on the surface an adhesive layer 1.0 to 1.5 times as thick as the circuit, the polyimide adhesive comprising a compound selected from the group consisting of a polyimide and a polyimide precursor said compound being optionally dissolved in a solvent ; to form a composite wherein the adhesive layer coating the surface treated to increase adhering property is interposed between the polyimide film and the surface bearing the circuit; subjecting the composite to heat and pressure to bond the composite into a laminate structure; and peeling off the adhesive layer coating the polyimide film on the surface not treated to increase adhering property from the laminate structure. DESCRIPTION OF THE PREFERRED EMBODIMENTIn the present invention, from the view point of high heat resistance, good flexibility and excellent dimensional stability, a polyimide film is used as a base film for a cover lay film. For the purpose of preventing the produced flexible printed-circuit board covered with a cover lay from curling, it is preferable to use a polyimide film of low thermal expansion which has a similar linear thermal expansion coefficient to that of the circuit materials. Preferred polyimide film has a linear thermal expansion coefficient of not larger than 2.5× 10-5deg-1 at a temperature of 50 to 250 °C. Typical examples of the preferred polyimide film include UPILEX-S (produced by Ube Industries, Ltd.), UPILEX-SGA (produced by Ube Industries, Ltd.), APIKAL-NPI (produced by Kanegafuchi Chemical Industry Co., Ltd.), and NOVAX (produced by Mitsubishi Chemical Industries Ltd.). One surface of the polyimide film is treated to improve adhering property. Some examples of the treatment for improving adhering property include a mechanical treatment, such as brushing and sandblasting, and a chemical treatment, such as an alkali treatment, a corona treatment and a plasma treatment. Plasma treatments are preferable because of their high efficiency in improving the adhering property. The plasma treatment may be carried out either continuously or batchwise. From the view point of efficiency, a continuous process is desirable. Some examples of the gas to be used for the plasma treatment include oxygen, nitrogen, helium, argon or CF4. These gases may be used individually or as a mixture of two or more kinds of gases. The pressure of the plasma treatment is preferably from 0.08 to 0.15 torr, and the plasma power density (throwing electric power/area of electrode) is preferably from 0.2 to 100 W/cm2, more preferably from 0.5 to 50 W/cm2. The period of the plasma treatment is preferably from 10 seconds to 30 minutes or more, and it depends on other conditions. The reverse of the surface treated to improve adhering property is not treated to improve adhering property or is subjected to a release treatment. The release treatment is generally performed by application of a release agent, such as a silicone release agent and a non-silicone release agent. Some typical examples of the non-silicone release agent include a polyethylene wax, a polyvinyl carbamate and a polyethylimine/alkyl glycidyl ether. Both surfaces of the polyimide film treated as described above are coated with a polyimide adhesive, and the applied polyimide adhesive is dried to form two adhesive layers coating the surfaces of the polyimide film. In an embodiment, first a polyimide adhesive is applied to the surface that was not treated to improve or was subjected to a release treatment, and is then dried to coat the surface with an adhesive layer. Subsequently, the same polyimide adhesive is applied to the reverse of the surface coated with the adhesive layer, namely the surface treated to improve adhering property, and is then dried to form another adhesive layer coating the surface treated to improve adhering property. The drying is conducted preferably by employing a full-float system so as to prevent contact between the applied polyimide adhesive and conveyer devices, etc. in a drying furnace. It is necessary to adjust the thickness of the applied polyimide adhesive so that, after drying, the adhesive layers are 1.0 to 1.5 times as thick as the circuit. If the thickness of the adhesive layers are smaller than that of the circuit, it will be difficult to bury the circuit completely in the adhesive layer during bonding by heating and pressing. If it is more than 1.5 times as thick as the circuit, reduction of residual volatile matter in the adhesive layers after drying will be difficult, and the cost will be increased. It is preferable to reduce the quantity of the residual volatile matter remaining in the adhesive layers after drying to not more than 1.5 % by weight of the adhesive layers, more preferably not more than 1 % by weight. A large quantity of residual volatile matter is undesirable because it causes void or peeling in the interface between the coverlay polyimide film and the flexible printed-circuit board at the time of bonding to the flexible printed-circuit board or solder-reflowing on the coverlaid flexible printed-circuit board. The polyimide adhesive used in the present invention comprises a compound selected from the group consisting of a polyimide and a polyimide precursor, each of the group members being generally dissolved in a solvent. The preferred examples of the polyimide precursor include a polyamic acid and a bis-maleimide compound. The preferred polyimide adhesive comprises a polyamic acid comprising a repeating unit represented by the following formula (1) wherein R1 is or or each R3, respectively, being hydrogen, a halogen or an alkyl group of from 1 to 4 carbon atoms and each X and Y, respectively, being -O- , -SO2- , or -S-, each R4, respectively, being hydrogen, an alkyl group of from 1 to 4 carbon atoms or -CF3, R2 is The preferred polyimide is an imidation product of a polyamic acid having the repeating unit represented by the formula (1). It is preferable to use a polyimide adhesive comprising the polyimide and a bis-maleimide compound dissolved in a solvent or a polyimide adhesive comprising the polyamic acid and a bis-maleimide compound dissolved in a solvent. The latter is more preferable. The polyamic acid having the repeating unit represented by the formula (1) is a reaction product of an aromatic diamine represented by the formula: H2N-R1-NH2 or a derivative thereof and a tetracarboxylic acid represented by the formula: R2(COOH)4 or a derivative thereof. Some examples of the aromatic diamine include 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4' -bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane. Diisocyanates thereof also may be used. The aromatic diamine or derivative thereof, which provides -R1- group, affects largely the glass transition temperature of the produced polyamic acid and polyimide. In order to lower the temperature required for bonding by heating and pressing, it is important that the polyamic acid has a molecular design so that imidation of the polyamic acid provides a polyimide having a low glass transition temperature, and it is preferable to use an aromatic diamine or a derivative thereof containing three or more benzene rings, more preferably, further containing one or more m- bonds. Monocyclic aromatic diamines, such as ophenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene and diaminodurene, and bicyclic aromatic diamines, such as benzidine, 4,4' -diaminodiphenylmethane, 4,4' - diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4.4' - diaminodiphenyl sulfone and 3,3' -diaminodiphenyl sulfone, may also be used. Some examples of the tetracarboxylic acid containing =R2= group include pyromellitic acid, 2,3,3' ,4' -tetracarboxydiphenyl, 3,3' ,4,4' -tetracarboxydiphenyl, 3,3' ,4,4' -tetracarboxydiphenyl ether, 2,3,3' ,4' -tetracarboxydiphenyl ether, 3,3' ,4,4' -tetracarboxybenzophenone and 2,3,3' ,3' -tetracarboxybenzophenone. Derivatives of the tetracarboxylic acid also may be used, and some examples of derivatives include an ester, an anhydride and an acid chloride thereof. These polyamic acids may be used individually or as a blend of two or more of them dissolved in a solvent, and those obtained by copolymerization may also be used. The use of a polyamic acid modified by blending or copolymerization is rather preferable for the purpose of adjusting the glass transition temperature of polyimides derived from polyamic acids at the time of drying. The more preferable polyimide adhesive comprises both the polyamic acid and a bis-maleimide compound in a state dissolved in a solvent. While the polyimide adhesive is being dried by heating to form an adhesive layer on both the surfaces of a polyimide film, the polyamic acid in the polyimide adhesive is imidized by the heating. In preparation of such a polyimide adhesive, it is therefore important for the control of glass transition temperature of the polyimide resulting from the imidation of the polyamic acid to design the molecular structure of the polyamic acid in consideration of the temperature for thermosetting of the bis-maleimide compound and the temperature for bonding to a flexible printed-circuit board. In the case of a polyimide adhesive containing both a polyamic acid and a bis-maleimide compound, the glass transition temperature of the adhesive layer after drying and imidation of the polyamic acid is lower than that of an adhesive layer containing no bis-maleimide compound. However, if the glass transition temperature is nonetheless extremely higher than the temperature for thermosetting of the bis-maleimide compound used, the bis-maleimide compound will be crosslinked in the course of the imidation of the polyamic acid so as to make the bonding with a flexible printed-circuit board by heating and pressing difficult. Further, the higher the glass transition temperature, the higher the temperature required to bond to a flexible printed-circuit board by heating and pressing. In view of these points, it is desirable that the polyimide derived from the polyamic acid has a glass transition temperature not higher than 260 °C. Among the polyamic acids having the repeating units represented by the formula (1), the preferred polyamic acid are those having the repeating units represented by the following formula (2) wherein each R3, respectively, is hydrogen, a halogen or an alkyl group of from 1 to 4 carbon atoms, and each R4, respectively, is hydrogen, an alkyl group of from 1 to 4 carbon atoms or -CF3. The preparation of the polyamic acid is carried out by reacting equimolar quantities of the above-described aromatic diamine or a reactive derivative thereof and the above-described tetracarboxylic acid or a reactive derivative thereof in a solvent, such as N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), phenol, a halogenated phenol, 1,4-dioxane, γ -butyrolactone, tetrahydrofuran and diethylene glycol dimethyl ether, at a temperature ranging from 0 to 150 °C. These solvents may be used individually or as a mixture of two or more of them. Selection of the solvents to be used is also important. It is undesirable to use a solvent the removal of which, at the time of drying of the applied polyimide adhesive, requires an extremely higher temperature than the temperature for thermosetting of the bis-maleimide compound, because the use of such a solvent causes crosslinking of the bis-maleimide compound prior to bonding by heating and pressing and makes adhesion to a flexible printed-circuit board difficult. The bis-maleimide compound which may be used in the present invention is represented by the following formula: Typical examples of the bis-maleimide compound include N,N' -m-phenylene-bis-maleimide, N,N' -p-phenylene-bis-maleimide, N,N' -(oxy-di-p-phenylene)bis-maleimide, N,N' -(methylene-di-p-phenylene)bis-maleimide, N'N' -(sulfonyl-di-p-phenylene)bis-maleimide and 2,2-bis(maleimide-phenoxyphenyl)propane, but the bis-maleimide compounds which may be used in the present invention are not limited to these examples. The quantity of the bis-maleimide compound used is not particularly limited, but the preferred quantity is 10 to 100 parts by weight, more preferably 20 to 60 parts by weight, per 100 parts by weight of the polyamic acid used. The cover lay film thus obtained, namely a polyimide film that has a surface treated to increase adhering property and another surface not treated to increase adhering property and is coated on each surface with an adhesive layer, and a flexible printed-circuit board that comprises a flexible base having a surface bearing a circuit are assembled to form a composite wherein the adhesive layer coating the surface treated to increase adhering property is interposed between the polyimide film and the surface bearing the circuit. The composite is then subjected to heat and pressure to bond the composite into a laminate structure. The bonding is generally carried out at a temperature not lower than the glass transition temperature of the polyimide or the mixture of a polyimide and a bis-maleimide compound in the adhesive layer and not lower than the temperature for thermosetting of the bis-maleimide compound. The pressure is not particularly limited, but it is preferably not lower than 100 N/cm2 (10 kgf/cm2), more preferable 200 to 400 N/cm2 (20 to 40 kgf/cm2). The time of the bonding by heating and pressing is not particularly limited so long as secure adhesion of the adhesive layer and, when a bis-maleimide compound is used, thermosetting of the bis-maleimide compound is attained. In an embodiment, preferable time for bonding by heating and pressing is 15 to 60 minutes. The flexible printed-circuit board used in the method of the present invention is not particularly limited so long as it comprises at least one flexible base which has at least one surface bearing a circuit. A typical example of the preferred flexible printed-circuit board is a flexible printed-circuit board having no adhesive layer or a flexible printed-circuit board having at least one adhesive layer therein. The flexible printed-circuit board having no adhesive layer may be produced by making at least one circuit on the copper foil-bearing surface of a copper foil/polyimide film laminate, namely a copper-clad polyimide film having no adhesive layer. The flexible printed-circuit board having at least one adhesive layer may be produced by making at least one circuit on the copper foil-bearing surface of a copper foil/adhesive/polyimide film laminate, namely a copper-clad polyimide film having an adhesive layer, or on both the copper foil-bearing surfaces of a copper foil/adhesive/polyimide film/adhesive/copper foil laminate, namely a double-sided copper-clad polyimide film. The copper-clad polyimide film having at least one adhesive layer may be produced by bonding a copper foil to at least one surface of a polyimide film through an adhesive, and the adhesive preferably has a glass transition temperature of not lower than 200 °C . If the glass transition temperature of the adhesive in a flexible printed-circuit board is lower than 200 °C , the circuit of the flexible printed-circuit board may get out of position by the heating and pressing at the time of bonding with a cover layer film and the flexible printed-circuit board may be deteriorated. In the present invention, bonding by heating and pressing is generally carried out at a temperature approximately 100 to 150 °C higher than the glass transition temperature of the acrylic or epoxy adhesives that have generally been used in the conventional three-layer flexible printed-circuit boards. An example of the copper foil/polyimide film laminate, namely the copper-clad polyimide film having no adhesive layer, is MCF-5000I (Trade name for a copper-clad film produced by Hitachi Chemical Company, Ltd.). An example of the copper foil/adhesive/polyimide film laminate, namely the copper-clad polyimide film having an adhesive layer, is MCF-5010I (Trade name for a copper-clad film produced by Hitachi Chemical Company, Ltd. wherein the adhesive used has a glass transition temperature of not lower than 200 °C ). Prior to the bonding, it is desirable to subject the circuit of the flexible printed-circuit board to be used to a treatment for improving adhering property, such as a browning treatment (cuprous oxide), a blackening treatment (cupric oxide) or a treatment with a coupling agent. Finally the adhesive layer coating the polyimide film on the surface that is not treated to increase adhering property or is subjected to a release treatment is removed from the laminate obtained by bondinq. The removal of the adhesive layer can be performed easily by peeling it from an end of the laminate with hands. According to the method of the present invention, cover lay films which do not curl and are excellent in heat resistance can be obtained. A combined use of such cover lay films and two-layer metal-clad films make it possible to produce heat resistant flexible printed circuit boards covered with cover lay. EXAMPLES 1 TO 3 AND COMPARATIVE EXAMPLES 1 AND 2PREPARATION EXAMPLE 1Into a 60-liter stainless reaction vessel equipped with a thermocouple, a stirrer, a nitrogen inlet and a condenser placed were 4.20 kg of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 42.5 kg of N,N-dimethylacetamide, and were then stirred to dissolve 2,2-bis[4-(4-aminophenoxy)phenyl]propane in N,N-dimethylacetamide, while dried nitrogen was made to flow through the reaction vessel. While the resulting solution was cooled to 20 °C or lower with a water jacket, polymerization was carried out by adding 3.30 kg of benzophenone tetracarboxylic dianhydride slowly into the solution, to obtain a viscous polyamic acid varnish. For the purpose of facilitating the following application operation, the polyamic acid varnish was cooked at 80 °C until the rotating viscosity of the polyamic acid varnish reached about 200 poise. The polyamic acid varnish contained 7.5 kg (15 % by weight) of a polyamic acid. A polyimide having a glass transition temperature of 245 °C was obtained by imidizing the polyamic acid. The polyamic acid varnish was then cooled to 40 °C , and 1.50 kg of N,N' -(methylene-di-p-phenylene)bis-maleimide, which corresponded to 20 parts by weight of N,N' -(methylene-di-p-phenylene)bis-maleimide per 100 parts by weight of the polyamic acid used, was added and dissolved therein to obtain a polyimide adhesive. EXAMPLE 1A surface of a polyimide film of 25 µm thick (produced by Ube Industries, Ltd., trade name: UPILEX-S) was subjected to an oxygen plasma treatment (pressure: 0.1 torr, plasma power density: 26 W/cm2, time: approximately 3 seconds), and the other surface of the polyimide film was kept untreated. The polyimide adhesive prepared in the Preparation Example 1 was applied to both the surfaces of the polyimide film, and was dried at 150 °C for 10 minutes and at 200 °C for 30 minutes, to dry the polyimide adhesive and imidize the polyamic acid therein. Each of the adhesive layers of the cover lay film thus obtained was 40 µm thick and contained 0.3 % by weight of residual volatile matter. A flexible printed-circuit board was produced from a two-layer copper-clad film (copper foil/polyimide film)(Trade name MCF-5000I, produced by Hitachi Chemical Company, Ltd.) by making the copper foil layer of the two-layer copper-clad film into a circuit of stripe lines (line width: 0.050-0.500 mm, thickness: 35 µm) and then subjecting the circuit surface to a browning treatment. The flexible printed-circuit board and the coverlay film were located together to form a composite wherein the circuit surface of the copper-clad film contacted the adhesive layer coating the plasma treated surface. The composite was tightened temporarily and was then pressed at 250 °C for 30 minutes under a pressure of 40 kgf/cm2. Subsequently, the adhesive layer coating the untreated surface of the polyimide film of the cover lay film was peeled off, to obtain a flexible printed-circuit board covered with a cover lay. The peel strength between the adhesive layer and the untreated surface of the polyimide film was 0.3 kgf/cm. The peel strength of the cover lay from the flexible printed-circuit board was 0.9 kgf/cm, and no abnormality was recognized after a solder-bath test conducted at 350 °C for three minutes. EXAMPLE 2A flexible printed-circuit board covered with a cover lay was produced in the same manner as in Example 1 with the exception that a three-layer copper-clad laminate (copper foil/adhesive having a glass transition temperature of 220 °C /polyimide film) (Trade name MCF-5010I, produced by Hitachi Chemical Company, Ltd.) was used in place of the two-layer copper-clad laminate used in Example 1. The peel strength between the adhesive layer and the untreated surface of the polyimide film was 0.3 kgf/cm. The peel strength of the coverlay was 0.9 kgf/cm, and no abnormality was recognized after a solder-bath test conducted at 350 °C for three minutes. EXAMPLE 3A flexible printed-circuit board covered with a coverlay was produced in the same manner as in Example 1 with the exception that a polyimide film of 25 µm thick having a surface treated to improve the adhering property (Trade name UPILEX-SGA, produced by Ube Industries, Ltd.) was used and no further surface treatment was carried out. The peel strength between the adhesive layer and the untreated surface of the polyimide film was 0.3 kgf/cm. The peel strength of the coverlay was 0.8 kgf/cm, and no abnormality was recognized after a solder-bath test conducted at 350 °C for three minutes. COMPARATIVE EXAMPLE 1A cover lay film was produced in the same manner as in Example 1 with the exception that a coverlay film was produced by forming an adhesive layer only on the plasma treated surface of a polyimide film. The obtained cover lay film curled severely so as to make it difficult to locate properly it and a flexible printed-circuit board together. A flexible printed-circuit board covered with a cover lay was produced in the same manner as in Example 1 with the exception that the thus obtained cover lay film was used, but, in the produced flexible printed-circuit board covered with a cover lay, the flexible printed-circuit board and the cover lay did not meet each other. COMPARATIVE EXAMPLE 2A flexible printed-circuit board covered with a cover lay was produced in the same manner as in Example 1 with the exception that a polyimide film having an epoxy adhesive layer on only one surface (Trade name CUSV, produced by Nikkan Kogyo Co., Ltd.) was used as a cover lay film. Delamination of the cover lay occurred after a solder-bath test at 350 °C .	A method of producing a flexible printed-circuit board covered with a cover layer comprising: assembling (a) a flexible printed-circuit board that comprises a flexible base having a surface bearing a circuit; and (b) a polyimide film having a surface treated to increase adhering property and another surface not treated to increase adhering property, each of the surfaces being coated with an adhesive layer by applying a polyimide adhesive to each of the surface and drying the applied polyimide adhesive by heating, thereby forming on the surface an adhesive layer 1.0 to 1.5 times as thick as the circuit, the polyimide adhesive comprising a compound selected from the group consisting of a polyimide and a polyimide precursor said compound being optionally dissolved in a solvent; to form a composite wherein the adhesive layer coating the surface treated to increase adhering property is interposed between the polyimide film and the surface bearing the circuit; subjecting the composite to heat and pressure to bond the composite into a laminate structure; and peeling off the adhesive layer coating the polyimide film on the surface not treated to increase adhering property from the laminate structure. The method of claim 1, wherein the polyimide film has a linear thermal expansion coefficient of not larger than 2.5×10-5deg-1 at a temperature of 50 to 250 °C. The method of claim 1 cr 2, wherein the flexible printed-circuit board is made from a copper-clad polyimide film comprising a polyimide film which bears on one surface directly a copper foil, the flexible base is the polyimide film of the copper-clad polyimide film, and the circuit is made on the copper foil-bearing surface of the copper-clad polyimide film. The method of claim 1 or 2, wherein the flexible base of the flexible printed-circuit board is a polyimide film, and the circuit is a circuit formed by bonding a copper foil to at least one surface of the polyimide film through an adhesive having a glass transition temperature of not lower than 200 °C to form a copper-clad polyimide film, and making the copper foil of the copper-clad polyimide film into a circuit. The method of any of claims 1 to 4, wherein the treatment for increasing adhering property is a plasma treatment. The method of any of claims 1 to 5, wherein the surface of the polyimide film that is not treated to increase adhering property is coated with a release agent. The method of any of claims 1 to 6, wherein the polyimide adhesive comprises a polyamic acid dissolved in a solvent, the polyamic acid having a repeating unit represented by the following formula (1) wherein R2 is or each R3, respectively, being hydrogen, a halogen or an alkyl group of from 1 to 4 carbon atoms and each X and Y, respectively, being -O- , -SO2- , or -S-, each R4, respectively, being hydrogen, an alkyl group of from 1 to 4 carbon atoms or -CF3, R2 is The method of any of claims 1 to 7, wherein the polyamide adhesive includes 20 to 60 parts by weight of a bis-maleimide compound per 100 parts by weight of the polyamic acid. The method of claim 8, wherein the bis-maleimide compound is selected from the group consisting of N,N' -m-phenylene-bis-maleimide, N,N' -p-phenylene-bis-maleimide, N,N' -(oxy-di-p-phenylene)bis-maleimide, N,N' -(methylene-di-p-phenylene)bis-maleimide, N,N' -(sulfonyl-di-p-phenylene)bis-maleimide and 2,2-bis(maleimide-phenoxyphenyl)propane. The method of claim 7, wherein the polyamic acid has a repeating unit represented by the following formula (2) wherein each R3, respectively, is hydrogen, a halogen or an alkyl group of from 1 to 4 carbon atoms, and each R4, respectively, is hydrogen, an alkyl group of from 1 to 4 carbon atoms or -CF3. The method of claim 7, wherein the polyamic acid is a reaction product of an aromatic diamine selected from the group consisting of 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4' -bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane and a diisocyanate thereof. and a tetracarboxylic acid compound selected from the group consisting of pyromellitic acid, 2,3,3' ,4' - tetracarboxydiphenyl, 3,3' ,4,4' -tetracarboxydiphenyl, 2,3,3' ,4' -tetracarboxydiphenyl ether, 3,3' ,4,4' - tetracarboxydiphenyl ether, 2,3,3' ,4' - tetracarboxybenzophenone, 3,3' ,4,4' - tetracarboxybenzophenone, an ester thereof, an anhydride thereof and an acid chloride thereof. The method of any of claims 7 to 11, wherein the solvent is selected from the group consisting of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, phenol, a halogenated phenol, 1,4-dioxane, γ -butyrolactone, tetrahydrofuran and diethylene glycol diethyl ether. The method of claim 8, wherein the treatment for increasing adhering property is a plasma treatment, the polyamic acid is a reaction product of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 3,3' ,4,4' - tetracarboxybenzophenone, the solvent is N,N-dimethylacetamide, the bis-maleimide compound is N,N' - (methylene-di-p-phenylene)bis-maleimide, and the flexible printed-circuit board is made from a copper-clad polyimide film comprising a polyimide film which bears on one surface directly a copper foil, the flexible base is the polyimide film of the copper-clad polyimide film, and the circuit is made on the copper foil-bearing surface of the copper-clad polyimide film. The method of claim 8, wherein the treatment for increasing the adhering property is a plasma treatment, the polyamic acid is a reaction product of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 3,3' ,4,4' - tetracarboxybenzophenone, the solvent is N,N-dimethylacetamide, the bis-maleimide compound is N,N' - (methylene-di-p-phenylene)bis-maleimide, and the flexible base of the flexible printed-circuit board is a polyimide film, and the circuit is a circuit formed by bonding a copper foil to at least one surface of the polyimide film through an adhesive having a glass transition temperature of not lower than 200 °C to form a copper-clad polyimide film, and making a circuit on the copper foil-bearing surface of the copper-clad polyimide film.	HITACHI CHEMICAL CO LTD; HITACHI CHEMICAL CO., LTD.	IMAIZUMI JUNICHI; KATOH YASUSHI; NAGAO KOUICHI; NOMURA HIROSHI; OTI TAKATO; SATOU EIKICHI; SUZUKI MASAKATSU; IMAIZUMI, JUNICHI; KATOH, YASUSHI; NAGAO, KOUICHI; NOMURA, HIROSHI; OTI, TAKATO; SATOU, EIKICHI; SUZUKI, MASAKATSU
EP-0489432-B1	489,432	EP	B1	EN	19,960,821	1,992	20,100,220	new	H01J29	null	H01J29	T01J229:48H2B, H01J 29/50B, T01J229:48H2C	Electron gun for color cathode-ray tube	An electron gun for a color cathode-ray tube for enhancing the convergence characteristics and removing the flare of beam spot formed at the boundary of screen, comprising first and second (9) grid electrodes and a first accelerating and focusing electrode (10) each having first, second and third electron beam passing holes (91-93) for allowing first, second and third electron beams emitted from cathodes to pass therethrough so as to be accelerated and focused; first and third slots formed around said first and third electron beam passing holes and having asymmetrical depth for allowing equipotential intervals at inner side to be larger than equipotential intervals at outer side, the first and third electron beam passing holes being symmetrical to each other with respect to the second electron beam passing hole; and a second slot formed around the second electron beam passing hole and provided with a symmetrical depth so as to have same equipotential interval at its inner and outer side with respect to the center of the second electron beam passing hole.	BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron gun for a color cathode-ray tube for enhancing the convergence by efficiently focusing electron beams emitted from three cathodes of in-line alignment on a fluorescent screen and removing the flare of beam spot which is produced around the fluorescent screen of color cathode-ray tube in terms of the deflection magnetic field for self-convergence. 2. Description of the Prior ArtsIn general, a color cathode-ay tube is structured, as shown in Fig. 1, such that three electron beams Bs, Bc and Bs are emitted from an electron gun 2 contained in a neck portion 1 in backward of a glass bulb and focused on a point of a shadow mask 3, and then combined with R.G.B. colors so as to reproduce desired images on a fluorescent screen 5 which is doped on the internal surface of a panel 4. The electron gun is of an in-line type for emitting three electron beams in parallel with the axis (A-A) of the color cathode-ray tube, and must have an electron beam focusing structure in order to focus the three parallel beams on one point of the fluorescent screen. Figs. 2 and 3 illustrate an electron gun which is generally applied to a color cathode-ray tube. As shown in Figs. 2 and 3, the electron gun comprises three cathodes 7 each having a heater 6 therein, first and second grid electrodes 8 and 9, first accelerating and focusing electrode 10 each of which has three electron beam passing holes 81, 82, 83, 91, 92, 93, 101, 102 and 103 being spaced with each other as much as a predetermined distance S and aligned in the same axial line, and second accelerating and focusing electrode 11 of which a central electron beam passing hole 112 is aligned in the same axial line as the electron beam passing holes 82, 92 and 102 of the first and second grid electrodes and first accelerating and focusing electrode 10 and side electron passing holes 111 and 113 are aligned eccentrically to the electron beam passing holes 81, 83, 91, 93, 101 and 103 of the first and second grid electrodes and first accelarating and focusing electrode 8, 9 and 10 as much as a predetermined distance ΔS toward the outer side. In the above structure, the amount of eccentricity ΔS is determined by establishing such that the diameters of the electron beam passing holes 111 and 113 of the second accelerating and focusing electrode 11 are larger than or the same as the diameters of the electron beam passing holes 101 and 103 of the first accelerating and focusing electrode 10, and the distance S' between the electron beam passing holes of the second accelerating and focusing electrode 11 is larger than the distance S between the electron beam passing holes of the first accelerating and focusing electrode 10. Referring to Fig. 4 which shows a convergence structure in which the electron beam passing holes 101, 103 and 111, 113 of the first accelerating and focusing electrode 10 and the second accelerating and focusing electrode 11 are formed in eccentric as much as the amount of eccentricity ΔS, when a voltage is applied from the outside of the electron gun 2, equipotential lines V1, V2 ..., which are called as a main electron lens, for focusing the electron beams Bs, Bc and Bs are formed at the space between the first and second accelerating and focusing electrodes 10 and 11 so that a plurality of electron beams which are emitted from the cathodes 7 can be focused on the fluorescent screen as a beam spot. At this moment, the equipotential lines at the second accelerating and focusing electrode 11 are formed In asymmetrical with respect to the electron beam path between the electron beam passing holes 101, 103, 111, and 113, by the eccentricity ΔS. Accordingly, the electron beam Bs which passes through the above path advances refractively toward the central beam Bc as much as predetermined angle ' by an equation of refraction VYQ=V'Y'Q', and then focused on a point on the fluorescent screen 5. Meanwhile, the main electron lens formed between the first accelerating and focusing lens 10 and the second accelerating and focusing lens 11 has to focus respective electron beams and converge the side beams Bs. However, in practice since the refranctive index of the main electron lens is varied when the focusing voltage is adjusted to enhance the focusing characteristics, and shape of the equipotential lines between the electron beam passing holes 101, 103, 111 and 113 becomes also varied. As a result, the focusing characteristics are varied so that the two requirements as above can not be satisfied. In addition, since the convergence rate must be varied depending upon the size of the color cathod-ray tube, there occurs a problem in that the eccentricity ΔS must be adjusted properly in correspondence with the size of the color cathode-ray tube, and also a further problem occurs in that the number of parts of the second accelerating and focusing electrode 11 Is large so that the workability for assembling the electron gun becomes lower. Furthermore, in the color cathode ray tube which adopts a circular symmetrical lens system, although a thin and round beam spot can be obtained at the center of the fluorescent screen by a strong quadrupole magnetic field within a color cathode-ray tube having a deflection yoke of non-uniform magnetic field for self-convergence, a flare that electronic density is low is formed at the circumferentical portion of the beam spot so that the focusing characteristics are deteriorated and thus the resolution of the color cathode-ray tube becomes lower. The self-convergence is a method for directing three electron beams to focus on a point by a deflection of electron beams even at the circumferential portion of the screen of a color cathode-ray tube. That is, the magnetic forces applied to three electron beams form non-uniform magnetic fields differently by means of the deflection yoke positioned just before the electron gun 2, as shown in Fig. 1. By such an arrangement, although the self-convergence characteristics may be obtained, but it is inevitable that the focusing characteristics of electron beams become deteriorated. Considering the problems mentioned above, an electron gun with a convergence structure as shown in Figs. 5A and 5B has been proposed. In such a type of electron gun, the second grid electrode 9 has longitudinal slots 94, 95 and 96 each of which has the same width as that of electron beam passing holes 91, 92 and 93. The slot 95 is positioned symmetrically with respect to the central electron beam passing hole 92 while other two slots 94 and 96 are in eccentric with respect to the center of the side passing holes 91 and 93. In Fig. 5A, the electron beam passing holes 101, 102 and 103 of the first accelerating and focusing electrode 10 and the electron beam passing holes 91, 92 and 93 of the second grid electrode 9 are disposed in the same axial line, and the dimension of the slots 94, 96 and 96 in lengthwise is determined by the equation of ℓ1 + ℓ2 = 2ℓ3 and ℓ2 > ℓ1. According to this type of electron beam convergence structure, the equipotential lines V1, V2 ... are formed asymetrically on the slots 94 and 95 of the second grid electrode 9 which are disposed asymetrically around the electron beam passing holes 91 and 93. That is, at the outer position ℓ1 where the length of the slot Is short with respect to the center of the electron beam passing hole, the gradient of the equipotential lines is abrupt, while at the inner position ℓ2 where the length of the slot is large the gradient thereof Is gentle. So, the electron beams Bs which have been passed through the side electron beam passing holes 91 and 93 pass through the second grid electrode 9 and then converged into the central beam by refracting toward inner side at a predetermined angle . Such an electron gun having a convergence structure at the second grid electrode 9 gets good convergence characteristics because the convergence structure between the first accelerating and focusing electrode 10 and the second accelerating and focusing electrode 11 compensates for the convergence deterioration caused by a variation of a convergence voltage. And, also since the slots 94, 95 and 96 strengthen the focusing operation in the breadthwise direction and deteriorates the longitudinal direction, the electron beams Bs, Bc and Bs passing through the passing holes 91, 92 and 93 are strongly focused in the breadthwise direction so that longitudinally extended electron beam is formed and then neutralized with an inverse quadrupole while passing through the main electron lens and the asymmetric magnetic field for self-convengence, thereby forming a beam spot of low density and low flare on the fluorescent screen, resulting in the increase in the resolution of the color cathode-ray tube. Such an electron gun is known of US-A-4 523 123. Another electron gun is revealed in JP-A- 2 012 740, wherein the influence to the static focus property of electron beams is reduced at an accelerating and focusing third grid electrode by forming inclines at both outer electron beam passing holes of that focusing electrode. The alignment of these inclines to the outer electron beam passing holes is asymmetrical. SUMMARY OF THE INVENTIONIt is, therefore, an object of the present invention to provide an electron gun for a color cathode-ray tube having a second grid electrode which is capable of being easily manufactured and applicable to various types irrespective of size of the cathode-ray tube. Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. The electron gun for a color cathode-ray tube of this invention comprises first and second grid electrodes and a first accelerating and focusing electrode each having first, second and third electron beam passing holes for allowing first, second and third electron beams emitted from cathodes to pass therethrough so as to be accelerated and focussed, wherein said second electron beam passing holes being centered on a center axis of said color cathode-ray tube; first and third slots formed around said first and third electron beam passing holes of the second grid electrode (9); and symetrically disposed with respect to the corresponding electron beam passing hole axis, said slots having an asymmetrical depth for producing equipotential intervals being on a side closer to the central axis of a color cathode-ray tube greater than on a side further from central axis of said cathode-ray tube, said first and third electron beam passing holes being symmetrical to each other with respect to the second electron beam passing hole of the second grid electrode (9); and a second slot formed around said second electron beam passing hole of the second grid electrode (9) having symmetrical depth to produce an uniform equipotential intervall with respect to the center axis of said color cathode-ray tube. According to a prefered embodiment of the invention said first and third slots are formed such that a depth of the first and the third slots on the side further from the center axis of said color cathode-ray tube is less than a depth of the first and third slots on the side closer to the central axis of said color cathode-ray tube and the depth of the first and third slots on the side closer to the central axis of said color cathode-ray tube and the depth of the first and third slots on the side closer to the central axis of said color cathode-ray tube is less than half of a thickness of the second grid electrode. In another prefered embodiment said second grid electrode including slots around said first and third electron beam passing holes on a side facing said electron gun and symmetrical slots around the first, second and third electron beam passing holes on a side opposite the side facing said electron gun. BRIEF DESCRIPTION OF THE DRAWINGSThe present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein: Fig. 1 is a longitudinal sectional view of a conventional color cathode-ray tube; Fig. 2 is a longitudinal sectional view of an electron gun of Fig. 1; Fig. 3 is a schematic sectional view of Fig. 2; Fig. 4 is a longitudinal sectional view of the conventional electron gun in partial, showing the electron beam convergence structure; Fig. 5A is a longitudinal sectional view of another type conventional electron gun, showing the electron beam convergence structure; Fig. 5B is a plane view of a second grid electrode of Fig. 5A; Fig. 6 is a longitudinal sectional view of an electron gun in partial, showing the electron beam convergence structure according to an embodiment of the present invention; and Fig. 7 is a view the same as Fig. 6, but showing another embodiment of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTSReferring now in detail to the drawings for the purpose of illustrating preferred embodiments of the present invention, the electron gun of the present invention is similar in structure to that in Figs. 1 to 3, but the structure of the second grid electrode 9 is changed as shown in Figs. 6 and 7. Accordingly, the present invention will now be described in connection with the second grid electrode 9 with reference to the first accelerating and focusing electrode 10. As shown in Fig. 6, longitudinally extended slots 94, 95 and 96 are formed around electron beam passing holes 91, 92 and 93 of the second grid electrode 9. The width of the slots 94, 95 and 96 is nearly the same as that of the passing holes 91, 92 and 93 and the length thereof is in symmetric with respect to the center of each of the passing holes 91 92 and 93 and larger than the diameter of each of the passing holes 91, 92 and 93. Furthermore, the depth of the central slot 95 is formed such that the depths(t) at both sides on the basis of the passing hole 92 are the same and has the relationship with the thickness(T) of the second grid electrode 9 of t ≤ T/2. And, the depth(t') of each of the slots 94 and 96 is the same as that of the central slot(t) in its inner side, but that in outer side is smaller than the depth(t) of the central slot 95 as t' < t. The second grid electrode 9 is disposed at a certain space from the first accelerating and focusing electrode 10 and the electron beam passing holes 91, 92, 93 and 101, 102, 103 of the second grid electrode 9 and the first accelerating and focusing electrode 10 are aligned in the same axial line. Referring to Fig. 7, longitudinally extended slots 94a and 96b are formed only at the inner side of the electron beam passing holes 91 and 93 of the second grid electrode 9 toward the first accelerating and focusing electrode 10, and the depth(t0) of each of the slots 94a and 96a has the relationship with the total thickness(T) of the second grid electrode 9 as t0 < T/2. In addition, on the opposite side of the slots 94a and 96a of the second grid electrode 9, longitudinally extended slots 94b, 96b and 96b are formed around the electron beam passing holes 91, 92 and 93 such that the width thereof is the same as the diameter of the passing holes 91, 92 and 93, and the length thereof is larger than and symmetrical with respect to the center of each of the passing holes 91, 92 and 93. And also the depth(to') of the slots 94b, 95b and 96b has the relationship with the total tickness(T) of the second grid electrode 9 as to' ≤ T/4. According to the present invention, equipotential lines V1, V2 ... having an abrupt gradient at their outer side and gentle gradient at their inner side are formed around the electron beam passing holes 91 and 93 at both sides, as shown in Fig. 6, and the electron beams Bs which have been passed through the passing holes 91 and 93 of the second grid electrode 2 are refracted toward inner side at an angle  by the refraction of the asymmetrical equipotential lines V1, V2 ... and thus converged toward the central beam Bc. Moreover, since the slots 94, 95 and 96 are formed such that the width thereof is the same as the diameter of the electron beam passing holes 91, 92 and 93 and the length thereof in the longitudinal direction is larger than the diameter of the passing holes 91, 92 and 93, the equipotential lines in the breadthwise are abrupt in their gradients so that their converging operation is strong while gentle in the longitudinal direction so that their converging operation is somewhat weak, thereby forming the electron beams Bs and Bc in the longitudinally extended shape. The electron beams Bs and Bc which have been focused in the longitudinally extended shape pass through the main electron lens to compensate for the magnetic quadrupole operation of the deflection yoke so that the flare of beam spot around the cathode-ray tube is suppressed. According to another embodiment of the present invention, as shown in Fig, 7, the longitudinally extended slots 94a and 96a formed around the passing holes 91 and 93 of the second grid electrode 9 function to converge the electron beams and the longitudinally extended slots 94b, 95b and 96b formed around the passing holes 91, 92 and 93 function to suppress a flare at the circumferential portion of a screen of the color cathode-ray tube. As described above in detail, the present invention provides the effect that it is possible to increase the convergence characteristics by converging efficiently the three electron beams on a point of the fluorescent screen and to remove the flare which may be produced at the circumferential portion of the screen in terms of the deflection magnetic field for self-convergence. Also, there is provided the effect that the manufacturing of the electrode is made simple by aligning the electron beam passing holes of the second grid electrode and the first accelerating and focusing electrode in the same axial line as well as forming the slots of the the second grid electrode in symmetrical, thereby being applicable to various types of cathode-ray tubes irrespective of the size thereof. The invention being thus described, it will be obvious that the same may be varied in many ways. Such modifications as would be obvious to one skilled in the art are intended to be included in the scope of the following claims.	An electron gun for a color cathode-ray tube, comprising: first and second grid electrodes (8,9) and a first accelerating and focusing electrode (10) each having first, second and third electron beam passing holes for allowing first, second and third electron beams emitted from cathodes to pass therethrough so as to be accelerated and focussed, wherein said second electron beam passing holes being centered on a center axis of said color cathode-ray tube; first and third slots (94,96,94b,96b) formed around said first and third electron beam passing holes (91,93) of the second grid electrode (9) and symmetrically disposed with respect to the corresponding electron beam passing hole axis, said slots having an asymmetrical depth for producing equipotential intervals being on a side closer to the central axis of a color cathode-ray tube greater than on a side further from central axis of said cathode-ray tube, said first and third electron beam passing holes (91,93) being symmetrical to each other with respect to the second electron beam passing hole (92) of the second grid electrode (9); and a second slot (95,95b) formed around said second electron beam passing hole (92) of the second grid electrode (9) having symmetrical depth to produce an uniform equipotential interval with respect to the center axis of said color cathode-ray tube. The electron gun of grid claim 1, wherein said first and third slots (94,96) are formed such that a depth of the first and the third slots (94,96) on the side further from the center axis of said color cathode-ray tube is less than a depth of the first and third slots (94,96) on the side closer to the central axis of said color cathode-ray tube and the depth of the first and third slots (94,96) on the side closer to the central axis of said color cathode-ray tube and the depth of the first and third slots (94,96) on the side closer to the central axis of said color cathode-ray tube is less than half of a thickness of the second grid electrode (9). The electron gun of claim 1, said second grid electrode (9) including slots (94a, 96a,) around said first and third electron beam passing holes (91, 93) on a side facing said electron gun and symmetrical slots (94b,95b,96b) around the first, second and third electron beam passing holes (91,92,93) on a side opposite the side facing said electron gun.	GOLD STAR CO; GOLDSTAR CO. LTD.	KOH NAM JE; KOH, NAM JE
EP-0489433-B1	489,433	EP	B1	EN	19,950,823	1,992	20,100,220	new	B01D53	B01J29	B01J29, B01D53	B01J 29/064, B01D 53/94K2C	Catalyst for purifying exhaust gas	A catalyst for purifying an exhaust gas comprising: a crystalline aluminosilicate containing a rare earth or alkaline earth metal produced by allowing a rare earth or alkaline earth metal salt to exist in reactants for a synthesis of a crystalline aluminosilicate, and introduced therein, at least one element selected from the consisting of the group Ib metals and VIII metals of the periodic table.	BACKGROUND OF THE INVENTION1. Field of the InventionThe present invention relates to a catalyst having an improved heat resistance and durability, to be used in the purification of an exhaust gas discharged from, for example, internal combustion engines of automobiles and the boilers of plants. 2. Description of the Related ArtVarious methods of purifying of an exhaust gas discharged from internal combustion engines of automobiles, industrial plants, etc. through the removal of toxic components therein have been studied. In a conventional method, toxic components of the exhaust gas are brought into contact with a catalyst to remove the toxic components, i.e., a catalytic reduction is one of the means used in the above-mentioned method. In this method, it is necessary to use a reducing agent, such as ammonia, hydrogen or carbon monoxide, and further, a special apparatus for recovering or decomposing an unreacted reducing agent. In the catalytic decomposition method, however, toxic components contained in an exhaust gas, particularly nitrogen oxides, can be removed by merely passing the exhaust gas through a catalyst bed without the use of a additional reducing agent, and as the process is simple, the catalytic decomposition method is especially desirable for use in the purification of an exhaust gas. A crystalline aluminosilicate catalyst having an SiO₂/Al₂O₃ mole ratio of 20 to 100 and containing a copper ion (see Japanese Unexamined Patent Publication (Kokai) No. 60-125250) has been proposed as a catalyst for use in this process. In gasoline engines, a lean burn is now considered necessary for a lowering of the fuel consumption and a reduction the amount of exhausted carbon dioxide, but an exhaust gas from this lean burn engine comprises an atmosphere containing an excessive amount of oxygen, and thus it is impossible to apply a conventional three-way catalyst to such an exhaust gas. Accordingly, a method has been proposed of removing toxic components by using a hydrophobic zeolite as the catalyst (see Japanese Unexamined Patent Publication (Kokai) No. 63-283727). The above-mentioned exhaust gas purification catalyst comprising a crystalline aluminosilicate containing a copper ion, however, has a problem in that the activity is significantly lowered when an operating temperature is high. Namely, an exhaust gas having a high temperature causes a significant lowering of the catalytic activity of a crystalline aluminosilicate containing a copper ion and having an SiO₂/Al₂O₃ mole ratio of 20 to 100. Also in the method of removing toxic components contained in an exhaust gas of a lean burn engine, wherein a hydrophobic zeolite is used, the catalytic activity is significantly lowered when the catalyst comes into contact with an exhaust gas having a high temperature, and thus this method also can not be practically used. In EP-A-0 310 398 a catalyst for treatment of exhaust gases from internal combustion engines is disclosed comprising a support which is a refractory inorganic oxide such as aluminosilicate having dispersed thereon lanthanum, at least one other rare earth component and at least one noble metal component selected from the group consisting of platinum, palladium, rhodium, ruthenium and iridium, the lanthanum oxide may be dispersed on said support by means such as coprecipitation or cogellation of a lanthanum compound and a precursor of that support. In EP-A-0 373 665 a catalyst for the treatment of exhaust gas is disclosed comprising a crystalline aluminosilicate containing ions of at least one metal of group Ib and/or group VIII of the periodic table. According to the preparation method disclosed in this document the crystalline aluminosilicate is formed at first, and, subsequently, subjected to an ion exchange method. SUMMARY OF THE INVENTIONAccordingly, the objects of the present invention are to solve the above-mentioned problems of the prior and to prevent the lowering in the exhaust gas purification activity of a catalyst for purifying an exhaust gas upon a contact of the catalyst with an exhaust gas having an elevated temperature. Other objects and advantages of the present invention will be apparent from the following description. In accordance with the present invention, there is provided a catalyst, for purifying an exhaust gas, comprising: a crystalline aluminosilicate containing a rare earth metal or a crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal salt to exist in reactants for a synthesis of a crystalline aluminosilicate; and introduced therein, at least one element selected from the group consisting of the group Ib metals and group VIII metals of the periodic table, wherein in the case of rare earth metal salt the silica source, alumina source and rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C. DESCRIPTION OF THE PREFERRED EMBODIMENTSThe present invention will now be described in more detail. The present inventors have made various studies with a view to solving the problem of the prior art, and as a result, have found that a catalyst comprising a crystalline aluminosilicate containing a rare earth metal or a crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal salt to exist in reactants for a synthesis of a crystalline aluminosilicate, wherein in the case of rare earth metal salt the silica source, alumina source and rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C, brings no lowering of the activity of purifying exhaust gas even when brought into contact with an exhaust gas at a high temperature, and thus have completed the present invention. The crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal for the base material of the catalyst of the present invention should be a crystalline aluminosilicate containing a rare earth metal or a crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal to exist in reactants for a synthesis of a crystalline aluminosilicate, wherein in the case of rare earth metal salt the silica source, alumina source and rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C. When the crystalline aluminosilicate is free from the above-mentioned metal, it is impossible to attain the object of the present invention, i.e., to prevent the lowering in the activity of purifying exhaust gas due to the contact of the catalyst with an exhaust gas having an elevated temperature. There is no limitation on the process for producing the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal so far as an rare earth metal or an alkaline earth metal can be introduced into the crystalline aluminosilicate at the time of preparation of reactants for crystal synthesis, and as far as in the case of rare earth metal salt the silica source, alumina source and rare earth metal source, and, if necessary, an alkali source or a template, are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C. However, for example, also the crystalline aluminosilicate containing an alkaline earth metal can be advantageously produced as well as the crystalline aluminosilicate containing a rare earth metal by mixing a silica source, an alumina source and an alkaline earth metal source, and if necessary, an alkali source or a template, with each other, while maintaining the mixture at a temperature in the range of from 60 to 200°C in an autoclave. Examples of the silica source include sodium silicate, colloidal silica, white carbon and water glass, and examples of the aluminum source include aluminum nitrate, aluminum sulfate, sodium aluminate, aluminum hydroxide and alumina. The conditions of preparation may be selected depending upon the kind of the intended zeolite. There is no limitation on the SiO₂/Al₂O₃ mole ratio of the crystalline aluminosilicate of the present invention, as long as the aluminosilicate contains a rare earth metal or an alkaline earth metal, but the mole ratio is preferably 20 or more, more preferably 20 to 200. When the mole ratio is less than 20, the heat resistance is often lowered. Lanthanum, cerium, praseodyminum, neodymium, promethium, samarium, and europium may be used as the rare earth metal added to reactants for a synthesis of a crystalline aluminosilicate. The particularly preferable rare earth metal is lanthanum or cerium. Examples of the alkaline earth metal are beryllium, magnesium, calcium, strontium, barium and radium. The particularly preferable alkaline earth metal is barium, calcium, strontium or magnesium. Examples of the above-mentioned rare earth metal source and alkaline earth metal source are inorganic salts and organic salts of the above-mentioned metals, such as chloride, bromide, carbonate, nitrate, nitrite, acetate, formate, benzoate and tartrate. The particularly preferable metal salt is a nitrate, acetate, or chloride. The content of the rare earth metal or alkaline earth metal in the exhaust gas purification catalyst of the present invention is preferably 0.05 to 10, more preferably 0.5 to 5, in terms of the atomic ratio of the rare earth metal or alkaline earth metal to aluminum. When the content of the rare earth metal or alkaline earth metal is less than 0.05, the required activity of purifying exhaust gas is not easily maintained after the catalyst is brought into contact with an exhaust gas having an elevated temperature. When the content is larger than 10, however, a sufficient effect cannot be attained for the content of the rare earth element or alkaline earth metal, and further, the heat resistance of the catalyst is adversely affected. The crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal to exist in reactants for a synthesis of a crystalline aluminosilicate, wherein in the case of rare earth metal salt the silica source, alumina source and rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C, has a higher heat resistance than the crystalline aluminosilicate containing a rare earth metal or an alkaline earth metal introduced by ion exchange. The catalyst of the present invention contains, as a catalytically active component, at least one metallic element selected from the group Ib metals and/or VIII metals, of the periodic table. The metallic element may be in the form of a metal, an ion, an oxide, a complex or the like. Although there is no limitation on the content of the metallic element, the content is preferably 0.05 to 0.8, more preferably 0.2 to 0.8, in terms of the atomic ratio of the metal to aluminum. When the content of the metallic element is less than 0.05, the toxic components contained in the exhaust gas may not be sufficiently removed, and when the content is more than 0.8, the effect is small for the content of the metallic element, and further, the heat resistance of the catalyst may be adversely affected. The expression aluminum in the crystalline aluminosilicate used herein is intended to mean aluminum forming the structure of the crystalline aluminosilicate and includes neither aluminum present in a substance added as a binder or a diluent, such as alumina sol, alumina or silica-alumina, nor an aluminum cation introduced by ion exchange with a cation. The at least one metallic element selected from the group Ib metals and/or VIII metals of the periodic table can be introduced into the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal by bringing the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal into contact with an aqueous solution or a nonaqueous solution (e.g., an organic solvent) containing the above-described metallic element. In this type of metallic element introduction method, water is an especially preferred medium, from the viewpoint of the operation. It is also possible to use an organic solvent, as long as the organic solvent can ionize the above-mentioned metal. Suitable examples of the solvent are alcohols such as methanol, ethanol and propanol, amides such as dimethylformamide and diacetamide, ethers such as diethyl ether and ketones such as methyl ethyl ketone. Copper, silver, gold, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium and osmium may be used as the metallic element. Copper, silver, platinum, cobalt, nickel, palladium, etc. are particularly preferable as the metallic element. Examples of the above-mentioned metallic element source include inorganic salts and organic salts of the above-mentioned metals, such as chloride, bromide, carbonate, sulfate, nitrate, nitrite, sulfide, acetate, formate, benzoate and tartrate of the above-described metals. A nitrate, acetate, or chloride of the metal is particularly preferred. There is no limitation on the method of introducing the metallic element, and either an ion exchange method or a supporting method may be used. In general, the introduction of the metallic element is introduced by a method into the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal is immersed in a solution containing at least one metallic element selected from the group Ib metals and/or VIII metals, or by a method wherein a solution containing the above-mentioned metallic element is made to flow through a contact column packed with the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal to bring the solution into contact with the aluminosilicate. In the introduction of the metallic element, it is also possible to use an amine complex of the above-described metal. The concentration of the metallic element in the solution, the amount of the solution, and the contact time, etc., may be selected in accordance with the conditions for introducing a predetermined amount of at least one metallic element selected from the group Ib metals and/or VIII metals in the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal. After the introduction of the metallic element, the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal is washed, and if necessary, then calcined at a temperature in the range of from 300 to 800°C, preferably from 400 to 700°C. When the crystalline aluminosilicate containing a rare earth metal or the crystalline aluminosilicate containing an alkaline earth metal after the introduction of the metallic element is calcined, it may be directly calcined. Alternatively, it may be calcined after mold with the use of a natural clay (for example, kaolin, halloysite or montmorillonite) and/or an inorganic oxide (for example, alumina, silica, magnesia, titania, zirconia, hafnia, aluminum phosphate, a binary gel such as silica-alumina, silica-zirconia or silica-magnesia, or a ternary gel such as silica-magnesia-alumina). To use the catalyst of the present invention for removing toxic components contained in an exhaust gas, it is preferred to mold the catalyst into a form that will provide a large area of contact with the exhaust gas and facilitate the flow of gas, such as a honeycomb form or a monolith catalyst form comprising the catalyst coated on a ceramic or metallic honeycomb structure. It is also possible to introduce the metallic element after the molding. The above-mentioned crystalline aluminosilicate containing a rare earth metal or crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal to exist in reactants for a synthesis of a crystalline aluminosilicate, wherein in the case of rare earth metal salt the silica source, alumina source and rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C, the crystalline aluminosilicate further comprising at least one metallic element selected from the group Ib metals and/or VIII metals, is used as a catalyst for purifying an exhaust gas. In this case, there is no limitation on the origin of the exhaust gas, and the exhaust gas may be simply brought into contact with the catalyst. The contact temperature is preferably about 200 to 1000°C, and the contact time is usually 100 to 500,000 hr⁻¹, preferably 500 to 200,000 hr⁻¹. In purifying exhaust gases discharged from internal combustion engines of automobiles and boilers of plants, etc., the catalyst according to the present invention can exhibit a high exhaust gas purification activity even after contact with a high temperature exhaust gas. ExamplesThe present invention will now be further illustrated by, but is by no means limited to the following Examples. Example 1 (Synthesis of crystalline aluminosilicate containing a rear earth metal)A 13.74 g amount of aluminum nitrate anhydride and 5.79 g of lanthanum acetate were dissolved in 400 g of water. To the solution were added 146.58 g of colloidal silica Cataloid SI-30 (manufactured by Catalysts and Chemicals Industries Co., Ltd.; SiO₂: 30.4%; Na₂O: 0.38%) and a solution of 6.84 g of sodium hydroxide in 127.04 g of water, while vigorously stirring the solution. Further, 19.5 g of tetrapropyl ammonium bromide was further added thereto, and the stirring was continued for about 15 min to prepare an aqueous gel mixture. The SiO₂/Al₂O₃ mole ratio in the starting material mixture was 40. The aqueous gel mixture was charged into an autoclave having an internal volume of one liter, and crystallization was conducted by stirring the mixture at 160°C for 16 hr. The product was subjected to solid-liquid separation, washed with water, and dried and calcined in the air at 550°C for 5 hr to give a La-1 at a crystalline aluminosilicate containing a rare earth metal. The La-1 was subjected to chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.23 Na₂O · 0.40 La₂O₃ · Al₂O₃ · 46.0 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the La-1 is given in Table 1. Lattice spacing (d value) Relative intensity 11.1 ± 0.3strong 10.0 ± 0.3strong 7.4 ± 0.2weak 7.1 ± 0.2weak 6.3 ± 0.2weak 6.04 ± 0.2weak 5.56 ± 0.1weak 5.01 ± 0.1weak 4.60 ± 0.08weak 4.25 ± 0.08weak 3.85 ± 0.07very strong 3.71 ± 0.05strong 3.04 ± 0.03weak 2.99 ± 0.02weak 2.94 ± 0.02weak Example 2 (Synthesis of crystalline aluminosilicate containing a rare earth metal)A Ce-1 was prepared in the same manner as that of Example 1, except that the aluminum nitrate anhydride and the sodium hydroxide were used in respective amounts of 6.87 g and 2.39 g and 2.90 g of cerium acetate was used, instead of lanthanum acetate. The zeolite was subjected to chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.24 Na₂O · 0.35 Ce₂O₃ · Al₂O₃ · 77.5 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Ce-1 was fundamentally the same as that given in Table 1. Example 3 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of La-1 and Ce-1 respectively prepared in Examples 1 and 2 was weighed and charged into in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were put in a 0.1 mol/liter aqueous copper acetate solution weighed so that the number of copper atoms was 5 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 50°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Cu-La-1 and Cu-Ce-1. The catalysts were subjected to a chemical analysis, to determine the copper content (CuO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 2. CuO/Al₂O₃ MO/Al₂O₃ Cu-La-10.600.57 Cu-Ce-10.620.55 M : La, Ce Example 4 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of La-1 and Ce-1 respectively prepared in Examples 1 and 2 was weighed and charged into a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were put in a 0.1 mol/liter aqueous cobalt acetate solution weighed so that the number of cobalt atoms was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Co-La-1 and Co-Ce-1. The catalysts were subjected to a chemical analysis, to determine the cobalt content (CoO/Al₂O₃ mole ratio) of the catalysts for purifying exhaust gas, and the results are given in Table 3. CoO/Al₂O₃ MO/Al₂O₃ Co-La-10.990.45 Co-Ce-10.950.47 M : La, Ce Example 5 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of La-1 and Ce-1 respectively prepared in Examples 1 and 2 was weighed and charged into a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were put in a 0.1 mol/liter aqueous nickel acetate solution weighed so that the number of nickel atoms was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Ni-La-1 and Ni-Ce-1. The catalysts were subjected to a chemical analysis, to determine the cobalt content (NiO/Al₂O₃ mole ratio) of the catalysts for purifying exhaust gas, and the results are given in Table 4. NiO/Al₂O₃ MO/Al₂O₃ Ni-La-11.500.43 Ni-Ce-11.550.40 M : La, Ce Example 6 (Preparation of Catalyst for Purifying Exhaust Gas)A 10 g amount of La-1 prepared in Example 1 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried product was charged into a 0.1 mol/liter aqueous silver nitrate solution weighed so that the number of silver atoms was 5 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalyst was designated as Ag-La-1. The catalyst was subjected to a chemical analysis, to determine the silver content (Ag₂O/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 5. Ag₂O/Al₂O₃ LaO/Al₂O₃ Ag-La-10.500.60 Example 7 (Preparation of Catalyst for Purifying Exhaust GasA 10 g amount of Ce-1 prepared in Example 2 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried product was charged into an aqueous solution having a tetraamminepalladium dichloride concentration of 0.1 mol/liter weighed so that the number of palladium atoms was one time the number of Al atoms in the zeolite, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalyst was designated as Pd-Ce-1. The catalyst was subjected to chemical analysis, to determine the palladium content (PdO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 6. PdO/Al₂O₃ CeO/Al₂O₃ Pd-Ce-10.800.40 Example 8 (Synthesis of crystalline aluminosilicate containing an alkaline metal)A Ba-1 was prepared in the same manner as that of Example 1, except that 4.68 g of barium acetate was used instead of lanthanum acetate. The Ba-1 was subjected to a chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.23 Na₂O · 0.72 BaO · Al₂O₃ · 46.8 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Ba-1 was basically the same as that given in Table 1. Example 9 (Synthesis of crystalline aluminosilicate containing an alkaline earth metal)A Ca-1 was prepared in the same manner as that of Example 1, except that the aluminum nitrate anhydride and the sodium hydroxide were used in respective amounts of 27.48 g and 7.91 g and 5.801 g of calcium acetate was used instead of lanthanum acetate. The Ca-1 was subjected to chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.27 Na₂O · 0.65 CaO · Al₂O₃ · 26.0 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Ca-1 was fundamentally the same as that given in Table 1. Example 10 (Synthesis of crystalline aluminosilicate containing an alkaline earth metal)A Sr-1 was prepared in the same manner as that of Example 1, except that the aluminum nitrate anhydride and the sodium hydroxide were used in respective amounts of 6.87 g and 2.39 g and 3.77 g of strontium acetate was used instead of lanthanum acetate. The Sr-1 was subjected to a chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.24 Na₂O · 0.70 SrO · Al₂O₃ · 78.5 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Sr-1 was fundamentally the same as that given in Table 1. Example 11 (Synthesis of crystalline aluminosilicate containing an alkaline earth metal)A Mg-1 was prepared in the same manner as that of Example 1, except that 2.61 g of magnesium acetate was used instead of lanthanum acetate. The Mg-1 was subjected to a chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.25 Na₂O · 0.70 MgO · Al₂O₃ · 47.5 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Mg-1 was basically the same as that given in Table 1. Example 12 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of Ba-1, Ca-1 and Sr-1 respectively prepared in Examples 8 to 10 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were charged into a 0.1 mol/liter aqueous copper acetate solution weighed so that the number of copper atoms was 5 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 50°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Cu-Ba-1, Cu-Ca-1 and Cu-Sr-1. The catalysts were subjected to a chemical analysis, to determine the copper content (CuO/Al₂O₃ mole ratio) of the catalysts for purifying exhaust gas, and the results are given in Table 7. CuO/Al₂O₃ MO/Al₂O₃ Cu-Ba-10.700.47 Cu-Ca-10.750.45 Cu-Sr-10.680.52 M: Ba, Ca, Sr Example 13 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of Ba-1, Ca-1 and Sr-1 respectively prepared in Examples 8 to 10 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were charged into a 0.1 mol/liter aqueous cobalt acetate solution weighed so that the number of cobalt atoms was 10 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Co-Ba-1, Co-Ca-1 and Co-Sr-1. The catalysts were subjected to a chemical analysis, to determine the cobalt content (CoO/Al₂O₃ mole ratio) of the catalysts for purifying exhaust gas, and the results are given in Table 8. CoO/Al₂O₃ MO/Al₂O₃ Co-Ba-10.930.49 Co-Ca-10.950.47 Co-Sr-10.950.55 M : Ba, Ca, Sr Example 14 (Preparation of Catalysts for Purifying Exhaust Gas)A 10 g amount of each of Ba-1, Ca-1 and Sr-1 respectively prepared in Examples 8 to 10 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried products were charged into a 0.1 mol/liter aqueous nickel acetate solution weighed so that the number of nickel atoms was 10 times the number of Al atoms in the Ba-1, Ca-1 and Sr-1, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalysts were designated respectively as Ni-Ba-1, Ni-Ca-1 and Ni-Sr-1. The catalysts were subjected to a chemical analysis, to determine the cobalt content (NiO/Al₂O₃ mole ratio) of the catalysts for purifying exhaust gas, and the results are given in Table 9. NiO/Al₂O₃ MO/Al₂O₃ Ni-Ba-11.550.43 Ni-Ca-11.590.40 Ni-Sr-11.550.47 M : Ba, Ca, Sr Example 15 (Preparation of Catalyst for Purifying Exhaust Gas)A 10 g amount of Mg-1 prepared in Example 11 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the Mg-1, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried product was charged into a 0.1 mol/liter aqueous silver nitrate solution weighed so that the number of silver atoms was 5 times the number of Al atoms in the Mg-1, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The resultant catalyst was designated as Ag-Mg-1. The catalyst was subjected to a chemical analysis, to determine the silver content (Ag₂O/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 10. Ag₂O/Al₂O₃ LaO/Al₂O₃ Ag-Mg-10.540.58 Example 16 (Preparation of Catalyst for Purifying Exhaust Gas)A 10 g amount of Mg-1 prepared in Example 11 was weighed and put in a 1 mol/liter aqueous ammonium chloride solution weighed so that the number of ammonium molecules was 10 times the number of Al atoms in the Mg-1, and the mixture was stirred at a temperature of 60°C for 2 hr. Then, the mixture was subjected to solid-liquid separation, washed with water, and dried at 100°C for 10 hr. The dried product was charged into an aqueous solution having a tetraamminepalladium dichloride concentration of 0.1 mol/liter weighed so that the number of palladium atoms was one time the number of Al atoms in the Pd-Mg-1, and the mixture was stirred at a temperature of 80°C for 20 hr. Then, the mixture was subjected to solid-liquid separation, washed with water and dried at 100°C for 10 hr. The resultant catalyst was designated as Pd-Mg-1. The catalyst was subjected to a chemical analysis, to determine the palladium content (PdO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 11. PdO/Al₂O₃ MgO/Al₂O₃ Pd-Mg-10.820.36 Comparative Example 1 (Synthesis of crystalline aluminosilicate)A base material Z-1 for a comparative catalyst was prepared in the same manner as that of Example 1, except that lanthanum acetate was not added to the starting materials for synthesis. The zeolite was subjected to chemical analysis, and as a result, was found to have the following composition represented by mole ratios of oxides on an anhydrous basis:0.65 Na₂O · Al₂O₃ · 45.5 SiO₂.The lattice spacing (d value) determined from a powder X-ray diffraction pattern of the Z-1 was fundamentally the same as that given in Table 1. Comparative Example 2 (Preparation of Comparative Catalyst)A comparative catalyst Cu-Z-1 was prepared in the same manner as that of Example 3. The catalyst was subjected to a chemical analysis, to determine the copper content (CuO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 12. Comparative Example 3 (Preparation of Comparative Catalyst)A comparative catalyst Co-Z-1 was prepared in the same manner as that of Example 4. The catalyst was subjected to a chemical analysis, to determine the copper content (CuO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 12. Comparative Example 4 (Preparation of Comparative Catalyst)A comparative catalyst Ni-Z-1 was prepared in the same manner as that of Example 5. The catalyst was subjected to a chemical analysis, to determine the copper content (NiO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas purification catalyst, and the results are given in Table 12. N-Z-1 CuO/Al₂O₃0.82 CoO/Al₂O₃0.94 NiO/Al₂O₃1.53 N : Cu, Co, Ni Comparative Example 5 (Preparation of Comparative Catalyst)A comparative catalyst Ag-Z-1 was prepared in the same manner as that of Example 15. The catalyst was subjected to a chemical analysis, to determine the copper content (Ag₂O/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 13. Ag₂O/Al₂O₃ Ag-Z-10.70 Comparative Example 6 (Preparation of Comparative Catalyst)A comparative catalyst Pt-Pd-Z-1 was prepared in the same manner as that of Example 16. The catalyst was subjected to a chemical analysis, to determine the palladium content (PdO/Al₂O₃ mole ratio) of the catalyst for purifying exhaust gas, and the results are given in Table 14. PdO/Al₂O₃ Pd-Z-10.85 Example 17 (Evaluation of Hydrothermal Stability of Catalysts for Purifying Exhaust Gas)An atmospheric pressure fixed bed reaction tube was packed with 2 g of each of the catalysts for purifying exhaust gas prepared in Examples 3 to 7 and 12 to 16, and the temperature of the oven was elevated at a rate of 10°C/min up to 900°C under conditions of a steam concentration of 10% and an air flow rate of 60 ml/min, and maintained at that temperature for 6 hr. The power source was turned off, and the reaction tube, as such, was allowed to stand until cooled to room temperature. The hydrothermal stability was evaluated based on the crystallinity which is represented by the ratio of the peak intensities before the hydrothermal treatment to that after the hydrothermal treatment, in an X-ray diffraction pattern determined by the powder X-ray diffractometry. The results are given in Table 15. Comparative Example 7 (Evaluation of Hydrothermal Stability of Comparative Catalysts)The comparative catalysts prepared in Comparative Examples 2 to 6 were treated in the same manner as that of Example 17 and evaluated in the same manner as that of Example 17. The results are given in Table 15. Catalyst Hydrothermal Stability (Degree of crystallization, %) Cu-La-175 Cu-Ce-180 Co-La-180 Co-Ce-182 Ni-La-185 Ni-Ce-187 Cu-Z-156 Co-Z-170 Ni-Z-175 Cu-Ba-178 Cu-Ca-166 Cu-Sr-183 Co-Ba-180 Co-Ca-169 Co-Sr-185 Ni-Ba-185 Ni-Ca-164 Ni-Sr-191 Cu-Z-156 Co-Z-159 Ni-Z-170 Ag-La-174 Pd-Ce-182 Ag-Mg-176 Pd-Mg-184 Ag-Z-155 Pd-Z-168 Example 18 (Evaluation of Durability in Terms of Capability of Purifying Exhaust Gas)An atmospheric pressure fixed bed reaction tube was packed with 0.65 g of each of the catalyst for purifying exhaust gas prepared in Examples 3 to 7 and 12 to 16, pretreated at 500°C for 0.5 hr, while passing a reaction gas having the following composition (600 ml/min) through the catalyst bed, and heated to 800°C at a constant rate, and the NOx conversions at each temperatures were measured (reaction 1). Composition of reaction gas NO1000 ppm O₂4% CO1000 ppm C₃H₆500 ppm H₂O4% CO₂10% N₂balance Subsequently, the reaction tube was maintained at 800°C for 5 hr for an endurance treatment. After the reaction tube was cooled and maintained at 200°C for 0.5 hr to conduct a pretreatment, it was again heated to 800°C at a constant rate to determine the NOx conversions at each temperatures (reaction 2). The results are given in Tables 16 to 34. Cu-La-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002020 3503330 4004442 4504340 5003535 Cu-Ce-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002019 3503430 4004645 4504443 5003535 Co-La-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002020 3502827 4005149 4504648 5003535 Co-Ce-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002020 3502727 4005049 4504644 5003432 Ni-La-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002018 3502320 4004440 4504036 5003330 Ni-Ce-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3001918 3502524 4004540 4504136 5003634 Ag-La-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003030 3504440 4005048 4504645 5003535 Pd-Ce-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003433 3503837 4003330 4502523 5001918 Cu-Ba-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002020 3503533 4004646 4504343 5002727 Cu-Ca-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002019 3503432 4004645 4504343 5002727 Cu-Sr-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3001919 3503433 4004745 4504543 5002826 Co-Ba-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002120 3502830 4005151 4504648 5002930 Co-Ca-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002020 3502727 4005049 4504647 5003029 Co-Sr-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3001817 3502726 4004949 4504443 5002927 Ni-Ba-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002018 3502524 4004640 4504036 5003027 Ni-Ca-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3001918 3502526 4004540 4504136 5003028 Ni-Sr-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3001918 3502627 4004540 4504236 5003129 Ag-Mg-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003030 3504037 4004845 4504341 5003535 Pd-Mg-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003533 3504038 4003231 4502524 5002020 The NOx conversion is represented by the following equation: NOx :NOx concentration at inlet of fixed bed type reactor tube NOx :NOx concentration at outlet of fixed bed type reactor tube Comparative Example 8 (Evaluation of Durability of Comparative Catalysts in Terms of Capability of Purifying Exhaust Gas)The comparative catalysts prepared in Comparative Examples 2 to 6 were evaluated in the same manner as that of Example 18, and the results are given in Tables 35 to 39. Cu-Z-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003015 3503826 4005030 4504836 5003529 Co-Z-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002715 3504629 4005132 4504038 5003032 Ni-Z-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3002412 3504027 4004630 4503834 5002920 Az-Z-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 3003025 3503830 4005340 4504835 5003830 Pd-Z-1 NOx conversion (%) Temp. (°C) Reaction 1 Reaction 2 300355 3504215 4003017 4502320 5001718 As apparent from Tables 16 to 39, the catalysts for purifying exhaust gas comprising a crystalline aluminosilicate, containing a rare earth metal, and the catalysts for purifying exhaust gas comprising a crystalline aluminosilicate containing an alkaline earth metal according to the present invention, are less liable to cause a lowering in the activity of purifying exhaust gas than the comparative catalysts, even when the catalysts for purifying exhaust gas are exposed in a reaction gas at 800°C for 5 hr. Namely, the catalysts of the present invention have an improved durability. As mentioned above, in the present invention, the catalyst for purifying exhaust gas according to the present invention comprising a crystalline aluminosilicate containing a rare earth metal or a crystalline aluminosilicate containing an alkaline earth metal produced by allowing a rare earth metal salt or an alkaline earth metal to exist in reactants for a synthesis of a crystalline aluminosilicate and introduced therein, at least one element selected from the group Ib metals and/or VIII metals of the periodic table, wherein in the case of rare earth metal salt, the silica source, the alumina source and the rare earth metal source are mixed and the resultant mixture is maintained at a temperature in the range of from 60° to 200°C, can advantageously purify an exhaust gas and maintain a high activity of purifying exhaust gas even after contact with an exhaust gas at a high temperature.	A catalyst for purifying an exhaust gas comprising: a crystalline aluminosilicate Containing a rare earth metal produced by mixing a silica source, an alumina source and a rare earth metal source, and maintaining the mixture at a temperature in the range of from 60 to 200°C; and, introduced therein, at least one element selected from the group consisting of the group Ib metals and VIII metals of the periodic table. A catalyst for purifying an exhaust gas as claimed in claim 1, wherein said rare earth metal is lanthanum or cerium. A catalyst for purifying an exhaust gas as claimed in claim 1, wherein the group Ib metals and VIII metals of the periodic table are copper, silver, platinum, cobalt, nickel and palladium. A catalyst for purifying an exhaust gas as claimed in claim 1, wherein an SiO₂/Al₂O₃ mole ratio of the crystalline aluminosilicate is 20 or more. A catalyst for purifying an exhaust gas as claimed in claim 1, wherein the content of the rare earth metal is 0.05 to 10, in terms of the atomic ratio of the rare earth metal to aluminum. A catalyst for purifying an exhaust gas comprising: a crystalline aluminosilicate containing an alkaline earth metal produced by allowing an alkaline earth metal salt to exist in reactants for a synthesis of a crystalline aluminosilicate; and, introduced therein, at least one element selected from the group consisting of the group Ib metals and VIII metals of the periodic table. A catalyst for purifying an exhaust gas as claimed in claim 6, wherein said alkaline earth metal is barium, calcium, strontium or magnesium. A catalyst for purifying an exhaust gas as claimed in claim 6, wherein the group Ib metals and VIII metals of the periodic table are copper, silver, platinum, cobalt, nickel and palladium. A catalyst for purifying an exhaust gas as claimed in claim 6, wherein an SiO₂/Al₂O₃ mole ratio of the crystalline aluminosilicate is 20 or more. A catalyst for purifying an exhaust gas as claimed in claim 6, wherein the content of the alkaline earth metal is 0.05 to 10, in terms of the atomic ratio of the alkaline earth metal to aluminum.	TOSOH CORP; TOSOH CORPORATION	INOUE SHUNJI; KASAHARA SENSHI; SEKIZAWA KAZUHIKO; INOUE, SHUNJI; KASAHARA, SENSHI; SEKIZAWA, KAZUHIKO
EP-0489434-B1	489,434	EP	B1	EN	19,980,708	1,992	20,100,220	new	B22D11	B22D11	B22D11	B22D 11/06L3D	Method and apparatus for sensing the condition of casting belt and belt coating in a continuous metal casting machine	Method and apparatus for continuously sensing and monitoring the conditions of tensed flexible endless metallic casting belts (12,14) and their insulative coatings in a continuous metal casting machine. The flatness of a casting belt (12, 14) is continuously monitored and thereby also the condition of its thermal protective coating. One or more non-contacting eddy-current sensing probes (36, 38) are placed in proximity to the reverse coolant side of a belt (12, 14) for sensing and measuring the distance of the belt from the probe to reveal irregularities in the flatness of the belt while it travels past the probe. A deficiency of insulative belt coating can cause variations in belt flatness during casting. By monitoring such variations an operator of the continuous casting machine is alerted that the coating needs to be retouched or replaced without interrupting the casting process. Or such monitoring can alert the operator that the belt (12, 14) has become inherently not flat.	In the early prior art of continuous casting utilizing one or more tensed endless metallic belts, the commercial casting of slab or thin metal strip sometimes had to be interrupted because of poor surface of the cast product or uneven product thickness or both. Such interruptions were especially likely to occur when certain difficult metals or alloys were being cast. Several advances in methods and apparatus evolved in more recent prior art and contributed to improvements in surface characteristics and uniformity of thickness in products being cast. Some of these improvements can become optimally effective only if continual ongoing information is immediately obtained during casting relating to the state of the casting belts and their insulating coatings. Such continual ongoing immediate information has heretofore not been reliably obtainable.A major proximate cause of defective cast metallurgy or surface flaws has been the inability of a metallic casting belt to maintain continual and continuous contact with the freezing product. Sometimes non-flatness inheres in a new casting belt. Sometimes non-flatness is due to the distortions of the belt under the thermal effects of molten metal becoming solidified. Either way, non-flatness, even a relatively small amount of non-flatness can interrupt uniform heat extraction. In consequence, zones of nearly frozen alloy may suck late-freezing constituents from less-frozen zones that have lost contact with a casting belt, resulting in a totally unacceptable metallurgical structure.Continuously moving casting belts are naturally subjected to great and varying thermally and mechanically induced stresses as the result of their exposure on one side to freezing molten metal, while on the other side being exposed to fast-flowing cooling water. At the same time, the belts in contact with the solidifying metal must lie flat and be steered or adjusted intermittently in order to conform approximately to true endless paths around which they are desired to be revolved. The heating of one surface of a metallic casting belt by molten metal naturally tends to expand that surface, causing compressive stress on that side. Because the other side of the belt near the fast-flowing liquid coolant remains relatively cold, the heating tends to distort the belt (in the area where it follows a nominally straight course), with the hot side tending to become convex. If the heating is non-uniform, as often occurs, flutes and ripples can be caused in the belt, and these distortions disturb the belt's contact with the freezing metal product, with the unwanted results mentioned above. Approximate flatness of the course of a belt is nevertheless maintained by exerting high tension on it, but tension alone may not be a sufficient mechanical control to prevent induced distortions in the casting of some metals.The casting belts which are employed for linear belt-type casting, as in twin-belt casting, may be made for example of mild cold-finished steel or of copper alloy as described in US-A-4 915 158. The belt thickness typically lies between 0.9 mm to 1.7 mm (0.035 and 0.065 of an inch), though the thickness may lie somewhat outside this range. US-A-4 915 158 discloses the continuous casting of molten metal employing a moving mold defined between front faces of two revolving, tensed, flexible, electrically-conductive, metallic casting belts wherein the front face of each belt is coated with an insulative coating and the front face is intended to follow a predetermined pass line position. The back face of each belt is cooled by aqueous coolant applied in the vicinity of the moving mold. Due to thermal stresses the revolving casting belts do not always remain flat. They are subject to distortion, buckling, wrinkling, rippling, or fluting. For casting slab, the belts must be relatively wide. They normally first undergo a process of roller-stretch leveling as described in US-A-2 904 860, or they are mechanically prestrained in zones as in US-A-4 921 037.Such pre-treatments result in an extremely flat or well-proportioned belt, suitable for all current twin-belt continuous casting purposes. However, the thinness, the long and wide dimensions, weight, and moderate yield point of such relatively wide casting belts all add up to relative fragility, such that the belt, in its ordinary handling involved in crating, shipping, and mounting on a casting machine, may yield locally and so develop subtle undulations ( loops or nodes ) which, though they may be difficult to see, impair usefulness in service despite the usual exertion of high tension during casting, which tends to keep belts flat. It is important for a casting operator to learn of such subtle belt imperfections before attempting to cast and during casting, so that the operator can correct the situation.The employment of thermally insulative coatings on the outside (casting side) of such belts, i.e., on the side next to the freezing metal, has proved necessary for maintaining belt flatness and desired belt surface characteristics and effects during casting and hence for maintaining high qualities in cast products. These coatings on metallic casting belts control the belt temperatures resulting from contact with molten metal on the hot side of the belt. Both solid and liquid coatings have been used, often in combination. They will be described in detail later.Degradation of the cast product is likely to occur when the insulative coating or coatings become thin or worn, or conversely when an uneven build-up occurs in a continually applied coating.It would seem easy to install a mechanical, directly-contacting device to sense and indicate variations in the flatness of belts as they revolve around their respective carriages in a twin-belt casting machine and travel past such a directly-contacting device. A directly-contacting device is disclosed in US-A-4 002 197. But in fact, wear, vibration, and sticking have prevented such directly-contacting devices from being as practical in various continuous casting installations during day-after-day operations. Through prolonged exposure to fast-moving coolant, directly-contacting devices accumulate dirt, oil, and minerals. Moreover, the high levels of sensitivity that have recently proven to be desirable for ensuring optimum casting have unexpectedly rendered contact-type mechanical devices relatively marginal in their performance. Further, there has been difficulty of access to such directly-contacting devices for providing maintenance to them, because they were located among numerous closely-spaced backup rollers, nozzles, and gutters.The present invention solves, or substantially overcomes, these problems of the prior art.The subject-matter of the invention is specified in the claims.Described are a method and apparatus for continually sensing flatness of a casting belt of a continuous casting machine before a cast and moreover for continuously sensing and monitoring flatness of the belt during casting and in such a way, and with such precision, as to supply continual ongoing immediate and sufficient information concerning the belt proper and its insulative coating for enabling optimization of belt conditions and characteristics during continuous casting. The continual ongoing immediate information which is provided enables line personnel to take steps while casting to adjust for any adverse conditions so as to forestall changes for retaining continuity of the cast and for achieving uniform high quality in the cast product. Such adjustments are often accomplished by selectively touching up the non-permanent, temporary topcoat if any, or else by replacing a topcoat to ensure its uniformity.Moreover, the invention greatly facilitates trying-out various changes in belt coatings and techniques and in determining their results for the establishment of belt-coating specifications when casting previously untried alloys.Such adjustments or try-outs of new belt-coating procedures may be accomplished without stopping a cast that is in progress. That is, adjustments and try-outs advantageously may be made on the fly. The present invention employs one or more movable or fixed electrical distance-sensing sensors called proximity probes, which are non-contacting but are positioned near to the belt, together with the required electrical powering and reading equipment. Such a distance-sensing transducing probe senses precisely the nearby position of a belt surface with respect to the plane of the pass line of the freezing product. In the illustrative embodiment of this invention, a distance-sensing transducing probe is mounted near the upstream part of the casting region near the coolant-cooled surface of a revolving casting belt. Thus, the position of the belt is sensed in relation to the plane of the pass line to determine on a continual, ongoing and immediate manner whether the casting belt (as it travels past this proximity probe) is in continuous intimate contact with the pass line of the freezing product as desired. A plot of the actual belt deflection versus time is readily displayed on a computer screen of a strip-chart recorder.Among the advantages of the present invention are those resulting from the fact that it involves no mechanical contact with the revolving casting belt. Hence, there is no disturbance or wear of the probe nor of the revolving belt. Unlike apparatus of the prior art, there is nothing to wear out, nor vibrate, nor clog nor stick. Moreover, a proximity probe causes little or no disturbance to the free-flow of cooling water along the belt surface. Other objects, aspects, features and advantages of the present invention will be apparent from the following detailed description of the presently preferred embodiments considered in conjunction with the accompanying drawings, which are presented as illustrative and are not intended to limit the invention. Corresponding reference numbers are used to indicate like components or elements throughout the various Figures.FIG. 1 is a side elevation view of a twin-belt continuous metal-casting machine, which is an illustrative example of a belt-type continuous metal-casting machine in which the present improvement may be employed to advantage.FIG. 2 is an enlarged plan view showing a proximity probe and its support as seen from the viewing position II-II in FIGS. 1 and 3.FIG. 3 is a cross-sectional detail of a proximity-sensing probe and its supports as seen taken along the line III-III in FIG. 2. FIG. 3 also shows a portion of an upstream main roll and two casting belts with a dummy bar between them as positioned at the start of a cast.FIG. 4 is a chart recording of the contour of a flat and properly coated casting belt as it repeatedly passes a proximity sensor installed as shown in FIGS. 2 and 3 for molten aluminum being satisfactorily cast.FIG. 5 is a chart recording made under conditions similar to FIG. 4 but illustrating a repair of insulative belt coating being made on the fly, i.e., while a continuous casting operation is being carried on without interruption. This belt happens to have slight inherent kinks causing indications which appear repetitively on this chart in FIG. 5.FIG. 6 is a schematic electrical diagram showing a circuit connected to an eddy-current proximity probe for producing chart recordings such as are shown in Figs. 4 and 5.Referring now to FIG. 1, a belt type of continuous casting machine 10, illustratively shown as a twin-belt caster, has molten metal fed into the entry end E between upper and lower casting belts 12 and 14. The molten metal is supplied from in-feed apparatus, generally indicated at 11, and the flow-rate of the molten metal into the machine is controlled by an in-feed flow controller 13, for example such as a movable gate (or stopper) associated with the tundish and its nozzle 15 which directs the molten metal into the entry E. Cast metal product P issues from the downstream or discharge end D of the machine 10. The casting belts 12 and 14 define between them a moving casting cavity C and are supported and driven by means of upper and lower carriage assemblies U and L respectively. The upper carriage U, as shown in this embodiment of the present invention, includes two main roll-shaped pulleys 16 and 18 around which the upper casting belt 12 is revolved as indicated by the curved arrows. The pulley 16 near the input end E of the machine is provided with multiple circumferential fins 17 (only one fin is seen in FIG. 3) and is referred to as the upstream pulley or nip pulley, and the other pulley 18 near the discharge end D is called the downstream or tension pulley. Similarly, the lower carriage L, in the embodiment of the invention as shown, includes main upstream (or nip) and downstream roll-like pulleys 20 and 22 respectively, around which the lower casting belt 14 is revolved (as indicated by the curved arrows).In order to drive the casting belts 12 and 14 in unison, pulleys 16 and 20, or 18 and 22 of both the upper and lower carriages are jointly driven at the same rotational speed through universal-coupling-connected drive shafts (not shown), by a mechanically synchronized drive (not shown). Two laterally spaced edge dams 28 (only one edge dam is shown in FIG. 1) travel around rollers 30 to enter the moving casting region C, defined between the casting belts 12 and 14. Typically, a multiplicity of backup rollers 32 (FIG. 1) each including fins 33 and a core 34 (FIGS. 2 and 3) restrain the casting belts 12 and 14 against the pressure of molten metal 35 and define the position of the belts during casting, doing so while permitting the free passage of coolant 82 traveling longitudinally past the fins 33. It is to be understood that the belt position may also be defined by sliding fins or by protrusions on stationary platens or by hydrodynamic devices.In carrying out the present invention in its preferred mode, a small position-sensing probe (proximity probe) 36 is employed, as illustrated in FIGS. 2 and 3. This probe includes a coil of fine wire (not shown) with its axis generally perpendicular to the surface of the object of measurement--in this case the upper casting belt 12. It is our present understanding of the operation of this proximity probe 36 that it works on an eddy-current principle, whereby the coil in the probe 36, which is energized by an alternating-current (AC) power supply 37 on a remotely-located electronic measurement unit 39, induces eddy currents in its object of measurement, namely, in the metallic belt 12, which is electrically conductive and whose distance from the probe 36 is being sensed and measured. The eddy currents so induced absorb energy from the probe. These eddy currents produce reflexively a decrease in impedance of the coil in the proximity probe or, in another way of speaking, produce an increase in the current through the proximity probe coil from what it would have been without the presence of the belt 12. The closer the belt 12 is to the probe 36 the greater the decrease in impedance in the coil 12.Through a coaxial cable 40 the probe 36 cooperates with the remotely placed electronic measurement equipment 37, 39 that energizes the probe coil and electronically amplifies and analyzes its output signal.A typically used proximity probe 36 and its associated electronic equipment 37, 39 was obtained from the company named Bently Nevada, having offices in Minden, Nevada, and called their 7200 Series 11mm Proximity Transducer System. This probe is small enough to fit unobtrusively into a twin-belt continuous casting machine. The measured results are recorded by means of a readout device such as a chart recorder 41 and simultaneously can be viewed by the operator on a cathode-ray tube monitor 43. Most conveniently, the measured data resulting from the proximity probe 36 is also displayed as part of a general data collection system in a control panel 43 that draws, displays and records information also on temperatures, speeds, speed ratios, and torques.This system 36, 37, 39, 40 accurately measures the distance of the metallic belt 12 from the face 38 of the probe 36 without need for contact of this face 38 against the belt 12 and with practically instant response. The farther the working face 38 of such a probe 36 is from the belt 12, the less the eddy-current energy loss. This energy loss is detected by the measuring equipment 37, 39 to result in a directly useful output signal. Within practicable limits, such a proximity probe 36 and associated equipment 37, 39, 40 in a system as shown provides surprisingly linear measurements. In our experience, a proximity sensing and measuring system as shown will indicate a change in distance of the belt 12 from the probe face 38 as small as 13 micro-meters 0.0005 of an inch; 1/2 mil) --more than sufficient for present purposes.It is to be understood that there is a similar proximity probe and measuring system (not shown) associated with the lower belt 14. Also, it is to be understood that a plurality of such proximity sensor probes may be employed for sensing each belt.Such a probe 36 is mounted in the casting machine 10 at a predetermined spacing (gap) 42 normally of about 3 mm 1/8 inch from each of the belts 12 and 14 on the coolant side or inside, as shown for the upper belt 12 in FIG. 3. This gap 42 could be fixed anywhere within the range of about 2 mm (0.08 of an inch) to 10 mm (0.40 of an inch), the higher end of this range being accessible to a larger, farther-reaching proximity probe 36. This predetermined spacing (gap) 42 allows clearance for the fast-flowing coolant 82 next to the casting belt without significantly disturbing the coolant flow. In an upstream/downstream (longitudinal) sense this probe 36 is placed near the mold entrance E, preferably being positioned within a longitudinal zone of about 254 mm (ten inches) downstream from (i.e., to the right of) a point F of first contact of molten metal with the casting belt. This longitudinal zone X is the zone in which is desired to be initiated the freezing of a film of metal against the mold side of the belt 12 or 14.The proximity probe 36 is shown mounted on a welded tubular frame 44 that stretches across the carriage U or L in which it is mounted. Setscrew 46 secures the probe 36 in a socket 49 secured to the mounting frame 44. The frame 44 is supported by flanged studs 48 which are secured by pins 50 in sockets in yokes 52 near the ends of the frame 44. The whole mounted assembly is located in the carriage U or L of the casting machine by the straddling of the yokes 52 against backup-roller pivot shafts 54. As seen in FIG. 3, the yokes 52 have two rounded V-shaped seats 55 which serve to capture the backup roller pivot shafts 54 for conveniently and precisely holding the mounted probe 36 in its desired position relative to the belt 12, because the nearby backup rollers 32 are defining the desired plane of travel of the casting belt 12. In other words, the yokes 52 are being positioned by means of the backup-roller pivot shafts 54 which are simultaneously positioning these rollers and hence are defining the desired path of travel of the belt 12. There are generally U-shaped clearance reliefs 57 formed in the inside surfaces of the yokes 52 so as to provide clearance for the ends of the respective backup rollers 32. Alternatively, the probe 36 may be mounted using other methods or mounted in other parts of the casting machine structure.Typical chart records are shown in FIGS. 4 and 5. If there is no fluctuation in the reading, and if the belts lie against smoothly running, undeflected backup rollers, the mold surface of the belt 12 is the same as the upper boundary of the casting pass line by definition. In our experiments, the presence of flowing coolant water 82 does not adversely affect the measured response of the proximity probe 36, except that materials in the coolant water, presumably mainly salts or ions which render the water conductive may, with some equipment designs, cause a steady offset that has been measured as 0.1 to 0.15 mm (4 to 6 mils) in the reading. That is, the gap 42 may appear smaller by the amount of this offset than it actually is. The cooling water used in these experiments would pass standards for potable water so far as salts were concerned. There appears to be no reason why this correction might not at times need to be substantially greater or less than the range just stated, but no further data have been gathered.We have discovered that, under some conditions as measured during casting, particularly in casting aluminum having low alloy content, that a casting belt may deviate up to 0.25 mm (0.010 of an inch) in one direction from the desired pass-line relationship without causing undesired degradation of the cast product P. However, at other times, deviations as small as 0.13 mm (0.005 of an inch) can cause problems, notably in casting an aluminum alloy of long-freezing-range, for example, one containing about 2.5 per cent or more of magnesium--as a specific example, AA 5052 alloy in the nomenclature of the Aluminum Association. The deviations from flatness just mentioned are nearly always in an away-from-sensor direction, toward the pass line. The casting results of employing the present invention involving proximity measurements are especially striking and advantageous in continuous casting of such long-freezing-range alloys, since such small deviations of flatness as are associated with degradation in casting 5052 alloy are indicated and can be adjusted and compensated for or overcome. The inherent flatness of the casting belt--its freedom from nodes, loops, or kinks--can be measured initially when no metal is being cast. If the inherent unflatness of the belt at any point is more than deemed suitable for the alloy to be cast, such as 0.25 mm (0.010 of an inch) as discussed above, then the belt is thereby indicated as a candidate to be leveled or re-leveled or mechanically prestrained, employing notably such a procedure as referred to in the above background.Later on, during casting, a belt which has passed such a preliminary measurement test may nevertheless produce measured indications that its desired unflatness limits have become exceeded due to the effects of heat in combination with worn coating, usually a worn temporary topcoat. An important feature of the present invention is the detection of defects in belts newly mounted on the casting machine. The typical defect is a transverse kink, which we refer to as a node. Nodes result from rough handling of these long, wide, limp belts during shipment or during placement on the casting machine, or from crates that do not support the insides of the belts during shipment. We measure the height or depth of these nodes while the belt is revolving on the casting machine 10 under a normal operating tension of 700 kilograms per square centimeter (10,000 pounds per square inch) or somewhat more. Under this condition, a node that measures less than 0.2 mm (0.008 of an inch) from the passline is considered to be a low-height node and is deemed acceptable for casting. A node of this low height or depth will almost always decrease during revolving travel of a belt while the belt is being employed for casting. On the other hand, a node greater than 0.2 mm (0.008 of an inch) will almost always increase in amplitude while a cast proceeds, and the belt will become unusable after a node height of about 0.25 mm (0.010 of an inch) is reached, because the slab P usually thereafter becomes unacceptable. The proximity probe readings taken during casting reliably indicate when to abort such a cast.Before starting a cast, non-permanent (temporary) insulative coatings or parting compounds ( topcoats ) are usually applied over a permanent insulative coating, as known in the art. Such an additional or temporary coating may be an oil such as polyalkylene glycol or silicone fluid. In the casting of aluminum, a film of soot (finely divided amorphous carbon) or diatomaceous silica, or both, together with binder and alcohol/water carrier, are more usually applied as a topcoat. Application of the topcoat, if any, is usually done before the start of a cast, with re-application or touch-up being carried out during casting as required.The permanent insulative coating layer next to the belt is normally provided according to US-A-4 487 157, 4 487 790 and 4 588 021 (previously referenced). Such a permanent insulative coating is normally not reapplied to a belt.FIGS. 4 and 5 show portions of the recordings of measurements made during actual casts of aluminum having 2.8 percent magnesium content. The relative smoothness of the recorded measurement line 58 on a chart 59 in FIG. 4 bears witness to a normal, untroubled period of casting. It is seen that the measurement record line 58 shows total overall changes in the spacing gap 42 of no more than about 0.12 mm (0.005 of an inch). The belt was inherently flat and the insulative coating was sufficient. On the charts 59 and 61 in FIGS. 4 and 5, respectively, a horizontal distance of 1 BELT REV. equals one full revolution of a belt, and a vertical distance as shown by two vertical arrows indicates a change in gap space 42 (FIG. 3) of 0.5 mm (0.020 of an inch). A downward movement of recorded measurement lines 58 and 60, on charts 59 and 61, respectively, indicates an increase in the gap space 42, i.e., an inward deflection of the belt toward the casting cavity C.At the left of FIG. 5, a measurement record line 60 illustrates the effect of a topcoat coating that has worn thin. The operator decided at about location 64 that it was time to remove the old, unevenly worn topcoat of binder, soot and diatomaceous silica so as to apply a renewed topcoat coating. Hence the relatively wide valley 62 appearing in the recorded measurement line in FIG. 5, reflecting the time period of about two full belt revolutions, during which time hand scouring with steel wool had, to a certain extent, removed the temporary topcoat insulative coating. The valley 62 represents the inward movement of the belt (toward the freezing metal) of an amount up to about 1.5 mm (0.060 of an inch) due in this case to heating effects of the metal being cast. During this time 62, the casting was of poor quality. Then the operator sprayed a new topcoat coating of binder, soot and silica onto the belt; this renewed topcoat coating entered the mold at about point 66. All this renewal of the topcoat coating was done quickly without interrupting the casting process, as FIG. 5 records, where the operation was accomplished in about two belt revolutions. Naturally, the material that is cast during such a repair operation on the fly is scrapped and remelted, a procedure normally less costly than stopping and re-starting the cast. Such coating adjustment, where possible, is usually done at the beginning or end of a coil of cast material P in order to avoid interrupting the manufacturing of full coils of rolled-down strip by the rolling mill downstream (not shown) and the coiler farther downstream (not shown). The cast product after rolling in line, is being coiled downstream.The record line in FIG. 5 in area 68 after the recoating (to the right of the valley 62) reveals less irregularity, indicating that casting conditions had been improved to an acceptable level. However, two persistent, repetitive peaks 69 appear to remain at regular intervals, each corresponding, respectively, with the time required for a full belt revolution. These peaks 69 evidently were caused by areas with particular coating deficiency which then required touch-up work.Narrow peaks may be caused by a slight kink or by a weld that was not quite smooth, either of which may activate the probe every revolution of the belt. Similarly, the probe senses dimples and bumps in the belt. All such data is highly useful. But the point here is that the proximity probe 36 senses something else, namely, the worn, unduly thin or absent condition of the temporary topcoat insulative soot-and-silica coating (or other temporary parting-agent coating) such as that indicated in the recorded line 60 to the commencement at 64 of the scouring process. The slow deterioration of a topcoat temporary coating can be observed as the deterioration gradually develops. Corrective action may then be planned to be taken prior to the starting of the winding of the next coil of rolled product downstream. There are provided immediate ongoing indications of the resulting indeterminate, heat-activated, fluctuating positions of the belt which are inconsistent with good cast product in certain alloys and of which the operator needs to be made directly aware at the earliest possible time.The speed of the casts whose measurements were recorded in FIGS. 4 and 5 was about 10.6 meters (35 feet) per minute. In the chart recordings 58 and 60, time is increasing toward the right in the direction of the TIME arrows. In order to enable the showing of recorded measurement lines 58 and 60 corresponding to at least about seven belt revolutions, the horizontal dimensions of an actual chart recording have been reduced by more than one hundred to one, while the vertical dimensions of the chart have been increased for clarity of illustration by a factor of more than ten to one; consequently there are exaggerations of the slope of the profile of the recorded measurement lines 58 and 60 in FIGS. 4 and 5 by more than three orders of magnitude.Fluting distortions of a belt are revealed by the present invention. Such fluting distortions can result from insufficient belt preheating, such pre-heating being described in US-A-4 002 197.In a twin-belt casting machine, it is desirable to monitor both upper and lower belts 12 and 14, or both belts of a vertical twin-belt caster. FIGS. 4 and 5 were made with a probe 36 positioned in longitudinal alignment with the middle of a 38 cm (15-inch) slab being cast. However, distortion is not necessarily maximized at the middle. The optimal mode for all but very narrow casting machines now appears to be to display on one common chart and/or one common cathode-ray tube the signals resulting from each of two or three probes each placed at the same downstream distance X from the point F of first contact of molten metal with the belt. These two or three probes are uniformly spaced laterally across the width of the casting cavity C. The one or two additional probes are not shown in the drawings herewith but are similar to the first probe. Alternatively, one transversely movable probe (not shown) can be used, which can be moved laterally so as to cover the entire width of the casting cavity C.The density (specific gravity) of metals to be cast is relevant. A lighter metal of relatively lower specific gravity, for example aluminum, will not press and flatten the belts against the backup rollers 32 or other backup means with the same consistency as occurs with a heavier metal, for example zinc or copper. Hence, the present invention is very well suited for use in casting aluminum and other light metals, though use of this invention is not at all limited to the continuous casting of lighter metals. The immediate ongoing and relatively precise measurements provided by the present invention have now revealed how very sensitive a continuous belt-type casting process is to what were formerly regarded as minor imperfections in casting belts, at least when certain alloys are being cast. How should the extreme sensitivity of casting quality to belt stability--i.e., flatness--be explained?It was noted above that long-freezing-range alloys, notably high-magnesium alloys such as AA 5052, are highly sensitive to lack of belt flatness and stability. Such long-freezing-range alloys remain mushy and friable until they are completely frozen, since the mush is like a mix of particulate sand and water. The particulate sand is the higher-melting, earlier-freezing alloying combinations, and the water is low-melting-point liquid, tending toward a eutectic mixture. It appears that the friability of the AA 5052 aluminum alloy gives rise to fissures and bleeding when a belt warps thermally, a situation that permits bleeding of low-melting-point liquid, thereby bringing molten metal into close localized contact with the belt and so giving rise to still further loss of belt stability. Alloy AA 3004 has a smaller freezing range than AA 5052 but behaves much the same in this respect.It is known that metals that are more nearly pure such as aluminum alloy AA 1070 are stronger and less friable when hot than an alloy such as AA 5052. The more nearly pure alloys set up solid relatively soon as they cool. Assume that in casting an AA 1070 alloy a probe is installed near an inherently flat belt at a point downstream from the place where a shell of metal is frozen hard, even a thin shell. The probe will detect little or no belt unevenness, even given a defective belt coating; only background noise such as backup roller runout will be detected. It is believed that the thin, initially frozen shell of AA 1070 alloy is strong enough, yet flexible enough, to accomodate itself to the leveling out of the belt as the heat flux or rate of heat transfer drops, which drop naturally occurs as the 1070 product proceeds downstream in the casting machine.Though this explanation of the difference between the behavior of various alloys represents merely the current theoretical explanation to date, the present invention can be employed to significant advantage in casting various metals and their alloys. The proximity sensing measuring system apparatus described herein is a valuable trouble-shooting or diagnostic tool when used in the methods described. When multiple proximity probes 36 are deployed across or along a moving belt, they reveal its shape. The pattern of the readings helps to pinpoint the causes of slab defects--for instance, thinning of belt coating, insufficient belt preheating, and interaction of these factors with various alloys, nodes, loops, or kinks in the belt, etc.Although the examples and observations stated herein have been the results of experimental work with a limited number of molten metals and alloys, this invention appears applicable to the continuous casting of any metal.Although specific presently preferred embodiments of the invention have been disclosed herein in detail, it is to be understood that these examples of the invention have been described for purposes of illustration. This disclosure is not to be construed as limiting the scope of the invention, since the described methods and apparatus may be changed in details by those skilled in the art, in order to adapt these systems and methods for sensing the conditions and characteristics of casting belts and their thermally insulative coatings, if any, so as to be useful in various particular belt-type continuous casting machines or various belt-type caster installation situations, without departing from the scope of the following claims.	A method of monitoring distortions in a revolving casting belt in the continuous casting of metal product (P) from molten metal (35) employing a moving mold (C) including at least one revolving, tensed, flexible, electrically-conductive metallic casting belt (12 or 14) having a front face defining a portion of the moving mold and having a predetermined desired pass line position, and said casting belt having a back face cooled by aqueous coolant (82) applied to said back face in the vicinity of said moving mold, the method comprising the steps of: positioning a face (38) of an eddy-current proximity sensor (36) in predetermined position spaced by a predetermined spacing (42) away from said back face of the revolving casting belt, said proximity sensor being positioned in a region opposite to the moving mold (C);said proximity sensor being positioned at a predetermined distance from said desired pass line position of the front face of the revolving casting belt;using the proximity sensor for sensing variations from the predetermined spacing (42) between the back face of the revolving casting belt (12 or 14) and the face (38) of said proximity sensor (36); andfrom the sensed variations from the predetermined spacing (42) between the back face of the revolving casting belt and the face (38) of said proximity sensor (36) determining deviations of the front face of the revolving casting belt (12 or 14) away from or toward said predetermined pass line .The method claimed in Claim 1, characterized in that: said front face of said casting belt (12 or 14) bears a thermally insulative coating, and wherein:said sensed variations from the predetermined spacing (42) between the face (38) of the proximity sensor (36) and the back face of the revolving casting belt (12 or 14) is used for determining status of said insulative coating on said front face.The method claimed in Claim 2, further characterized by the steps of: predetermining a maximum acceptable value for variations from said predetermined spacing (42) for determining a maximum acceptable deviation of the front face of the revolving casting belt from the predetermined pass line ; andupon exceeding said maximum acceptable value, refurbishing the insulative coating on the front face of the revolving casting belt while continuing to perform continuous casting.The method in Claim 1, 2 or 3, characterized by the steps of: immersing at least part of said proximity sensor (36) in said aqueous coolant (82); andin using the proximity sensor for sensing variations from the predetermined spacing (42) between the back face of the revolving casting belt and the face (38) of said proximity sensor (36), making an allowance for effects of said aqueous coolant and any materials therein, such effects causing sensing of said spacing to seem smaller than actual spacing.The method claimed in Claim 1, 2, 3 or 4, wherein: the face (38) of said proximity sensor (36) is positioned at a predetermined spacing (42) in the range of about 2mm (about 0.08 of an inch) to about 10.2mm (about 0.40 of an inch) from said back face of the revolving casting belt.The method claimed in Claim 4, further characterized by the steps of: positioning the face (38) of said proximity sensor (36) at a predetermined spacing (42) from said back face of the revolving casting belt in the range of about 2mm (about 0.08 of an inch) to about 10.2mm (about 0.40 of an inch) andmaking an allowance for the electrical conductivity effects of said aqueous coolant (82) and any materials therein, said allowance being in the range from about 0.1mm (about 0.004 of an inch) to about 0.15mm (about 0.006 of an inch).The method claimed in Claim 1, 2, 3, 4, 5 or 6, wherein molten metal (35) being introduced into the moving mold (C) initially comes into thermally conductive relationship with said front face at a point (F) of first contact, characterized further by the step of: positioning the face (38) of said proximity sensor (36) at a point within a range of distance X from said point (F) of first contact;said range of distance (X) being measured in the downstream direction of motion of said moving mold (C); andsaid range of distance (X) being no more than about 254 mm (about 10 inches).The method claimed in Claim 3 for casting aluminum alloy (35) having a low alloy content, characterized by the further step of: predetermining said maximum acceptable value for said variations from said predetermined spacing (42) to be about 0.25mm (about 0.010 of an inch) for casting such aluminum alloy having low alloy content.The method claimed in Claim 3 for casting aluminum alloy (35) containing at least bout 2.5 percent by weight of magnesium and thereby having a long-freezing range , characterized by the further step of: predetermining said maximum acceptable value for said variations from said predetermined spacing (42) to be about 0.13mm (about 0.005 of an inch) for casting such aluminum alloy having such long-freezing range.The method as claimed in Claim 8 or 9, characterized by the further steps of: initially testing the casting belt (12 or 14) by revolving the tensed casting belt prior to introducing molten aluminum alloy (35) into the moving mold (C) and determining the maximum variation from said predetermined spacing (42); andavoiding use of the casting belt for continuous casting until after the belt has been subjected to flattening if the initial testing reveals a variation from said predetermined spacing (42) exceeding said maximum acceptable value.A method of testing each of two new casting belts prior to employing the belt for casting in preparing for the operation of a twin-belt continuous casting machine (10) wherein two tensed, flexible, steel casting belts (12, 14) are simultaneously revolved, and each of said casting belts has a front face and a back face, and said front faces are to be used for defining a moving mold (C) between them as said casting belts are simultaneously revolving, and the back faces of the revolving belts are cooled by aqueous coolant (82) applied to the back faces in the vicinity of the moving mold, the method comprising the steps of: revolving the new casting belt while tensed under a tension of at least about 700 kilograms per sq. cm. (at least about 10,000 pounds per square inch);positioning a face (38) of an eddy-current type of proximity sensor (36) at a predetermined spacing (42) from the back face of the revolving, tensed casting belt (12 or 14);using the proximity sensor (36) for sensing variations from said predetermined spacing (42) between the face (38) of the proximity sensor (36) and the back face of the revolving casting belt;determining whether there is any variation from said predetermined spacing at least as great as a critical value of about 0.2mm (about 0.008 of an inch);in the absence of any variation amounting to such critical value, proceeding to employ the new casting belt for continuous casting in a twin-belt machine; andwith the occurrence of any variation as large or larger than such critical value, proceeding to subject the new casting belt to a levelling operation prior to employing the new casting belt for continuous casting in a twin-belt casting machine.The method as claimed in Claim 11, in which: the face (38) of the proximity sensor (36) is positioned at a predetermined spacing (42) in the range of about 2mm (about 0.08 of an inch) to about 10.2mm (about 0.40 of an inch) from the back face of the revolving, tensed casting belt.A casting machine comprising a twin-belt continuous casting machine and an apparatus for monitoring characteristics of the front face of at least one casting belt as said one belt is revolving during continuous casting in the twin-belt continuous casting machine (10) wherein two tensed, flexible, electrically-conductive casting belts (12, 14) are simultaneously revolved, and each of said casting belts has a front face and a back face, and said front faces are used for defining a moving mold (C) between them as said casting belts are simultaneously revolving, and said back faces are cooled by aqueous coolant (82) applied to the back faces in the vicinity of the moving mold, and each of said belts is desired to follow a predetermined pass line during continuous casting, said apparatus comprising: an eddy-current type of proximity sensor (36);mounting means (49, 44, 48) holding the face (38) of said proximity sensor (36) in predetermined spacing (42) away from the back face of said one belt;said mounting means holding said proximity sensor in a region where said one belt is desired to move along said pass line ;energizing means (37) for energizing said proximity sensor with an alternating current; and means (39) for determining variations from the predetermined spacing (42) between said face (38) of the proximity sensor (36) and said back face of the revolving casting belt for determining deviations of the revolving casting belt from said pass line .The apparatus as claimed in Claim 13, wherein: said mounting means (49, 44, 48) holds the face (38) of said proximity sensor (36) at a predetermined spacing (42) in a range of about 2mm (about 0.08 of an inch) to about 10.2mm (about 0.40 of an inch) from said back face.The apparatus as claimed in Claim 13 or 14 wherein: said mounting means holds said proximity sensor downstream from a point of first contact (F) of molten metal (35) with the front face of the revolving casting belt (12 or 14) at a distance (X) no more than about 254mm (about 10 inches) from said point of first contact (F).	HAZELETT STRIP CASTING CORP; HAZELETT STRIP-CASTING CORPORATION	BERGERON NORMAN J; GRAHAM THOMAS S; BERGERON, NORMAN J.; GRAHAM, THOMAS S.
EP-0489435-B1	489,435	EP	B1	EN	19,990,421	1,992	20,100,220	new	C08K5	C08K3	C08K5, C08J3, C08L27, C08K3	C08K 3/00P5+L27/12, C08K 5/00P4+L27/12, C08K 5/00P4+L33/06, C08K 3/00P5+L33/06	Crosslinkable elastomer composition	An elastomeric composition containing a fugitive tracer compound that fluoresces on exposure to radiation, but which loses its fluorescence during postcuring treatment permits monitoring of the completeness of the cure.	BACKGROUND OF THE INVENTIONElastomers are typically compounded with fillers, crosslinking agents and other additives, followed by forming or shaping into the desired configuration for the article to be made from the elastomer. This forming can be by calendaring or extrusion, but most often is done by compression or injection molding. After shaping, the elastomer molecules are crosslinked by the action of the crosslinking agents to establish a three-dimensional structure that provides strength and form stability. Such crosslinking, or curing, is usually effected by heat and time. An elastomer is often first press-cured at an elevated temperature and pressure when confined in a mold, and then post-cured at elevated temperatures and ambient pressures for an additional period to complete the curing.Many elastomers can be cured in relatively short periods, while other elastomers, and particularly fluoroelastomers and ethylene/acrylic elastomers, require several hours for full development of the desired mechanical and aging properties of the finished product. Since these properties are dependent on the completion of this curing or postcuring process, techniques have previously been developed to test the degree of curing in an elastomeric composition. Such techniques have heretofore often required time-consuming destructive physical testing of lot samples. SUMMARY OF THE INVENTIONThe present invention provides a quick and simple non-destructive means by which a manufacturer of elastomeric articles can determine whether the article has, in fact, been subjected to the post-curing process. In a preferred embodiment of the present invention, there is further provided a means to identify the origin or manufacturing lot of an elastomeric material by a non-destructive test.Specifically, the instant invention provides a crosslinkable elastomer composition comprising (a) a fluoroelastomer and(b) from 0.025 to 3 parts by weight, per hundred parts of the elastomeric polymer, of a fugitive fluorescent compound which is stable at temperatures of from 145-205°C for at least 1-60 minutes and which decomposes or is volatilized from the composition at temperatures of from 170°C-250°C within 1-24 hours.The composition preferably further comprises from 0.05 to 5 parts by weight of an inorganic phosphor that fluoresces at a wavelength which is different from that of the fluorescent compound and that is stable at a temperature of at least 170°C for a period of at least one hour.DETAILED DESCRIPTION OF THE INVENTIONA wide variety of crosslinkable elastomeric polymers can be used in the present invention, including those that develop form stability by press-curing or crosslinking in a mold after a period of 1-60 minutes at temperatures of 145-205°C, but which, in order to develop their optimum physical properties, are subjected to a postcure cycle in a circulating air oven at temperatures of 170-250°C for 1-24 hrs. Representative crosslinkable fluoroelastomers which can be used in the present invention include fluoropolymer elastomers comprising copolymerized units of one or more monomers containing fluorine, such as vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, and perfluoro(alkyl vinyl ether), as well as other monomers not containing fluorine, such as propylene. Elastomers of this type are described in Logothetis, Prog. Polym. Sci., Volume 14, pages 251-296 (1989).Representative fluoroelastomers include copolymers of vinylidene fluoride and hexafluoropropylene and, optionally, tetrafluoroethylene; copolymers of tetrafluoroethylene and propylene; and copolymers of tetrafluoroethylene and perfluoro(alkyl vinyl ether), preferably perfluoro(methyl vinyl ether). Each of the above fluoroelastomers can optionally also include a curesite monomer. Copolymers of ethylene, tetrafluoroethylene, perfluoro(alkyl vinyl ether) and a bromine-containing curesite monomer, as described in Moore, U.S. Patent 4,694,045, can also be used in the present invention. The fluoroelastomer is preferably a perfluoroelastomer.Depending on their composition, fluoroelastomers are generally crosslinked by the action of diamines or polyols in conjunction with an accelerator such as a quaternary ammonium or phosphonium compound, or by organic peroxides together with a polyfunctional coagent. Metal oxides or hydroxides and fillers or carbon black are also usually present in the compounded elastomer. Copolymers of tetrafluoroethylene and perfluoro(alkyl vinyl ether) require special cure sites and curing systems as described in Logothetis, U.S. Patent 4,948,853.In the curing of the above fluoroelastomers, the compositions are first cured in a closed mold, or press-cured, and then postcured in an oven in an atmosphere of air or an inert gas. The initial curing is generally for periods of 1-60 minutes at temperatures of 145-205°C, depending on the particular fluoroelastomer composition used. During the initial curing, the fluoroelastomer composition is generally maintained under a pressure in the mold of from 0 to 3500 MPa. The post cure is typically at ambient pressure, and temperatures of from 170° to 250°C for periods of 1-24 hours. As recognized by those skilled in the art, crosslinking is typically accomplished by heating for short periods of time at temperatures of 160-180°C in a closed mold. The resulting products are then usually postcured in an air oven for 1-24 hours, and preferably 1-8 hours. The postcuring temperatures are generally in the range of 170-250°C, and often 170-190°C.The elastomer compositions of the present invention contain from 0.025 to 3 parts by weight, per hundred parts of the elastomer, of a fugitive fluorescent compound or dye which is insoluble in the crosslinkable elastomer, and is stable at the curing temperature, pressure, and time of the elastomer for a period of at least 1 hour. The term fugitive refers to a compound which decomposes or volatilizes from the elastomer when heated at a temperature of at least 170°C and ambient pressure for 1-24 hours. Accordingly, the fluorescent compound is stable under the conditions of press cure, but, after the postcure process, is no longer detectable under the conditions first used for its observation. Preferably, the fugitive compound fluoresces in the visible range when exposed to black light.The specific amount of the fugitive fluorescent compound will vary with the particular elastomer, the intensity with which the dye fluoresces and the concentration of fillers and other additives used. In general, however, from 0.05 to 0.3 parts, per 100 parts by weight of elastomer, are preferred for the present compositions. In general, it will be desired to use the minimum operable amount of the fugitive compound to avoid unnecessary contamination of operating equipment or other samples by excess fugitive compound on the surfaces of the molded parts. The fugitive fluorescent compound should not react with curing agents present in the elastomer compound, or interfere in any other substantial way with the curing process.It has been found that during the molding cycles described, in closed molds, at least a portion of the fluorescent compound migrates or exudes to the surface of the molded part, and is thereby concentrated and more readily observable. While a wide variety of fugitive fluorescent compounds can be used, those that are visible under black or ultraviolet light have been found particularly convenient, and are accordingly preferred.It is also preferred that the fugitive fluorescent compound be insoluble in the elastomer, to facilitate the exuding or blooming of the fugitive compound to the surface of the molded article. In addition, the compound should degrade or volatilize from the elastomer under the conditions of the postcure treatment, so that its identifying fluorescence is no longer detectable under the conditions first used for its observation.A wide variety of fugitive fluorescent compounds can be used in the present compositions. The fugitive fluorescent compound is preferably organic. Recognized classes of such compounds which can be used include coumarin, xanthene, methine, napthalimide, anthraquinone, and stilbene derivatives, as well as heterocyclic compounds containing one or more of nitrogen, oxygen and sulfur atoms. Coumarin dyes and sulfur heterocyclic compounds such as thiophenes and thiophene derivatives are preferred. Other heterocyclic compounds which can be used include benzoxazole and benzopyranone. 7-diethylamino-4-methylcoumarin has been found to be particularly satisfactory.The compositions of the present invention preferably further comprise an inorganic phosphor that fluoresces at a wavelength which is distinguishable from that of the fugitive fluorescent compound, and that is non-fugitive under postcuring conditions used for the elastomer. Preferably, the inorganic phosphor fluoresces when activated by ultraviolet light. It is also preferred that the phosphor fluoresce in the visible spectrum. The effective amount of the phosphor will, of course, vary with the particular phosphor used, but will generally be from 0.05 to 5 parts, and especially 1-2.5 parts, per 100 parts of elastomer. The phosphor should be substantially uniformly distributed throughout the elastomer.Since the phosphor is finely dispersed in the matrix, it does not migrate to the surface or interfere with the detection of the fluorescent organic fugitive fluorescent compound at the surface. Although the phosphors can be detected by examination of molded surfaces, their presence is most readily detected in the interior of the sample when a freshly cut surface is observed under black light. Detection of a particular phosphor color thereby serves as a convenient method for identifying a particular elastomer as to source, production lot or other history. It has also been found that the inorganic phosphors, after postcure, readily reveal the presence of flaws on the surfaces of molded articles as regions of more intense fluorescence under black light. Such flaws are often not easily observed under ordinary visual examination, and use of the phosphor thus serves as an improved quality control sensor for demanding applications.Phosphors which can be used in the present invention include those that are commonly used for manufacture of cathode-ray tubes, fluorescent lights photocopier lamps, x-ray intensifying screens and the like. Their utility is a function of the relative brightness of the phosphor, and it is desirable that, when activated by long wave radiation, they emit at least 50% of the absorbed radiation. Representative of the many known phosphors which can be used are those classified by the Joint Electronic Device Engineering Council (JEDEC) under classifications P-4, P-15, P-22, and P-43. The phosphors generally comprise an activator. Representative phosphors and preferred activators are summarized in the following Table. PhosphorActivatorColor(Zn,Cd)SAgyellowZnSAgblueZnOZngreenY2O2SEuredGd2O2STbgreenCaWO4PbblueBaMg2Al16O27EublueCa5F(PO4)3Sb:MnyellowGd2O2STbgreen(Zn,Cd)SCu:Algreen(blend) ZnS (Zn,Cd)SAg Cu:AlwhiteZnS Cu:AlgreenZn2SiO4 Mn green Y2O3EuredMg4(F)GeO6MnredCaSiO3Pb:MnorangeY3Al5O12CeyellowSr3(PO4)2EublueBa3(PO4)2EubluePreferred phosphors are ZnS:Cu:Al (green) and ZnS:Ag (blue).Fluorescence due to either the fugitive fluorescent compound (before postcure processes) or the inorganic phosphor can be observed on exposure of the molded specimens to ultraviolet radiation at frequencies near the peak excitation range of the fluorescing substrate, typically 200 - 400 nm. For reasons of eye safety, however, it is desirable to use radiation having a wavelength of from 365 to 400 nm. Such radiation is alternatively referred to as long wave ultraviolet or black light. Sources of such radiation having intensities of at least 600 µW/cm2 are preferred and are readily available commercially. For ease of observation, it is expedient to carry out the observation in a darkened area, most preferably in a totally enclosed and darkened housing.The compositions of this invention can be prepared by known mixing procedures for compounding the elastomers with crosslinking agents, fillers, pigments and reinforcing agents, processing aids and antioxidants. For example, high shear mixing devices such as Banbury internal mixers, mixing extruders, or two-roll rubber mills can be used to intimately disperse the fluorescent dye and inorganic phosphor at moderately elevated temperatures, e.g., 90-120°C or below for a few minutes, e.g., 2-6 minutes.Either or both of the fugitive compound and phosphor can be added, if desired, as a concentrate in a carrier that does not interfere with the cure of the elastomer. If used, the carrier is preferably a polymeric carrier, and especially one that is compatible with the elastomer. A polymeric carrier that will be the elastomer of the composition is particularly desirable.The fugitive fluorescent compound and phosphor of the invention can be added at a time prior to, subsequent to or simultaneously with mixing of the normal curatives, fillers, process aids, antioxidants or other adjuvants commonly used with the elastomers of the invention. However, to minimize any potential interaction between the fugitive fluorescent compound and polymer curatives, it may in some instances be advantageous to add the fugitive compound after the curatives are fully dispersed and diluted.When the compositions of the present invention are heated in a closed mold for short periods of time, the fluorescent compound often exudes to the surface of the molded article, where it is more readily visible in black light. In further, long term heating outside the mold, the fluorescent compound or dye either degrades chemically, or volatilizes from the elastomer under the the conditions of post-cure so that it is no longer detectable under black light, thus verifying the postcure treatment. After the fluorescence of this component has been lost, then the identifying fluorescence of the inorganic phosphor, if present, can be readily observed.The present invention is more fully illustrated in the following examples, in which Fluoroelastomer A was a composition containing 97.5 parts of a copolymer having a nominal composition of 60 wt% vinylidene fluoride and 40 wt% hexafluoropropylene, having a Mooney viscosity at 121°C of 60 and containing blended therein 2.5 parts of a 1:1 salt obtained by reacting benzyltriphenylphosphonium chloride and 4,4'-hexafluoroisopropylidene diphenol.Fluoroelastomer B had a nominal composition of 60 wt% vinylidene fluoride and 40 wt% hexafluoropropylene and had a Mooney Viscosity of 60 at 100°C.Fluoroelastomer C had a nominal composition 34 wt% vinylidene fluoride, 38 wt% perfluoro(methyl vinyl ether) 26 wt% tetrafluoroethylene and a small amount of a bromine-containing curesite monomer for peroxide cure. Fluoroelastomer C had a Mooney viscosity of 65 at 121°C.The ethylene/acrylic copolymer had a nominal composition of 41 wt% ethylene, 55 wt% methyl acrylate and 4 wt% of a curesite monomer and had a Mooney Viscosity of 16 at 100°C.All of these polymers, when cured by typical recipes in commercial use, had physical properties that were not substantially changed by incorporation of the fugitive fluorescent dyes or inorganic phosphors as described hereinbelow.Two sources of long wave radiation were used for the detection of fluorescent material. Both were obtained from UV Products, Inc. Black Light #1 (BL-1) was Model UVGL-58 (6 watt), emitted with an intensity of 600 µW/cm2 at a wavelength of 365 nm. and was used with a CC-10 housing. Black Light #2 (BL-2) was Model B-100A, gave 7000 µW/cm2 of long wave radiation and was also used in a darkened enclosure for sample viewing.All inorganic phosphors were obtained from GTE Products Corporation, Towanda PA. EXAMPLE 1Fluoroelastomer A was mixed on a cold mill with 3 parts per hundred of rubber (phr) of magnesium oxide (Maglite D), 6 phr of calcium hydroxide, 30 phr of N990 MT carbon black and 0.3 phr of an organic fluorescent dye. The dye is commercially available from Day-Glo Color Corporation as Columbia Blue, and was identified as 7-diethylamino-4-methylcoumarin. O-ring specimens having an outer diameter of 2.54 cm. and a thickness of 0.353 cm were compression molded in a press for 5 min at 177°C and then unloaded while still hot. After cooling the specimens were examined using BL-1 and were found to have a highly visible blue fluorescent coating but were black in the absence of UV light. The specimens were then postcured in a circulating air oven for 24 hours at 232°C. They were again examined under BL-1 and were found to have no significant blue fluorescence on the surface.EXAMPLE 2Fluoroelastomer A was compounded with curatives as described in Example 1, and in addition, contained 1 phr of Columbia Blue and 2.5 phr of a ZnS phosphor, activated with copper and aluminum (JEDEC No. P-22 Green). After press cure as in Example 1, the specimens had a bright fluorescent blue color when examined under BL-1. After postcure for 24 hours at 232°C, the surfaces had a dull green fluorescence. When the o-rings were cut and a fresh surface examined under BL-1, they exhibited the brighter fluorescent green color of the phosphor.EXAMPLES 3-6Fluoroelastomer A was compounded with curatives as in Example 1, and additionally contained 2.5 phr of ZnS:Cu:A1 phosphor. Examples 3-6 further contained 0.025, 0.05, 0.1 and 0.3 phr Columbia Blue dye, respectively. After press cure as in Example 1, blue fluorescence on the surfaces was easily discerned under BL-1 for Examples 4-6, and was faintly visible for Example 3. After postcure there was no visible blue fluorescence on the o-ring surfaces, and a green fluorescence was readily visible.EXAMPLE 7Fluoroelastomer A compounded with curatives as in Example 1 and containing 0.05 phr of Columbia Blue was press cured into o-rings for the following cycles: 30 min/148°C, 10 min/177°C and 30 min/162°C. After removal from the press and examination under BL-2 all samples showed the blue fluorescence of the dye on the surface.EXAMPLE 8Fluoroelastomer B was compounded with 1.5 phr hexamethylenediamine carbamate, 20 phr MT black, 15 phr magnesium oxide (Maglite Y), 0.05 phr Columbia Blue dye and 2.5 phr ZnS:Cu:A1 phosphor and o-rings press cured and postcured as described in Example 1. Under BL-2 the blue fluorescence of the dye was readily observed after press cure, but not after postcure. The phosphor was readily observable under the black light at all stages of processing.EXAMPLE 9Fluoroelastomer C was compounded with 30 phr MT black, 3 phr each of litharge, 2,5-dimethyl-2,5-bis-(t-butylperoxy)hexyne-3 (45% on calcium carbonate) and triallyl isocyanurate, 0.05 phr Columbia Blue dye, and 2.5 phr Mg4(F)GeO6:Mn phosphor (red, Type 236 from GTE) and o-rings were then press cured and postcured as in Example 1. Under BL-2, after press cure, the typical blue color of the dye was observed and after postcure only the red color of the phosphor was observable, especially on a freshly cut surface. EXAMPLE 10Fluoroelastomer A was compounded with curatives as in Example 1. To each of five equal aliquots was added 0.1, 0.5, 1, 1.5, and 2 phr, respectively, of ZnS:Cu:Al phosphor. The phosphor was green Type 1260 from GTE. O-rings were presscured and postcured as in Example 1 and viewed under BL-2. With the higher power of BL-2, 1.5 parts of phosphor 1260 could easily be seen, and levels as low as 0.5 phr of the phosphor could also be seen but appeared less uniform.EXAMPLE 11Ethylene/acrylic elastomer was compounded on a cold mill with the following ingredients: 55 phr SRF black, 1.25 phr hexamethylenediamine carbamate, 4 phr di-o-tolylguamidine (DOTG), 2 phr 4,4'-di(a,a-dimethylbenzyl) diphenylamine antioxidant (Naugard 445), 0.5 phr complex organic ester free acid (Vanfree VAN), 0.5 phr octadecyl amine crosslinking agent and 0.05 phr Columbia Blue fluorescent dye and 2.5 phr of ZnS:Cu:Al phosphor. Slab specimens, 1.6 mm (1/16 inch) thick were cured in a press for 10 min at 180°C and then postcured for 4 hours at 180°C. The blue surface color of the dye was observable under BL-2 after press cure and the green color of the phosphor was slightly visible after post cure.EXAMPLES 12-21Compounds were prepared as in Example 2, except that the phosphor concentration was 1.5 phr, using 0.2 phr of the fluorescent organic compounds or dyes listed in the Table. The dyes for Examples 12-17 were obtained from Aakash Chemicals & Dye-Stuffs, Inc., while the dyes for Examples 18-21 were obtained from Keystone Aniline Corp. O-rings were molded as in Example 1 except that pressing time was 10 minutes. After cooling, the o-rings were examined under black light and all were found to fluoresce in a color which is characteristic of each dye and not necessarily the color in its identification. After postcure as in Example 1, the o-rings all fluoresced in the green which is characteristic of the phosphor. Ex.Supplier's IdentificationChemical Name or Description12Acid Red 52Rhodamine B (a xanthene dye)13Basic Yellow 40coumarin dye14Disperse Yellow 82methine dye15Disperse Yellow 184napthalimide dye16Solvent Yellow 43anthraquinone dye17Solvent Yellow 44napthalimide dye18Keyfluor White PLbenzoxazole (a nitrogen/oxygen heterocyclic dye)19Keyfluor White CXDPoxazinone derivative (a mixed heterocyclic dye)20Keyfluor White STtriazinyl stilbene derivative21Keyfluor White RWPBenzopyranone brightenerEXAMPLES 22-24Compounds were prepared as in Example 1 except that three different fluorescent dyes obtained from Aldrich Chemical Co., Inc. were used at the 0.1 phr level instead of the Columbia Blue. O-rings were molded as in Examples 12-21. The o-rings of Examples 22 and 23 fluoresced in different shades of blue. After postcure as in Example 1, fluorescence was not discernible. Fluorescence could not be detected for the o-rings of Example 24. However, when the dye concentration was increased to 0.2 phr, light blue fluorescence was observed. The fluorescence vanished with postcure. This illustrates that the minimum effective dye concentration will vary with the dye. Ex.Supplier's CodeChemical Name or Description22D8,775-97-diethylamino-4-methylcoumarin2322,399-92,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene2429,418-74,4'-diamino-2,2'-stilbene sulfonic acidEXAMPLE 25The fluorescent dye of Example 21 was incorporated at a concentration of 0.2 phr in compounds as in Examples 1 and 2, except that the phosphor was used at the 1.5 phr level. After molding, o-rings exhibited a bright blue fluorescence in both cases. When cut, the interior of the o-ring without phosphor fluoresced blue while the interior of the o-ring with phosphor fluoresced green. This is interpreted to indicate migration of the dye toward the surface, reducing the dye concentration in the interior. After postcure, there was no dye fluorescence either on exterior or exposed interior surfaces, with or without phosphor. EXAMPLE 26The compound of Example 2 was prepared except that the phosphor concentration was 1.5 phr and the Columbia Blue dye concentration was 0.002 phr, achieved by using an extended dye preparation from Day-Glo Color Corporation called Invisible Blue. Fluorescence was not detected on o-rings molded from this compound.EXAMPLE 27Compounds were prepared as in Example 2 except that the dye concentration was 0.05 phr and the phosphor concentration was 1.5 phr. After molding, o-rings exhibited the characteristic fluorescence of the dye. O-rings were placed in curing ovens at various temperatures and the disappearance of the dye fluorescence was monitored. At 232°C and 204°C, the blue fluorescence was nearly gone in 20 minutes. At 177°C, the blue fluorescence was nearly gone in 2 hours. At 121°C, there were still traces of blue fluorescence after 23 hours. This illustrates the time-temperature dependence for elimination of the tracer dye fluorescence.	A crosslinkable elastomer composition comprising (a) a fluoroelastomer and(b) from 0.025 to 3 parts by weight, per hundred parts of the elastomeric polymer, of a fugitive fluorescent compound which is stable at temperatures of from 145-205°C for at least 1-60 minutes and which decomposes or is volatilized from the composition at temperatures of from 170°C-250°C within 1-24 hours.A composition of claim 1 further comprising from 0.05 to 5 parts by weight of an inorganic phosphor that fluoresces at a wavelength which is different from that of the fugitive fluorescent compound and is stable at a temperature of at least 170°C for a period of at least one hour.A composition of claim 1 wherein the fugitive fluorescent compound is organic and is insoluble in the crosslinkable elastomeric polymer.A composition of claim 1 wherein the fugitive fluorescent compound fluoresces in the visible range on exposure to ultraviolet light.A composition of claim 2 wherein the inorganic phosphor fluoresces in the visible range on exposure to ultraviolet light.A composition of claim 3 wherein the fugitive fluorescent organic compound is a coumarin and preferably consists essentially of 7-diethylamino-4-methylcoumarin. A composition of claim 3 wherein the fluorescent compound is a sulfur heterocyclic compound and preferably consists essentially of a thiophene.A composition of claim 2 wherein the inorganic phosphor is selected from the group consisting of ZnS, Zn2SiO4, and Mg4FGeO6 and preferably consists essentially of ZnS.A composition of claim 8 wherein the ZnS is activated with copper and aluminum or wherein the ZnS is activated with silver.A composition of claim 1 wherein the fluoroelastomer is a perfluoroelastomer.	DU PONT; E.I. DU PONT DE NEMOURS AND COMPANY	ALEXANDER JAMES ALEN; BROTHERS PAUL DOUGLAS; MAZZOLA PHILIP CHARLES; STEPANEK MARK ALAN; ALEXANDER, JAMES ALEN; BROTHERS, PAUL DOUGLAS; MAZZOLA, PHILIP CHARLES; STEPANEK, MARK ALAN
EP-0489436-B1	489,436	EP	B1	EN	19,970,312	1,992	20,100,220	new	A61B17	null	A61B17, A61B19	A61B 17/072, K61B19:00Q10	Surgical fastening apparatus with locking mechanism	An improved apparatus for applying surgical fasteners to body tissue comprising a cartridge (101) containing a plurality of fasteners, an anvil (108) positioned opposite the cartridge (101, 218, 313), and a locking mechanism (103, 315, 220) to prevent re-approximation of the cartridge towards the anvil when the cartridge is withdrawn from the anvil after the fasteners are fired.	BACKGROUND OF THE INVENTION1. Field of the InventionThis invention relates to surgical fastening apparatus, and specifically to an improved surgical fastening apparatus containing a locking mechanism. A fastener applying apparatus in accordance with the pre-characterising part of claim 1 below is disclosed in EP-A-0 136 948. 2. Background of the ArtSurgical fastening apparatus for simultaneously applying an array of surgical staples or other types of fasteners are known in the art. Such apparatus are used for suturing body tissue such as, for example, intestinal and gastric walls with spaced parallel rows of longitudinally aligned staples. These surgical stapling apparatus reduce the time of wound closure in a surgical procedure. Typically these devices include a fastener holder disposed on one side of the tissue to be fastened, and an anvil assembly parallel to the fastener holder on the other side of the tissue to be fastened. The fastener holder is moved linearly towards the anvil assembly so that the tissue is clamped between them. The fasteners are driven from the fastener holder so that the ends of the fasteners pass through the tissue and form finished fasteners as they make contact with the anvil assembly, thereby producing an array of finished fasteners in the tissue. Optionally, the fastening apparatus may include a knife mechanism for creating an incision between rows of fasteners. The fasteners can be made of metal, non-absorbable polymers, or bioabsorbable polymers such as polyglycolide, polylactide, and copolymers thereof. In common use are apparatus in which the fastener holder comprises a disposable cartridge removably mounted in or on a permanent actuator for supporting and actuating the cartridge. The cartridge is disposable after a single use, i.e. after the fasteners are fired. The permanent actuator is reusable in the same surgical procedure after reloading with a fresh cartridge, and is reusable in another surgical procedure after cleaning, sterilizing, and reloading. Also known are disposable surgical apparatus, in which the entire apparatus is disposed of after use. Examples of surgical stapling apparatus may be found in U.S. Patent No. 4,354,628 to Green, U.S. Patent No. 4,665,916 to Green, and U.S. Patent Des. 283,733 to Rawson et al. In the use of surgical fasteners the possibility arises that the fastener apparatus may be actuated when the cartridge is empty of fasteners. This can occur when the apparatus has been fired once, but the cartridge is not reloaded or discarded. This can also occur if the apparatus is inadvertently reloaded with a spent cartridge. Under such circumstances the fastening apparatus will fail to suture the body tissue, which can cause harm to the patient and result in the surgeon's loss of valuable time. The risk of harm is greatly increased if the apparatus contains a knife mechanism, since it will create an unsealed incision. To eliminate these dangers to the patient it would be beneficial to provide a mechanism which alerts the user that a new cartridge is required. It would further be beneficial if such a mechanism can provide a lock to actually prevent the surgeon from trying to fire a cartridge that has already been fired and prevent reloading of a spent cartridge. This would save valuable time and reduce the risks to the patient. The present invention relates to such an apparatus. A lock-out mechanism to prevent refiring of staples from a cartridge is disclosed in EP-A-0 373 762. SUMMARY OF THE INVENTIONClaim 1 below defines an apparatus in accordance with the invention for applying a plurality of surgical fasteners to body tissue. The fasteners can be metal staples having deformable legs or two-part fasteners fabricated from bioabsorbable polymer such as polyglycolide, polylactide, and glycolide/lactide copolymer. In embodiments of the invention, the apparatus includes means for holding a fastener carrying cartridge; means for moving the fastener carrying cartridge between a proximal first position and a distal second position wherein the cartridge is in close approximation to fastener closing means; means for substantially simultaneously ejecting the fasteners from the cartridge for closure thereof by the fastener closing means; approximation blocking means; and a locking member movable in response to the ejection of the fasteners and movement of the cartridge from the second cartridge position to the first cartridge position whereby the locking member becomes engageable with the approximation blocking means and prevents movement of the cartridge from the first cartridge position to the second cartridge position. The locking member is associated with the cartridge and is at least partially located inside the cartridge. In one embodiment the approximation blocking means comprises a member having first and second slots, and the locking member includes a slot engaging rod which is movable between a first position wherein it is slidable into the first slot of the approximation blocking means and a second position wherein it is slidable into the second slot of the approximation blocking means. In another embodiment the approximation blocking means comprises a surface for blocking distal movement of the locking member and the locking member is a drop bolt slidably mounted within the cartridge and movable from a first position to a second position wherein it is engageable with said approximation blocking means. Means is provided for biasing the locking member to the second position, and restraining means is provided for preventing the locking member from moving to the second position. The restraining means is movable from an initial restraining position to a non-restraining position when the fasteners are ejected from the cartridge. BRIEF DESCRIPTION OF THE DRAWINGSEmbodiments of the invention are described in more detail hereinbelow wherein: Fig. 1 illustrates a fastener applying apparatus in elevated perspective view. Figs. 2a, 2b and 2c, illustrate in elevational sectional view the distal portion of the fastener applying apparatus in the pre-firing, fired, and after firing positions, respectively. Fig. 3a illustrates a side view of the resilient locking clip. Fig. 3b is a perspective view of an alternative locking clip with ribbed hook portion. Fig. 4 is a side elevational view of a two-part surgical fastener. Figs. 5 to 8 illustrate partially cut away side elevational views of an alternative embodiment of the locking mechanism of the present invention in four stages of operation, respectively: apparatus preclosed condition, apparatus closed but unfired, apparatus fired, apparatus reopened with attempted reclosure with spent cartridge. Fig. 9 illustrates the T-shaped locking member embodiment of Figures 5-8 of the present invention in perspective view. Fig. 10 illustrates a detailed partially sectional side elevational view of the T-shaped locking member and the approximation blocking means. Figs 11 to 14 illustrate partially cut away side elevational views of another embodiment of the present locking mechanism of the present invention in four stages of operation, respectively: apparatus preclosed condition, apparatus closed but unfired, apparatus fired, and apparatus reopened with attempted reclosure with spent cartridge. Fig. 15 illustrates the drop bolt embodiment of the locking mechanism of Figures 11-14 in perspective view. Figs. 16a and 16b illustrate, in plan view, the drop bolt and the leaf spring bolt retainer in apparatus prefired, and apparatus fired condition, respectively. DETAILED DESCRIPTION OF THE INVENTIONFig. 1 illustrates a surgical stapler 100 having an elongated carrier portion 100a, a handle 100b, an actuating lever or trigger 100c, a safety latch 100d for locking the trigger 100c, an approximating lever 100e, a U-shaped distal portion 100f, a staple holder cartridge 101, and an anvil assembly 122 comprising an anvil 108 for closing or crimping the staples and an anvil support arm 102. The instrument operates by positioning body tissue between the staple holder cartridge 101 and the anvil 108, then, by pivoting the approximating lever 100e, pivoting and sliding the staple cartridge 101 into a closed position wherein it is in close approximation to the anvil 108 so that it can grip tissue held therebetween. Next, the apparatus is fired by pressing the trigger 100c towards handle 100b, thereby substantially simultaneously driving surgical staples into the body tissue, the staple legs being crimped by anvil 108. Finally, the apparatus is opened by pivoting the approximation lever 100e to withdraw the cartridge 101 proximally away from the anvil assembly, thereby releasing the body tissue. The term fasteners is used herein as a generic term which includes surgical staples, and the staple-shaped portion of two-part surgical fasteners, and equivalents thereof. Thus, although the surgical fastener of the present invention is exemplified in Figures 1-3 as a staple embodiment, the inventive features described herein are applicable to instruments for applying metal staples, as well as staples and two-part fasteners made from non-bioabsorbable or from bioabsorbable polymers (e.g. polyglycolide, polylactide and copolymers thereof). A two-part fastener is illustrated in Fig. 4. Unlike one piece staples which are closed by crimping the legs, the two piece fasteners are typically closed by joining and interlocking the two parts of the fasteners together. Typically, a two-part fastener includes a fastener portion 151 and a retainer portion 152. The fastener portion has prongs 153 which are adapted to be received into apertures 154 in the retainer and locked therein. The term anvil assembly is used herein as a generic term to include the anvil used to clinch surgical staples, the retainer holder and retainer member of two-part resinous surgical fasteners, and the equivalent of these elements. The anvil assembly of a fastener applying instrument holds the retainer portions until the fasteners are locked therein, whereupon the retainers are released. Thus, the present invention should not be construed as being limited only to instruments for applying metal staples, but rather more generally to surgical fastener applying apparatus. The locking mechanism of the present invention enables the apparatus to be fired only once in a single use, as it prevents reclosing of the apparatus, i.e., re-approximation of cartridge 101 after the fasteners have been fired and the cartridge 101 is retracted to its open position. If the cartridge 101 is adapted to be disposable and replaceable the apparatus can be refired by substituting a new cartridge loaded with staples. If reloaded with a spent (already fired) cartridge, the locking mechanism will prevent approximation of the cartridge and thereby not allow the instrument to be fired. In general, the apparatus of the present invention includes a locking mechanism associated with the cartridge and an interference means, i.e. an approximation blocking means, associated with the anvil assembly. The approximation blocking means cooperates with the locking mechanism to prevent closure of the apparatus, that is, the cartridge 101 cannot be moved into close approximation with the anvil 108. In the illustrated embodiment (Figure 2A), the approximation blocking means comprises a slot 104 formed in the anvil support arm 102 to provide a blocking surface at approximately a right angle to the motion of the cartridge. Alternately, one or more slots at differing angles could be provided to receive the locking mechanism. Clearly, the number, position, and configuration of the slots will vary depending on the locking mechanism employed. For example, if the locking mechanism is designed to extend linearly, the slot will extend longitudinally. Moreover, other blocking means besides slots can be provided as long as they achieve the function of engaging the locking mechanism to restrict movement of the cartridge. As noted above, the locking mechanism of the present invention is associated with the cartridge and cooperatively engages the approximation blocking means so as to prevent distal movement of the cartridge beyond a predetermined position. The lockout mechanism is actuated after two movements have been completed: 1) firing of the fasteners from the cartridge, and 2) reopening the apparatus i.e. proximal movement of the cartridge to permit removal of tissue. In the embodiment shown in Figures 2 and 3, approximation blocking means is in the form of slot 104. The locking mechanism in this embodiment is designated by reference numeral 103 and includes a detent or hook 103d for engaging the slot. Cooperation between the locking mechanism and the walls of the slot 104 prevents movement of the cartridge 101 from the open (proximal) to the closed (distal) position. The hook 103d is moved out of its pre-fired position and into engagement with the slot 104 in response to actuation of the fastener driver which fires the fastener. The locking mechanism 103 is associated with the cartridge 101 so that removal and replacement of the cartridge effects a change of lockout mechanisms as well. More specifically, the single use locking mechanism 103 in the embodiment of Figures 2 and 3 comprises locking clip 103 which is slidably mounted within chamber 118 of the cartridge 101. Referring additionally now to Figs. 3a and 3b, locking clip 103 is preferably in the form of a leaf spring having a first, upper arm portion 103a and a second, lower arm portion 103b which are integrally united at curved proximal end 103c, and a hook or detent 103d projecting downwardly from the distal end of the lower arm 103b. The upper arm 103a and lower arm 103b define an angle A which is about 10° to 50° depending on material thickness and condition, and preferably about 30°. The lower arm 103b and the hook 103d define an angle B which is preferably from about 75° to 120°. This area may be ribbed to provide additional resistance to bending when actuated. Fig. 3b illustrates a locking clip 103 with ribbed hook 103d'. The ribs may optionally also extend along lower arm 103b. The upper arm 103a is braced against the roof of the chamber 118,thereby providing a biasing force to resiliently urge lower arm 103b in a downward direction. The lower arm 103b illustratively extends longitudinally beyond that of upper arm 103a so that when the locking clip is moved distally as discussed below, the distal end of lower arm 103b with detent 103d is pushed outside chamber 118 while the upper arm 103a is still maintained inside the chamber 118 for providing the downward biasing force. In the initial position of locking clip 103, the hook 103d rests on base 115, which is preferably a strip of metal defining the floor of chamber 118. In this position the detent 103d is non-engageable with slot 104. The hook can be integrally connected into a single piece to the locking clip in, for example, a resilient clip or a leaf spring with a hooked end. Alternately, the hook can be a separate piece connected to the locking clip. Fig. 2a illustrates the distal portion of the apparatus 100 including the locking mechanism. In this embodiment the hook and locking member are integral. Fastener holder 101 is typically a rectangular shaped replaceable cartridge which is pivotally and slidably mounted to the anvil support arm 102 via mounting pin 105. The mounting pin 105, which is fixed to the lower portion of the staple cartridge 101, is adapted to be received into mounting slot 104 of the anvil support arm 102. Staples 111 are disposed within slotted grooves 112, and are pushed distally towards the anvil assembly by staple drivers 113 when the instrument is fired. The anvil assembly 122 comprises the anvil support arm 102 and, seated in the anvil support arm 102, an anvil 108 for crimping the legs of staples 111. Alignment pin 117, which is mounted to leaf spring 116, serves to align the cartridge 101 when the cartridge 101 is closed onto the body tissue. Spring 106 biases the cartridge 101 proximally, i.e., away from anvil assembly 122. The distal end of spring 106 abuts the proximal end of post 107, which is an integral part of anvil support arm 102. Projections 114 project outwardly from the cartridge 101, and are adapted to abut the edge of U-shaped distal portion 100f when the apparatus is closed. Projections 114 serve to align the cartridge 101. Further illustrations of fastener cartridges may be found in U.S. Patent Nos. 4,568,009 and 4,915,100, herein incorporated by reference. Fig. 2b illustrates the cartridge 101 in the fired position. Actuator 120 is moved distally when release toggle 100e is rotated clockwise, and the camming surface 120a is biased into contact with leaf spring 116. This moves the cartridge distally to close the apparatus on body tissue 119 located between the cartridge 101 and the anvil 108. Upon moving distally, spring 106 is compressed which then exerts a force for proximally biasing the cartridge back into the open position when the release toggle 100e is opened. When the actuating lever 100c is rotated counterclockwise, driver 121 is moved distally into contact with the pusher bar 110, moving the pusher bar 110 distally. The pusher bar, in turn, moves staple drivers 113 distally, thereby driving staples 111 through body tissue 119 and into the anvil 108 where the staple legs are crimped. Upon moving distally, the pusher bar 110 also pushes locking clip 103 distally such that the detent 103d is moved out of chamber 118 and onto the sloped contact surface 109 of the anvil support arm 102. In this intermediate position, the detent does not yet engage the approximation blocking means. After the stapling is completed, the apparatus is opened by rotating the approximating lever 100e counterclockwise back into the open position. As can be seen in Fig. 2c, after firing and release of approximation lever 100e, the cartridge 101 is moved proximally back into the open position to release the body tissue which was operated upon. However, the locking clip 103 does not fully return into chamber 118. Rather, the detent 103d slides down surface 109 and into the mouth of slot 104. The detent is held in this position by spring tension to prevent dislodging. Slot 104 in the anvil assembly thereby provides a catch means for engaging detent 103d. Once engaged therein, the locking clip prevents the apparatus from being reclosed, for if the user once again attempts to rotate lever 100e, the distal detent 103d will abut the edge of sloping surface 109 thereby preventing the cartridge 101 from being moved distally by actuator 120. At this time, either the expended cartridge can be removed, discarded, and replaced with a new cartridge, or the entire instrument can be discarded for a new instrument. The locking clip also prevents a fired or spent cartridge which has been removed and reinserted, from being closed since a spent cartridge when loaded will have its detent 103d seated in slot 104. An unfired cartridge on the other hand will have its detent 103d resting on the base 115 of the chamber 118 and therefore out of engagement with the slot in the anvil arm when inserted into the apparatus. In an alternate embodiment of the locking mechanism shown in Figures 5-10, the locking mechanism is a T-shaped member pivotally mounted within the cartridge and removably held in sideways (longitudinal) position such that the trunk portion of the T is distally oriented. After firing of the fasteners, the T-shaped member is released. When the apparatus is opened, the T-shaped lockout member pivots downward and into alignment with a slot in an approximation blocking means associated with the U-shaped distal portion of the apparatus. If the user attempts to reclose the apparatus, i.e., move the cartridge distally by rotating lever 100e the trunk portion of the T-shaped locking mechanism will abut the distal wall of the slot and prevent further distal movement of the cartridge. Referring now more particularly to Fig. 5, the fastener applying apparatus 200 includes an elongated carrier 201 extending longitudinally and a U-shaped portion 204 at the distal end of the elongated carrier 201. The elongated carrier 201 includes driver 202 and actuator 203 extending longitudinally therein. The U-shaped distal portion 204 includes an anvil support arm 205 and anvil 206 mounted thereto. A cartridge 218 is mounted in the U-shaped distal portion 204 and is movable between an initial proximal position and a distal position wherein it comes into close proximity to anvil 206 for gripping body tissue therebetween. The cartridge 218 may be removable and replaceable, and includes body portion 219, a leaf spring 207, alignment pin 208, pusher bar 209, and staple driver 210. The fasteners, illustrated in Fig. 5 as staples 211, are located within slots in the cartridge 218 and are pushed by respective staple drivers 210 when the instrument 200 is fired such that the legs of staples 211 penetrate body tissue and are crimped by anvil 206. The U-shaped distal portion includes a stopping means, i.e., member 212, which includes an upper longitudinally oriented, preferably cylindrical, slot 213, and a lower slot 214 oriented at an angle from the longitudinal orientation of the apparatus 200, and of lesser depth than the upper slot 213. Clearly the slots can be formed of other shapes as long as they are configured and dimensioned to receive the locking mechanism. Referring now to Figs. 5, 9, and 10, the T-shaped locking member 220 is pivotally mounted in cartridge 218. In the initial position, the back portion 221 of the locking member 220 is held upright by pusher bar 209. The back portion 221 includes depending legs 221a and 221b which are rotatably mounted to laterally extending shaft 217. Shaft 222 projects distally and perpendicularly from back 221. In the initial position of the locking member 220, shaft 222 is longitudinally oriented, and the distal end of shaft 222 projects a short distance into a reception area of the stopping means 212 where upper and lower slots 213 and 214 are joined. Helical compression spring 215 applies a force for biasing the locking member 220 proximally. Preferably, spring 215 is of such length so as to apply biasing force when the locking member 220 is moved distally, but to apply little or no biasing force when the locking member 220 is in the initial or proximal position. Torsion spring 216 is coiled around shaft 217 and urges the locking member to pivot to a downward pointing position. In its downward pointing position, the distal end of the shaft 222 rests on the bottom edge 214a (Figure 10) of the lower slot 214. The operational sequence of movements of the locking member 220 is explained more fully below. In the initial prefired and open position, the apparatus 200 is in the condition as shown in Fig. 5. The cartridge 218 is in a proximal position, and, within the cartridge, the locking member 220 is held upright by the pusher bar 209, which is proximally located. Referring to Fig. 6, when the apparatus is closed onto body tissue, i.e., when the cartridge 218 is approximated, actuator 203 is moved distally thereby moving cartridge 218 distally into close approximation with the anvil 206 so as to clamp body tissue therebetween. As can be seen in Fig 6, the locking member 220 is moved distally against the biasing force of compression spring 215 such that shaft 222 is received into upper slot 213. Referring now to Fig. 7., when the instrument is fired, driver 202 moves distally through slot 207a in the leaf spring and drives pusher bar 209 forward. Staple drivers 210 are, in turn, advanced so that staples 211 are substantially simultaneously driven through body tissue 230 and into the anvil 206 where they are crimped. The pusher bar 209 which had previously been restraining locking member 220 from pivoting downward, is moved to a position where it no longer provides such restraint and remains in the distal position even after the apparatus is reopened. When the apparatus 200 is opened, i.e., the cartridge 218 is retracted to its proximal position and the actuator 203 is drawn back, the cartridge 218 is moved by the biasing force of compression spring 215 back to its proximal location. The distal end of the shaft 222 of locking mechanism 220 slides back out of the upper slot 213. Since there is no pivoting restraint, when the distal end of the shaft 222 rides over the bottom edge 213a of the upper slot (see Fig. 10), it drops down to the bottom edge 214a of the lower slot 214 under the biasing force of torsion spring 216. Once the apparatus has been both fired and reopened, it cannot be reclosed, which is to say that the cartridge 218 cannot be reapproximated if it is spent. If an attempt is made to reapproximate the spent cartridge, the distal end of the shaft 222 will ride into the lower slot 214, which is not as deep as upper slot 213 and which cannot accommodate the full length of the shaft 222 (see Fig. 8). As shown in Fig. 10, slot 214 has a backstop surface 214b which prevents further distal movement of the locking member 220 or the cartridge 218. Thus, unless the spent cartridge 218 is replaced with a new cartridge, the instrument cannot be reclosed. In another embodiment illustrated in Figures 11-16b, the locking mechanism may comprise a slidable shaft or drop bolt which is released upon firing of the apparatus, and which slides downwardly into a slot when the apparatus is opened (i.e. the cartridge is moved proximally) so that a portion of it protrudes beyond the lower surface of the cartridge thereby interfering with distal movement of the cartridge if an attempt is made to reclose the apparatus. Referring now to Fig. 11, the fastener applying apparatus 300 includes an elongated carrier 301 extending longitudinally and U-shaped portion 304 at the distal end of the elongated carrier 301. The elongated carrier 301 includes driver 302 and actuator 303 extending longitudinally therein. The U-shaped distal end portion 304 includes an anvil support arm 305 and anvil 306 mounted thereto. A cartridge 312 is mounted in the U-shaped distal portion 304 and is movable between an initial proximal position and a distal position wherein it comes into close proximity to anvil 306 for gripping body tissue therebetween. The cartridge 312 may be removable and replaceable, and includes body portion 313, a leaf spring 307, alignment pin 308, pusher bar 309, and staple drivers 310. The fastener, illustrated in Figs. 11, 12, and 13 as staples 311, are located within slots in the cartridge 312 and are pushed by staple drivers 310 when the apparatus 300 is fired, such that the legs of staples 311 penetrate body tissue and are crimped by in corresponding depressions 306a in anvil 306. Referring to both Figs. 11 and 15, the cartridge 313 includes a drop bolt 315 maintained in an initial upper position as shown in Fig. 11, by a movable drop bolt retaining leaf spring 317. The leaf spring 317 includes an overhang portion 317c having a keyhole-shaped aperture 318 having a smaller and larger diameter portions 318a and 318b, respectively. The drop bolt 315 is mounted to the leaf spring retainer 317 such that the circumferential groove 315a of the drop bolt is disposed in the smaller diameter portion 318a of the aperture 318. The top portion 315b of the drop bolt 315 has a diameter smaller than that of aperture 318b so that it may pass through when the leaf spring is moved. Helical compression spring 316 is disposed around drop bolt 315 such that the lower end of the spring 316 abuts the upper surface of collar 315c of the drop bolt. The upper end of spring 316 abuts the bottom surface of the overhang 317C, thereby applying a biasing force to urge the drop bolt to move downward. The drop bolt has a lower portion 315d which is receivable through aperture 319 (Figure 11) in the cartridge so as to provide a stop means for engaging edge 320 of the U-shaped distal portion 304. The operational sequence of the locking mechanism of this embodiment is explained more fully below. In the initial prefired and open position, the apparatus 300 is in the condition as shown in Fig. 11. The cartridge 312 is in a proximal position, and, within the cartridge, the drop bolt 315 is held in the upward position by leaf spring 317. Referring to Fig 12, when the apparatus 300 is closed onto body tissue, i.e., when cartridge 312 is approximated, actuator 303 is moved distally, moving cartridge 312 distally into close approximation with the anvil 306 so as to clamp body tissue therebetween. As can be seen in Fig. 12, the cartridge 312 is moved distally against the biasing force of compression spring 314. Referring now to Fig. 13, when the instrument 300 is fired, driver 302 moves distally through slot 307a in leaf spring 307, and drives pusher bar 309 forward. Staple drivers 310 are, in turn, advanced so that staples 311 are substantially simultaneously driven through body tissue 330 and into depressions 306a in the anvil 306 where the legs of staples 311 are crimped. The pusher bar 309, which had moved from its initial proximal position to the distal, or fired position, remains in the distal position even after the apparatus is opened. As can be seen from Fig. 13 and Figs. 16a and 16b, when the staple driver 302 moves distally, the forward bottom edge 302a contacts proximal camming edge 317a of the drop bolt retaining leaf spring 317 and moves the top of the leaf spring 317 distally. When leaf spring 317 is moved distally, as shown in Figs. 16a and 16b, the top portion 315b of the drop bolt 315 aligns with large diameter portion 318b of aperture 318, thereby permitting drop bolt 315 to disengage leaf spring 317 and to fall through. Spring 316 furthers this disengagement and, by providing biasing force on the drop bolt 315, insures that the drop bolt will disengage even if the apparatus is upside down with respect to gravity. Upon disengagement of the drop bolt 315 with the leaf retainer 317, the bottom portion 315d of the drop bolt drops through aperture 319 in the bottom of the cartridge and rests upon a shelf 304a of the U-shaped distal portion. When the apparatus 300 is reopened, the actuator 303 is drawn back and the cartridge 318 is moved by the biasing force of compression spring 314 back to its proximal location. The bottom end of the drop bolt 315 slides over and down past edge 320. Collar 315c has a diameter larger than that of aperture 319 and, therefore, limits the distance which 315 drops. Once the apparatus 300 has been both fired and reopened, it cannot be reclosed which is to say that cartridge 218 cannot be reapproximated if it is spent. If an attempt is made to reapproximate the spent cartridge, as shown in Fig 14, the bottom end 315d of drop bolt 313 will abut stop edge 320 and further distal movement of the cartridge 312 is prevented. As is apparent from the above description, the locking mechanisms of the present invention can be utilized in stapling apparatus designed for single use, i.e., non-replaceable cartridges, which will prevent refiring of the spent cartridge. The locking mechanisms can also be used in apparatus utilizing replaceable cartridges and will prevent refiring if the apparatus is reloaded with a spent cartridge. While the above description contains many specifics, these specifics should not be construed as limitations, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other possible variations that are within the invention as defined by the claims appended hereto.	Apparatus for applying a plurality of surgical fasteners to body tissue, which comprises: a) support means; b) a cartridge (101) supported by said support means and containing a plurality of surgical fasteners; c) means (108) positioned opposite said cartridge for closing said fasteners; d) means for approximating said cartridge toward said closing means to grip body tissue therebetween; andcharacterised by: e) means (103, 104, 220, 214, 315, 320) for blocking said approximating means from movement toward a fastener firing position when said cartridge is spent. Apparatus as claimed in claim 1, wherein said blocking means (103, 104,220, 214, 315, 320) prevents approximation of said cartridge (101) toward said closing means (108) after said fasteners are fired and said cartridge is withdrawn from said closing means. Apparatus as claimed in claim 1 or 2, wherein the blocking means comprise co-operating surfaces associated with the cartridge (101) and the closing means (108) respectively, the said surfaces being provided on a locking mechanism (102, 220, 315) and an interference means (104, 214, 320). Apparatus as claimed in claim 2 or 3 wherein: a) the locking mechanism includes detent means (103 d) movable from a first position when said fasteners are positioned in said cartridge, to a second position after said fasteners are fired therefrom, and to a third position when said cartridge is withdrawn from said closing means; and b) the interference means (104) is connected to said support means and is positioned to interfere with said detent means when said detent means is in the third position so as to prevent approximation of said cartridge toward said closing means past a predetermined position when said cartridge is devoid of fasteners. Apparatus as claimed in claim 3 or 4, wherein the locking mechanism (103, 220, 315) is associated with said cartridge and is actuated by withdrawing said cartridge from the body tissue after firing the fasteners to prevent reapproximation of said cartridge. Apparatus as claimed in any one of claims 3, 4 or 5, wherein said locking mechanism is at least partially located inside of said cartridge. Apparatus as claimed in claim 6, wherein actuation of said locking mechanism (315) comprises movement of said locking mechanism from an initial position within said cartridge to a final position wherein at least a portion of said locking mechanism extends beyond the periphery of said cartridge so as to become engageable with said interference means. Apparatus as claimed in any one of claims 3 to 7 wherein said locking mechanism comprises a leaf spring (103). Apparatus as claimed in claim 8, wherein the interference means comprises means to engage a detent portion of the leaf spring, said engaging means comprising a slot (104). Apparatus as claimed in claim 8 or 9, wherein said leaf spring (103) is located within a chamber in the cartridge and movable in response to firing of the fasteners from a first position wherein said detent portion is not engageable with said slot (104) to an intermediate position wherein said detent portion is located outside said chamber, and wherein said detent portion is resiliently movable into engagement with said slot in response to proximal movement of the cartridge. Apparatus as claimed in any one of claims 3 to 10, wherein said locking mechanism is initially actuated by a firing means and further actuated by retraction of said cartridge. Apparatus as claimed in any one of claims 3 to 7, and wherein the locking mechanism comprises a drop bolt (315) Apparatus as claimed in any one of claims 3 to 12, wherein said fasteners are substantially simultaneously fired. Apparatus as claimed in any one of claims 3 to 13, wherein said cartridge is a removable cartridge which may be loaded into the apparatus, expended of fasteners, and replaced with another removable cartridge. Apparatus as claimed in any one of claims 3 to 14 wherein said interference means comprises a member (212) having first (213) and second (214) slots, and said locking mechanism comprises a member (221) which includes a slot engaging rod (222) movable between a first position wherein it is slidable into said first slot of said interference means and a second position wherein it is slidable into said second slot of said approximation blocking means. Apparatus as claimed in claim 15 wherein said second slot includes a wall surface (214a) for blocking distal movement of said slot engaging rod. Apparatus as claimed in any one of claims 3 to 16, further including means (316) for biasing said locking member in a first position and restraining means (317) for preventing said locking member from moving into a second position, wherein said restraining means comprises a resilient member (317) having means (318) to releasably engage one of two end portions of said locking member, said resilient member being movable to a non-restraining position in response to application of a fastener driving force. Apparatus as claimed in any one of claims 3 to 17, wherein said locking member comprises a cylindrical shaft (315) having a circumferential groove (315a) at said one end portion. Apparatus as claimed in claim 18, wherein said means to releasably engage said one end portion of the locking member comprises an aperture (318) in said resilient member (317) having a narrow portion (318a) and a wide portion (318b), said narrow portion having a width less than the diameter of said locking member but of sufficient width to engage the locking member at said groove, and said wide portion of the aperture having a greater size than the diameter of the locking member so as to allow said locking member to pass therethrough. Apparatus as claimed in any one of claims 17, 18 and 19, wherein the cartridge includes an aperture (319) for permitting passage of the other of the two end portions of the locking member to a position wherein it is engageable with the interference means. Apparatus as claimed in any one of claims 17 to 20, wherein said locking member includes a generally cylindrical shaft portion (315) movable from a first position to a second position wherein it is engageable with a blocking surface (320) associated with said interference means. Apparatus as claimed in any one of the preceding claims, wherein said fasteners comprise metal staples. Apparatus as claimed in any one of the claims 1 to 21, wherein said fasteners comprise two-part fasteners (151, 152) fabricated from bioabsorbable polymer.	UNITED STATES SURGICAL CORP; UNITED STATES SURGICAL CORPORATION	RODAK DANIEL P; RODAK, DANIEL P.
EP-0489438-B1	489,438	EP	B1	EN	19,940,928	1,992	20,100,220	new	B01J27	C07C2	C07C11, B01J27, B28B3, C07C2, C07B61, B01J23	B01J 23/04, C07C 2/24+11/113, C07C 2/24, M07C527:232, M07C523:04, B01J 27/232	Potassium carbonate supports, catalysts, and olefin dimerization processes therewith	Catalyst supports, catalyst systems, methods for the preparation thereof, and dimerization process therewith are provided catalyst supports are extruded from a thick paste of potassium carbonate and water catalyst systems comprise at least one elemental alkali metal deposited on the catalyst support. Optionally, the catalyst system further comprises at least one promoter.	BACKGROUND OF THE INVENTIONThis invention relates to alkali metal carbonate supported alkali metal catalysts. It is known in the art to employ alkali metal carbonate supported alkali metal catalysts for such conversions as propylene dimerization. It is also known in the art to prepare alkali metal carbonate catalyst supports by making a thick paste in a liquid and eventually forming a pelletized, tabletted, or granular support, see EP-A-0 351 748 and EP-A-0 313 050 which both disclose potassium carbonate supports, catalysts and olefin dimerization processes therewith. In these references the catalyst supports are prepared from an alkali metal carbonate, water water soluble ketone (EP-A-0 351 748) and alcohol (EP-A-0 313 050), respectively, and optionally at least one carbonaceous compound. The support prepared in such a manner subsequently can be treated with an elemental alkali metal to form a catalyst system. Alkali metal carbonate catalyst supports prepared from a water-based paste are difficult to process because the alkali metal carbonate to water ratio must be closely controlled or the paste can have the wrong consistency and be unworkable. Additionally, all of the mixing and drying conditions must be carefully controlled in order to form a useable support. Extrusion of an alkali metal carbonate and water paste is much more efficient than forming individual pellets or tablets, but is extremely complex because of either high solubility of higher molecular weight alkali metal carbonates or the low solubility of lower molecular weight alkali metal carbonates in water. Thus, it is difficult to process and easily form a useable catalyst support from an alkali metal carbonate and water. SUMMARY OF THE INVENTIONIt is an object of this invention to provide a process to easily prepare a potassium carbonate catalyst support. It is a further object of this invention to provide an easily processed potassium carbonate catalyst support. It is yet another object of this invention to provide a method to prepare an improved potassium carbonate supported elemental alkali metal catalyst system. It is yet a further object of this invention to provide an improved catalyst system for the dimerization of olefins. It is yet another object of this invention to provide an improved process for the dimerization of olefins. In accordance with the present invention, a potassium carbonate catalyst support is prepared from a thick paste comprising potassium carbonate and water. The resultant thick paste is extruded into an extrudate product, dried, and calcined to give a catalyst support, wherein the water to potassium carbonate weight ratio is from 0.23 to 0.29 grams water per gram potassium carbonate, and potassium carbonate and water are mulled for a time of up to about 60 minutes prior to extrusion and actively mixed for 1 to 50 percent of the total mulling time. Additionally, at least one elemental alkali metal can be contacted with the extruded support to form an olefin dimerization catalyst system. DESCRIPTION OF THE PREFERRED EMBODIMENTSThe present invention provides a process to prepare a catalyst support which comprises the steps of forming a thick paste comprising potassium carbonate and water, and extruding said paste to form an extrudate, wherein the water to potassium carbonate weight ratio is from 0.23 to 0.29 grams water per gram potassium carbonate, and potassium carbonate and water are mulled for a time of up to about 60 minutes prior to extrusion and actively mixed for 1 to 50 percent of the total mulling time. In order to form a catalyst support, the extrudate then must be dried and subsequently calcined. In accordance with yet another embodiment of the invention, the previously prepared extruded potassium carbonate catalyst support can be contacted with at least one elemental alkali metal to produce a catalyst composition which is useful to dimerize olefins. In accordance with yet a further embodiment of the invention, the potassium carbonate catalyst support and the elemental alkali metal catalyst composition can be contacted with at least one promoter. SupportsCommercially available potassium carbonate, in the form of, e.g. powder or granules, is mixed with water to form a thick paste. The support must be prepared from potassium carbonate in order to be able to extrude a water/potassium carbonate mixture that forms a useful catalyst support. Other alkali metal carbonates are either too insoluble or too soluble in water to be used easily in an extrusion process. Additionally, a potassium carbonate support is more easily impregnated with an elemental alkali metal than other supports. As used in this disclosure, the term support refers to a carrier for another catalytic component. However, by no means, is the support necessarily an inert material; it is possible that the support can contribute to catalytic activity and selectivity. In order to be able to extrude a water/potassium carbonate mixture, the final ratio of water to potassium carbonate during the extrusion process is critical. Generally, the mass ratio (gram/gram) during extrusion of water to potassium carbonate is within the range of 0.23 to 0.29, when using dried potassium carbonate, and preferably within the range of 0.24 to 0.28. Most preferably, the water to potassium carbonate weight ratio is within the range of 0.25 to 0.27 grams of water per grams potassium carbonate in order to provide a consistent, durable catalyst support which can be used to obtain high selectivity, high olefin conversion, and a high ratio of desired isomers to undesired isomers. The water to potassium carbonate ratio during the extrusion process can also be expressed in terms of moles of water per mole of potassium carbonate. Generally a molar ratio within the range of 1.8 (i.e., 1.8 moles of water per mole of potassium carbonate) to 2.2 is used during extrusion; preferably within the range of 1.8 to 2.1. Most preferably, for the reasons given above, a molar ratio of water to potassium carbonate is within a range of 1.9 to 2.1. If too much water is used, the potassium carbonate can completely dissolve and be unextrudable. If too little water is used, the paste will not extrude either because it is too dry or too thick. Preferably, in order to better control temperature, since the reaction between water and potassium carbonate is exothermic, and to prepare a porous extrudate with an appropriate pore size distribution, the water is pre-mixed with a minor amount of potassium carbonate to form a dilute aqueous potassium carbonate solution prior to contacting the major portion of the potassium carbonate. Any source can be used for the minor amount of potassium carbonate which is pre-mixed with the water. For example, commercially available new potassium carbonate can be used. Other sources include, but are not limited to, catalyst support waste material, i.e., non-useable support material generated during the support preparation process, such as, for example, dried and/or calcined fines; off-specification catalyst support; and/or catalyst support. Usually, the concentration of the dilute potassium carbonate solution is at least about 0.001M (0.001 moles K₂CO₃/liter H₂O) and preferably within the range of 0.002 M to 0.01 M, for the reasons stated above. Preferably, although not required, mixing occurs as the liquid, i.e., water, or dilute water/potassium carbonate solution, is being added to the potassium carbonate. The liquid is added to the potassium carbonate in such a manner so as to affect thorough contacting of the water and potassium carbonate. Good liquid/carbonate mixing occurs if the liquid is not poured, but is distributed evenly over the potassium carbonate. Most preferably the liquid is sprayed onto the potassium carbonate for best contacting. The amount of time used to add the liquid is any amount of time necessary to effect thorough contacting of the liquid and potassium carbonate. However, the liquid addition time can vary with the volume of liquid and mass of potassium carbonate used. For example, when preparing up to about 100 pounds of catalyst support, liquid addition times up to about one hour is sufficient, preferably within the range of 3 to 15 minutes. Most preferably, times within the range of 3 to 6 minutes are used for best mixing and contacting. Faster, more rapid, addition times are preferred so that all of the liquid and potassium carbonate can be contacted nearly simultaneously and, thus, forming a better, more durable, catalyst support. After the liquid is added to the potassium carbonate, mixing, or mulling occurs. Once again, the mix time can vary with the quantity of potassium carbonate and liquid combined. The mulling time, after all the liquid is added, is up to about 1 hour, and preferably within the time range of 10 minutes to 1 hour. Most preferably, the mixing time is within the range of 10 to 40 minutes, in order to ensure that the potassium carbonate reaction with water is complete, for good extrusion rates, and to give a consistent ratio of desired to undesired isomer products. Although there is mixing time, the entire mixing time usually is not considered active mixing time. As defined in this disclosure, mixing time is the contact time of liquid and potassium carbonate, i.e., mixer residence time. Active mixing time is the mixing time, expressed in terms of percent, wherein the mixer, or muller, is actually operating. Usually, the liquid/potassium carbonate is actively mixed for 1 to 50 percent of the time, preferably for 1 to 40 percent of the total mixing the time. Preferably, the liquid/potassium carbonate is actively mixed for 5 to 20 percent of the time for good liquid/solid contacting and to maintain potassium carbonate particle integrity. The temperature of the liquid and newly formed thick paste during the liquid addition and subsequent mixing generally is maintained at or below room temperature, and preferably is within the range of 0° to 10°C. Most preferably, the temperature during mixing is within the range of 0° to 5°C. High temperatures can cause increased dissolution of the potassium carbonate, which can cause the dried extrudate to be less porous, and therefore less suitable as a catalyst support. Low temperatures, i.e., below the freezing point of water, can cause solidification of the thick paste. After liquid addition and the water/potassium carbonate mulling, the paste optionally can be aged. Generally, aging times of greater than 24 hours do not produce any additional benefits. Preferably, the paste is aged for times within the range of 0 to 8 hours and most preferably for times within the range of 0 to 2 hours. Longer aging times tend to improve extrusion rates, but long aging times also tend to slow production and can be uneconomical. Once the liquid/potassium carbonate thick paste is prepared, i.e., mulled and, if desired, aged, the thick paste is then ready for extrusion. The paste can be formed into an extrudate using an extruder. The extrudate can be any diameter, but for best catalytic activity and ease of handling and processability, the extrudate is from 1/16 to 1/4 inch in diameter. Larger or smaller diameter extrudates can be prepared, depending on the desired use of the resultant extrudate. After the extrudate passes through the extruder dye, the extrudate can be cut into uniform lengths, if desired. However, uniform lengths are not always necessary, so the extrudate can be allowed to break on its own, into any lengths. If the extrudate is allowed to break on its own, it will usually have a length of 2 to 7 times the diameter width. Usually, the extrudate is allowed to break of its own accord because of ease of manufacture and economics. In order to prepare a catalyst support that can be easier to impregnate with an elemental alkali metal, the barrel temperature of the extruder should be closely controlled. Generally, extruder barrel temperatures within the range of 0° to 60°C are acceptable, although the temperature range can vary based on the subsequent drying process. For example, if the extrudate is to be vacuum dried, extruder barrel temperatures within the range of 10° to 30°C are preferred and most preferably temperatures within the range of 20° to 30°C are used. If a convection drying process is to be used, preferably, the extruder barrel temperatures are within the range of 20° to 60°C, and most preferably within the range of 20° to 50°C. Lower temperatures usually result in easier elemental alkali metal impregnation; higher temperatures can inhibit elemental alkali metal impregnation. The extrusion rate, expressed in terms of mass of extrudate produced per unit time, i.e., grams (pounds) per minute, depends on many factors, such as, for example, particular equipment used, water level, mixing time, extruder auger speed, and/or aging time. For example, a higher auger speed (expressed in terms of rotations per minute, rpm) will increase the extrusion rate. However, if the auger rpm is too fast or too slow, the extruder can become plugged. Therefore, it is desirable to increase auger rpm, but not at the expense of plugging the extruder and/or producing poor extrudate. When using a large, single screw extruder, such as, for example, a 5,72 cm (2¼ inch) Bonnot single screw extruder, the extruder auger rpm is preferably within a range of from 20 to 100 rpm, preferably within a range of from 30 to 80 rpm. Most preferably, for the reasons given above, the extruder auger rpm, when using a large single screw extruder, is within a range of from 45 to 70 rpm. Once the extrudate is formed, the extrudate can be dried and calcined according to any manner known in the art. Exemplary methods of drying include, but are not limited to, static drying, microwave drying, freeze drying, vacuum drying, and/or convection drying. For ease of use and due to ready availability, vacuum drying and/or convection drying are preferred drying methods. If vacuum drying of the extrudate is employed, generally the drying temperatures are within the range of 145° to 170°C, and preferably within the range of 145° to 165°C. Most preferably, temperatures within the range of 145° to 160°C are used in order to maintain the integrity of the support. Higher drying temperatures can cause fracturing of the extrudate particles and therefore unacceptable fines, and lower temperatures can result in ineffective moisture removal. Generally, the vacuum drying process is considered complete when the extrudate moisture content is within the range of 0 to 3 weight percent water, based on the total weight of the extrudate, and preferably within the range of 0 to 2 weight percent water. Most preferably, the final moisture content is within the range of 0 to 1 weight percent water in order to facilitate elemental alkali metal impregnation. Too high of a residual moisture content makes the subsequent calcination more difficult, and can inhibit the subsequent elemental alkali metal impregnation. If convection drying of the extrudate is employed, generally drying temperatures within the range of 100° to 260°C are used, and preferably temperatures within the range of 120° to 230°C are used. Most preferably, temperatures within the range of 145° to 205°C are used in order to maintain the integrity of the support, as well as the reasons regarding vacuum drying. Generally, the convection drying process is considered complete when the extrudate moisture content is within the range of 0 to 10 weight percent water, based on the total weight of the extrudate, and preferably within the range of 0 to 6 weight percent water. Most preferably the final moisture content is within the range of 0 to 3 weight percent water in order to facilitate elemental alkali impregnation. Since drying is more economical than the subsequent step of calcining, preferably as much water as possible is removed during the drying step. Preferably, the support is convection dried. Convection drying is more economical than vacuum drying. More importantly, the surface of a convection-dried support is different from a vacuum-dried support. A convection-dried support has more large pores penetrating the thick wall, or shell, of the potassium carbonate extrudate at the edge of the extrudate; a vacuum-dried extrudate has far fewer pores. After the subsequent calcination step, the shell of a convection-dried, extruded support seems to disappear, and interior and exterior potassium carbonate particles are nearly indistinguishable; and the surface appears rough, similar to dried foam. The shell of a vacuum-dried, extruded support, after calcination, remains thick and distinct; the surface is smooth except for deep fractures and fissures where the few pores were originally visible. This difference in the surface affects the ease of elemental alkali metal impregnation. A convection-dried support can be easier to impregnate than a vacuum-dried support. The drying atmosphere can be any type of atmosphere. For ease of use and economics, the preferred drying ambient is air. After the extrudate is dried, it is then calcined to remove any residual water. Calcining, like drying, can be done in any atmosphere. For ease of use and economics, air is the preferred atmosphere. However, if drying or calcining is done in an inert atmosphere and the support is maintained and stored in an inert atmosphere, the amount of oxygen carried into the elemental alkali metal impregnation step can be reduced, thus making the elemental alkali metal impregnation easier and more efficient. Another optional method to minimize exposure to air and for economic efficiency is to perform the drying and calcining processes in the same apparatus, i.e., the same oven, heater, or dryer. Calcining temperatures and times are interdependent. For example, higher temperatures require shorter calcination times and lower calcination temperatures require longer heating times. Preferably, for economic reasons, lower temperatures and short calcination times are preferred, when possible. Usually, temperatures within the range of 200° to 400°C are employed for calcination, and preferably temperatures within the range of 230° to 350°C are used. Most preferably, for economic reasons, temperatures within the range of 250° to 350°C are used. The calcination time can be any amount of time sufficient to remove substantially all of the water in the support. Generally, calcination times of up to about 5 hours are sufficient, preferably times within the range of 5 minutes to 3 hours are employed. Most preferably, times within the range of 15 minutes to 3 hours are used. The potassium carbonate support can contain additional components which do not adversely affect the extrusion process or the subsequent drying or calcining steps. For example, pigments, dyes, processing aids, inert fillers, and/or binders can be added. Graphite, or any form of a carbonaceous compound, should not be added to the support prior to support calcining unless it is fully removed during calcining; a carbonaceous compound can have detrimental effects on the catalyst system. For example, the catalyst system wherein the support contains a carbonaceous compound, can fracture and/or disintegrate during the dimerization process due to formation of carbon-alkali metal intercalation compounds. Catalysts and PromotersCatalysts systems employed in the practice of this invention comprise one of the potassium carbonate supports described above, at least one elemental alkali metal catalyst, and optionally one or more of the following additional promoters: a carbonaceous compound, elemental copper, elemental cobalt, finely divided stainless steel, finely divided glass, and mixtures of two or more thereof. It should be recognized, however, that the catalyst systems of the invention can contain additional components which do not adversely affect the catalyst performance, such as, for example, pigments, dyes, processing aids, inert fillers, binders, and the like. The alkali metals contemplated to be within the scope of the invention include lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. While the proportion of alkali metal combined with the potassium carbonate support can vary appreciably, generally at least about one weight percent of alkali metal based on the total weight of calcined support will be employed. Generally, 1 to 20 weight percent alkali metal will be employed with 2 to 15 weight percent preferred. An alkali metal loading of 3 to 10 weight percent based on the total weight of calcined support is most preferred for most efficient use of reagents, high catalyst activity and selectivity, and ease of catalyst preparation. Potassium is the preferred elemental alkali metal due to its ready availability, good catalytic activity and selectivity, as well as ease and safety in handling. However, some elemental sodium can be combined with the potassium. The addition of sodium to potassium can be beneficial in that the elemental alkali metal impregnation temperature can be lowered. For example, a mixture of up to about 25 weight percent sodium/75 weight percent potassium does not harm selectivity or activity, but greater than about 25 weight percent sodium can adversely affect the catalyst system. Preferably, if using a sodium/potassium mixture to impregnate the support, the mixture will comprise from 0.01 to 10 weight percent sodium, with the balance being potassium, for the most beneficial effects. The proportion of optional promoter on the potassium carbonate support can vary appreciably, but generally, at least one weight percent of the optional promoter based on the total weight of treated support will be employed. Usually, if the promoter is elemental cobalt or finely divided glass, not more than 50 weight percent will be used. With elemental copper, usually not more than about 30 weight percent will be used and usually not more than about 80 weight percent finely divided stainless steel will be used, all based on the total weight of treated support employed. The general procedure for preparation of the catalyst systems, after calcining the support, of the invention involves heating the potassium carbonate support to a temperature in the range of 80° to 350°C, preferably slightly above the melting point of the particular alkali metal used, cooling the particulate support and then contacting the particulate support with at least one elemental alkali metal in a dry, oxygen-free atmosphere, such as, for example N₂, Ar, or the like, at a temperature sufficient to cause the alkali metal to melt. The contacting, done in an oxygen-free atmosphere, is preferably carried out with suitable mixing to ensure even distribution. Suitable temperatures for the contacting step will vary with the particular alkali metal employed. For example, with elemental potassium, temperatures in the range of 80° to 100°C are preferred, while with elemental sodium, temperatures in the range of 100° to 140°C are preferred. While the alkali metal treated support is maintained at or above the melting point of the particular alkali metal used, in an oxygen-free atmosphere, any desired promoter(s), such as for example, finely divided stainless steel or elemental copper, can be gradually added while the treated catalyst is continuously stirred. For example, with potassium, temperatures in the range of 80° to 100°C are employed. The catalyst system is then ready to be charged to the reactor. Optionally, prior to charging the reactor, the catalyst system can be mixed with an inert substance to dilute the catalyst system and decrease the rate of olefin dimerization. Any inert substance which has little or no catalytic activity in an olefin dimerization reaction can be used. One example of such an inert substance is glass beads. Another example is potassium carbonate extrudates with no alkali metal. As indicated by the variety of supports, alkali metal components, and promoters included within the scope of the invention, numerous catalyst combinations are possible. Any combination of the alkali metal and optional promoters disclosed can be supported on any alkali metal carbonate support disclosed. Some possible combinations are described in detail in the examples which follow. The combination of support, alkali metal, and promoter(s) which one may choose to employ will depend on a variety of variables such as for example, reactor configuration, reaction temperature and pressure, olefin feed employed, rate of olefin feed, and conversions desired. Reactants Reactants applicable for use in the process of the invention are olefinic compounds which can (a) self-react, i.e., dimerize, to give useful products such as, for example, the self-reaction of propylene gives 4-methyl-1-pentene; and/or (b) olefinic compounds which can react with other olefinic compounds, i.e., co-dimerize, to give useful products such as, for example, co-dimerization of ethylene plus propylene gives 1-pentene, co-dimerization of ethylene and 1-butene gives 3-methyl-1-pentene and so forth. As used herein, the term dimerization is intended to include both self-reaction and co-dimerization as defined above. Suitable dimerizable olefinic compounds are those compounds having from 3 to 30 carbon atoms and having at least one olefinic double bond and at least one allylic hydrogen atom, i.e., at least one hydrogen atom attached to a carbon atom adjacent to a double-bonded carbon atom. Exemplary compounds include, but are not limited to, acyclic and cyclic olefins such as for example propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes and so forth; 3-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-pentene 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene and tetramethylethylene; cyclopentene, cyclohexene, methylcyclopentene and methylcyclohexene, and mixtures of any two or more thereof. Suitable co-dimerizable olefinic compounds are those compounds having from 2 to 30 carbon atoms, including all the compounds contemplated within the scope of dimerizable olefinic compounds as indicated above. In addition, olefinic compounds which do not have at least one allylic hydrogen atom are also included within the scope of co-dimerizable olefins. Exemplary compounds in addition to those indicated above, include, but are not limited to ethylene, 3,3-dimethyl-1-butene and ditertiarybutyl ethylene, and mixtures of any two or more thereof. The compounds indicated above as dimerizable olefinic compounds are capable of undergoing both self-reaction, i.e., dimerization, and cross-reaction, i.e., co-dimerization, with other members of the same group or with those compounds designated as co-dimerizable. The co-dimerizable compounds which do not have at least one allylic hydrogen may be capable of isomerization to form an olefin having an allylic hydrogen under the reaction conditions employed. If such isomerization is not possible, then those non-isomerizable, co-dimerizable compounds which do not have at least one allylic hydrogen must be contacted with at least one of the dimerizable compounds in order to facilitate the desired co-dimerization reaction. In other words, the co-dimerizable compounds which do not have at least one allylic hydrogen atom and are not capable of isomerization to produce an olefin having at least one allylic hydrogen are therefore not capable of reacting with themselves under the reaction conditions employed for the dimerization reaction. Reaction Conditions The dimerization reaction of the invention can be carried out using either batch or continuous types of operation, although the catalysts of the invention are particularly well suited for continuous, fixed bed, operation. Suitable equipment, such as, for example, autoclaves, tubular reactors, as are well known in the art can be employed. No special materials of construction are required so that steel, stainless steel, glass-lined reactors, or the like can be employed. The reaction temperature can vary depending on the catalyst and feed(s) employed. Typically, a temperature range of 50° to 250°C is suitable. Temperatures of 80° to 200°C are preferred with a range of 120° to 170°C most preferred because optimum reaction rates are obtained with minimum by-product formation. The dimerization reaction can be carried out by contacting the dimerizable olefins with catalyst in the liquid phase or the gas phase, depending on the structure and molecular weight of the olefin, as well as reaction temperature and pressure employed. Pressure during the dimerization reaction can vary between wide limits. In general, higher pressures favor the progress of the reaction. Thus, pressures of atmospheric up to about 69,1 MPa (10,000 psig) and higher are suitable. Preferably, pressures of 0.79 to 34,6 MPa (100 to 5,000 psig) are employed, with pressures of 3.55 to 13.9 MPa (500 to 2,000 psig) most preferred in order to achieve a good balance between reaction rate and minimize equipment and operating costs necessitated by very high reaction pressures. If the reaction is carried out in the liquid phase, solvents or diluents for the reactants can be used. Saturated aliphatic hydrocarbons, e.g., pentane, hexane, cyclohexane, dodecane; aromatic compounds, preferably those without an alpha-hydrogen (which would be capable of undergoing alkylation under the reaction conditions) such as benzene and chlorobenzene are suitable. If the reaction is carried out in the gaseous phase, diluents such as aliphatic hydrocarbons, for example methane, ethane and/or substantially inert gases, e.g., nitrogen, argon, can be present. The contact time required for the dimerization reaction depends upon several factors, such as, for example, the activity of the catalyst, temperature, pressure, structure of the reactants employed, and level of conversion desired. The length of time during which the dimerizable olefinic compounds are contacted with catalyst can vary conveniently between 0.1 seconds and 24 hours although shorter and longer contact times can be employed. Preferably, times of one minute to 5 hours are employed. Where reaction is carried out in continuous fashion, it is convenient to express the reactant/catalyst contact time in terms of weight hourly space velocity (WHSV), i.e., the ratio of the weight of reactant which comes in contact with a given weight of catalyst per unit time. Thus, a WHSV of 0.1 to 40 will be employed. A WHSV of 1 to 30 is preferred, with 1 to 20 WHSV most preferred for optimum catalyst productivity. ProductsThe olefinic products of the invention have established utility in a wide variety of applications, such as, for example, as monomers for use in the preparation of homopolymers, copolymers, terpolymers, e.g., as the third component of ethylene-propylene terpolymers useful as synthetic elastomers. A further understanding of the present invention and its advantages will be provided by reference to the following examples. EXAMPLESExample 1A) Water and Alcohol Catalyst Support PreparationTwenty pounds of potassium carbonate (K₂CO₃) (JT Baker, ACS reagent grade) were added to a large Lancaster mix-muller. The amount of water added was adjusted to account for moisture in the K₂CO₃ such that the final mixture had 0. 24g H₂O/1g K₂CO₃. The water was evenly added to the mix-muller over a time of about three (3) minutes. Then, n-propanol (C₃OH₈) (JT Baker, ACS reagent grade) was evenly added to the mix-muller over a time of about 5 minutes, such that the final mixture had 0. 16g C₃OH₈/1g K₂CO₃. The K₂CO₃, water and alcohol mixture was mixed for 12 minutes, and then a cycle of 4.5 minutes of no mixing (stand time) and 0.5 minutes of mixing commenced and continued for 35 minutes thereafter. The paste was fed to a 5.72 cm (2¼ inch) Bonnot single screw extruder, with a barrel temperature of 30°C. The extrudate was 0.32 cm (⅛ inch) diameter. The extrudate was vacuum dried at 157°C (315°F) overnight. The dried extrudate was calcined at 270°C (518°F) for 3 hours, under air, to form a support. For impregnation, potassium was heated to 75°C and the support was heated 100°C, under an inert atmosphere. Potassium was added to the support, with good mixing. Potassium impregnation, or loading, was 8 weight percent, based on the weight of the calcined support. B) Water Only Catalyst Support PreparationThe procedure of the Water and Alcohol Catalyst Support Preparation was followed exactly, except for two variations. The water/K₂CO₃ mixture comprised 0.27g H₂O/1g K₂CO₃. Secondly, no alcohol (n-propanol) was added to the mixture. C) Dimerization ReactionThe dimerization of propylene was carried out in a steam heated 316 stainless steel tubular reactor (1,3 x 50,8 cm (½ x 20 )). The catalyst system (50 grams) was loaded into the reactor. The contents of the tubular reactor were heated to a reaction temperature of about 160°C, at about 11.14 MPa (1600 psig), and propylene was pumped into the reactor with a weight hourly space velocity of 1.2. After about 1.5 hours of reaction time and each one hour thereafter for the following 6 hours, a sample was collected and analyzed by gas liquid chromatography (glc) from each run. Three runs were performed with each type of catalyst. The summarized results represent the average analysis of the last dimerization sample collected from each of the 3 runs (see Table I). Propylene Conversion, % Selectivity to 4MP1, % 4MP1/4MP2 Water & Alcohol Extruded Support19.887.216 Water Only Extruded Support20.387.517 The data show that there is no substantial difference in dimerization results between the two types of catalyst support preparation procedures. However, the use of alcohol requires additional solvent handling and recovery equipment, as well as significant safety precautions. Therefore, a catalyst support extruded using only water as a solvent is much more preferable for economic, as well as safety reasons. Example II (Comparative Example)Catalyst support was prepared by adding varying amounts of alkali metal carbonate to a small mix-muller. Sodium carbonate (Fisher, reagent grade) and cesium carbonate (Henley Chemicals, technical grade) were tested. Sodium carbonate (Na₂CO₃) has a solubulity in cold water of 7.1g Na₂CO₃/100g H₂O. Cesium carbonate (Cs₂CO₃) has a solubility in cold water of 260.5g Cs₂CO₃/100g H₂O. Potassium carbonate has a solubility in cold water of 112 gK₂CO₃/100g H₂O. The paste was fed to a BB-Gun Bonnot single screw extruder, with a barrel temperature of 30°C, through a stainless steel die with 4 holes of 0.32 cm (1/8 inch) diameter. The extrudate was dried in a convection or vacuum oven overnight. The dried extrudate was calcined at 343°C (650°F), under air, for 30 minutes, to form a support. The results of the extrusions are listed in Table II. The data in Table II show that sodium carbonate and cesium carbonate can be extruded from a water-only based paste. However, the sodium carbonate extrudates are inferior to potassium carbonate extrudates (see Example IV), in that sodium carbonate extrudates have a rough exterior and have relatively weak crush strengths. Cesium carbonate extrudates have acceptable crush strengths, compared to potassium carbonate extrudates, but cesium carbonate and water is difficult to extrude and the resultant extrudate cannot be vacuum dried. Example IIICatalyst support was prepared by adding 20 pounds of potassium carbonate (JT Baker, ACS reagent grade) to a large Lancaster mix-muller. The amount of water added was adjusted to account for moisture in the K₂CO₃, such that the final mixture had 0.26g H₂0/g K₂CO₃. The water, which had a temperature of 4°C, was evenly added to the mix-muller over a time of about 6 minutes. The total residence time of the K₂CO₃ and water in the mix-muller was 20 minutes after completion of the water addition. The paste was fed to a 5.72 cm (2¼ inch) Bonnot single screw extruder, with a barrel temperature of 30°C, through a stainless steel die with 48 holes of 0.32 cm (⅛ inch) diameter. The extrudate was dried in a convection oven at 177°C (350°F), under air, for 3 hours. The dried extrudate was calcined at 343°C (650°F), under air, for 30 minutes, to form a support. Catalysts with various levels of elemental sodium and elemental potassium were prepared by weighing out solid sodium and potassium, and then melting them together. For impregnation, elemental alkali metal(s) was heated to 75°C and the support was heated to 100°C, under an inert atmosphere. The molten elemental alkali metal was added to the support, with good mixing. Elemental alkali metal(s) impregnation, or loading, was 4 weight percent, based on the weight of the calcined support. The dimerization of propylene was carried out in a steam heated 316 stainless steel tubular reactor (1,3 x 50,8 cm (½ x 20 )). The catalyst system (40 grams) was loaded into the reactor and was bounded above and below by a total of about 10g of glass beads. The contents of the tubular reactor were heated to a reaction temperature of about 150°C, at about 11.14 MPa (1600 psig), and propylene was pumped into the reactor with a weight hourly space velocity of 3.75. After about 1.5 hours of reaction time and each one hour thereafter for the following 10 hours, a sample was collected and analyzed by gas liquid chromatography (glc). Three runs were performed with each type of catalyst. The summarized results represent the average analysis of the last dimerization sample collected from each of the three runs (see Table III). Run % Na* % K4MP1/4MP2 301010045 302109045 303158537 304208038 305257535 The 4MP1 (4-methylpentene-1) to 4MP2 (4-methylpentene-2) ratio is critical because 4MP2 is undesirable, and is very difficult to separate from 4MP1. The data was obtained from the plots of ratio versus selectivity. By comparing the performance at equal selectivity and conversion, a fair comparison of the effects can be given. A selectivity of about 90% 4MP1 was used because that was an average selectivity. The data show that at 10% Na/90% K (Run 302) there was no loss of selectivity compared to pure potassium (Run 301). While not wishing to be bound by theory, this is probably due to the exchange of sodium of the elemental alkali metal with potassium ions from the potassium carbonate support producing additional potassium and generating sodium ions. At higher sodium levels, this exchange of sodium with potassium is probably much less effective. Example IVThe following Example describes the variable (parameter) screening process to determine the dominant variable (parameter) factors and the optimization process of the dominant factors of the catalyst support preparation procedure. Unless otherwise specifically stated, catalyst support was prepared as follows. Seventy-five pounds of potassium carbonate (K₂CO₃) (JT Baker, ACS reagent grade) were added to a large Lancaster mix-muller. The amount of water added was adjusted to account for moisture in the K₂CO₃, such that the final mixture had from 0.24g H₂O to 0.28g H₂O per gram K₂CO₃. The water was evenly added, i.e. sprayed, onto the mix-muller at a rate of 1.2 kg (2.6 lbs) H₂O/min. Water addition temperature ranged from 0°C (32°F), i.e., ice water, to 20°C (68°F) during the screening process and from 0°C (32°F), i.e., ice water, to 4°C (40°F) during the optimization process. The mixing time ranged from 20 to 60 minutes. The paste was fed to a 5.72 cm (2¼ inch) Bonnot single screw extruder. The extrudate was vacuum or convection dried and then calcined, under air, to form a support. Tables IV and V, below, give the parameters and ranges, if appropriate, for the variable (parameter) screening (Table IV) and optimization (Table V) analyses. A multiple linear regression analysis, Systat®, was performed by computer to determine the dominant variable (parameter) factors. The Systat® computer program is commercially available from Systat, Inc., Evanston, IL. The dominant variable (parameter) factors analyzed are those listed as Parameters in Table IV. Based on the multiple linear regression analysis, the most important variables are: 1) H₂O to K₂CO₃ Ratio 2) Mixer Residence Time 3) Fraction of Active Mixing 4) Extruder Auger rpm 5) Drying Temperature These five variables were studied for optimization. The analytical results, in Tables VI and VII below, were also analyzed with Systat®, a multiple linear regression analysis computer program, to determine the true optimization. The data in Table VI provides support and catalyst properties. The data in Table VII provides support and catalyst properties, as well as propylene dimerization process results. The dimerization results were obtained under dimerization conditions similar to those previously described in Example I. The multiple linear regression analysis performed on the experimental data given in Tables VI and VII resulted in optimum conditions needed to perform an efficient extrusion, as well as produce the best overall catalyst and catalyst support. The results, as determined by the Systat® program, given in Table VIII below, are given as ranges in order to account for reasonable deviations from the computer-generated optimized conditions. Parameter Broad Range Optimized Range Computer-Generated Optimized Condition gH₂O/gK₂CO₃0.23 - 0.290.25 - 0.270.26 Total mixing time (min.) after initial water additionup to one (1) hour20 - 40 min.20 min. Active mixing, % time1 - 505 - 2010% Extruder auger, rpm20 - 10045 - 7060 rpm Convection Drying100 - 260°C145 - 205°C177°C temp., °C (°F)(212 - 500°F)(293 - 401°F)(350°F) While none of the Runs correspond exactly to the computer-generated optimized conditions, Runs 414 and 453 correspond very closely to the computer-generated optimized conditions. The only variances are gH₂O/gK₂CO₃ of 0.25 and drying temperature of 149°C (300°F). Runs 414 and 453 show good elemental alkali metal (potassium) impregnation, as well as good propylene conversion, 4MP1 selectivity, and 4MP1/4MP2 ratio. The examples have been provided merely to illustrate the practice of the invention and should not be read so as to limit the scope of the invention or the appended claims in any way.	A process for preparing a catalyst support comprising preparing a thick paste comprising potassium carbonate and water, extruding said paste to form an extrudate and drying said extrudate as well as, optionally, calcining said dried extrudate, wherein the water to potassium carbonate weight ratio is from 0.23 to 0.29 grams water per gram potassium carbonate, characterized in that said potassium carbonate and water are mulled for a time of up to about 60 minutes prior to extrusion and actively mixed for 1 to 50 percent of the total mulling time. The process of claim 1 wherein said potassium carbonate and water are mulled at a temperature from 0 to 25 °C. The process of claim 1 or 2 wherein said potassium carbonate and water are aged for a time of up to about 24 hours after mulling. The process of any of the preceding claims wherein said paste is extruded through an extruder with a barrel temperature from 0 to 60 °C. The process of any of the preceding claims wherein said drying is a vacuum drying process. The process of claim 5 wherein said vacuum drying is done at a temperature from 145 to 170 °C. The process of claim 5 or 6 wherein the vacuum-dried extrudate comprises up to about 3 weight percent water, based on the total weight of the extrudate. The process of any of claims 1-4 wherein said drying is a convection drying process. The process of claim 8 wherein said convection drying process is done at a temperature from 100 to 260 °C. The process of claim 8 or 9 wherein the convection-dried extrudate comprises up to about 10 weight percent water, based on the total weight of the extrudate. The process of any of the preceding claims wherein said calcining occurs at a temperature from 260 to 400 °C. The process of claim 1, characterized by (a) preparing a thick paste comprising potassium carbonate and water, wherein the water to potassium carbonate weight ratio is about 0.29 grams water per gram potassium carbonate; (b) mixing said thick paste for a time of up to 60 minutes, wherein said thick paste is actively mixed for 1 to 50 percent of the total mixing time, at a temperature from 0 to 25 °C; (c) extruding said paste through an extruder to form an extrudate, wherein said extruder barrel temperature is from 0 to 60 °C; (d) drying said extrudate at a temperature from 100 to 260 °C to obtain a dried extrudate comprising up to about 10 weight percent water, based on the total weight of the extrudate; and (e) calcining the thus-dried extrudate at a temperature from 260 to 400 °C. The process of any of the preceding claims comprising contacting the calcined extrudate with at least one elemental alkali metal to produce a catalyst system. The process of claim 13 wherein said elemental alkali metal is selected from lithium, sodium, potassium, rubidium, cesium, and mixtures thereof, preferably sodium, potassium, and mixtures thereof. The process of claims 13 or 14 wherein said elemental alkali metal comprises from 1 to 20 weight of the catalyst system, based on the weight of the support. The use of the catalyst system as defined in any of claims 13 to 15 for the dimerization of olefins. A process for the dimerization of olefinic compounds comprising contacting olefinic compounds having from 3 to 30 carbon atoms per molecule with the catalyst system as defined in any of claims 13 to 15, wherein said dimerization is carried out at a temperature from 80 to 200 °C, a pressure from 6.9 to 27.6 MPa, and a weight hourly space velocity from 0.1 to 10. The use of claim 16 wherein propylene is dimerized to 4-methyl-1-pentene.	PHILLIPS PETROLEUM CO; PHILLIPS PETROLEUM COMPANY	BONNELL RALPH E; EWERT WARREN MATTHEW; FENTRESS DENTON C; FREEMAN NORMAN LEE JR; KUBICEK DONALD HUBERT; LOWERY RICHARD E; MITCHELL KENT EDWARD; SCHUBERT PAUL FREDERICK; BONNELL, RALPH E.; EWERT, WARREN MATTHEW; FENTRESS, DENTON C.; FREEMAN, NORMAN LEE, JR.; KUBICEK, DONALD HUBERT; LOWERY, RICHARD E.; MITCHELL, KENT EDWARD; SCHUBERT, PAUL FREDERICK
EP-0489441-B1	489,441	EP	B1	EN	19,950,329	1,992	20,100,220	new	C01B33	null	B01J23, B01J21, C01B33	C01B 33/107D4	Metal catalyzed production of tetrachlorosilane	The present invention is a process for the production of silanes from the contact of hydrogen chloride with silicon. The silicon may be in the form of silicon metal or a silicon containing material. The described process employs a catalyst which increases the yield of tetrachlorosilane. The catalyst is selcted from a group consisting of tin and tin compounds, nickel and nickel compounds, arsenic and arsenic compounds, palladium and palladium compounds and mixtures thereof. The process is run at a temperature of about 250°C. to 500°C.	The present invention is a process for the production of silanes from the reaction of hydrogen chloride with silicon. The silicon may be in the form of silicon metal or a silicon containing material. The process employs a catalyst, selected from a group of metal and metal compounds, optionally on a solid support, which increases production of tetrachlorosilane. Chemical Abstracts 95 (20), No. 171975n, referring to SU-A 79-2 794 636, teaches a process for the production of trichlorosilane and tetrachlorosilane wherein a Si-Cu mass is heated with HCl in a fluidized bed and wherein the yield of tetrachlorosilane is improved by feeding HCl in pulses. The present invention is a process for the production of silanes from the contact of hydrogen chloride with silicon. The silicon may be in the form of silicon metal or a silicon containing material. The described process employs a catalyst which increases the yield of tetrachlorosilane. The catalyst is selected from a group consisting of tin and tin compounds, nickel and nickel compounds, arsenic and arsenic compounds, palladium and palladium compounds and mixtures thereof;, rhodium and rhodium compounds, platinum and platinum compounds, iridium and iridium compounds, and aluminum and aluminum compounds on a solid support. The process is run at a temperature of about 250°C. to 500°C. The present invention is a catalyzed process for preparing silanes of formula HnSiCl4-n, where n is an integer from zero to four. The described process is especially useful for the production of tetrachlorosilane. The process comprises contacting silicon with hydrogen chloride in the presence of an effective concentration of a catalyst at a temperature of about 250°C. to 500°C. The described process can be used to prepare silane (SiH₄), chlorosilane, dichlorosilane, trichlorosilane and tetrachlorosilane. However, the catalysts described herein preferentially select for the production of tetrachlorosilane. Therefore, tetrachlorosilane is a preferred product of the process. The silicon can be in the form of silicon metal or a silicon containing material. The term silicon metal refers to a metalloid type material consisting essentially of elemental silicon. The term silicon containing material refers to alloys or intermetallic compounds of elemental silicon with, for example, iron copper or carbon. Preferred are alloys and intermetallic compounds comprising greater than about 50 percent by weight of elemental silicon. The silicon is contacted with hydrogen chloride in the presence of an effective concentration of a catalyst. The surface area of the silicon is important in determining the rate of reaction of silicon with hydrogen chloride. Therefore, the silicon should be finely divided or powdered. The silicon can be, for example, ground or atomized silicon. It is preferred that the particle size of the silicon be less than 100 mesh. Larger particle sizes of silicon may be used, but the conversion rate to product silanes may be reduced. The lower limit of the silicon particle size is determined by the ability to produce and handle the silicon. The described process employs an effective concentration of a catalyst. By effective concentration, it is meant a concentration of catalyst which increases the yield of the process for the production of tetrachlorosilane over the yield obtained in the absence of a catalyst. Preferred are those catalyst which increase the yield of tetrachlorosilane by at least 10 percent over yields obtained in the uncatalyzed process. The term yield refers to the absolute amount of tetrachlorosilane produced. Useful catalysts, for the described process, comprise those selected from the group consisting of tin and tin compounds, nickel and nickel compounds, arsenic and arsenic compounds, palladium and palladium compounds and mixtures thereof. When the catalyst is selected from a group consisting of tin and tin compounds, nickel and nickel compounds and arsenic and arsenic compounds an effective catalyst concentration is about 250 to 4,000 parts per million (ppm) of combined silicon and catalyst. Higher catalyst concentrations may be used, but to no perceived advantage. When the catalyst is selected from a group consisting of palladium and palladium compounds an effective catalyst concentration is about 600 to 4000 ppm of combined silicon and catalyst. All catalyst concentrations are expressed as the concentration of catalytic metal contacted with the silicon. The metal catalyst compounds can be organic or inorganic compounds. Preferred are inorganic metal catalyst compounds. The inorganic metal catalyst compounds can be, for example, halide or oxide compounds of tin, nickel, arsenic or palladium. The inorganic compounds can be, for example, NiBr₂, NiCl₂, AsBr₃, As₂O₅, SnCl₄, SnO₂, PdBr₂, PdCl₂ or PdO. The preferred catalysts are tin and tin compounds. The most preferred catalyst is tin metal. For the catalyst to be effective in the described process, the catalyst must have high interfacial contact with the silicon. Standard methods for establishing contact between reactants and a catalyst may be employed for this purpose. The catalyst may be, for example, in the form of a powder which is mechanically mixed with the silicon. The catalyst may be, for example, an alloy with the silicon. Useful catalysts for the described process comprise metals and metal compounds bound to a solid support. Metals and metal compounds useful in the described process are, for example, palladium and palladium compounds, rhodium and rhodium compounds, platinum and platinum compounds, iridium and iridium compounds, tin and tin compounds, nickel and nickel compounds and aluminum and aluminum compounds. The supported metal compounds can be, for example, inorganic oxide and halide compounds of the described metals. The inorganic metal compounds can be, for example, PdBr₂, PdCl₂, PdO, RhCl₃, RhO₂, Rh₂O₃, PtF₄, PtF₆, PtO₂, IrBr₃, IrCl₃, IrO₂, SnCl₄, SnO₂, NiBr₂, NiCl₂, Al₂O₃, AlCl₃ and AlF₃. The preferred supported metals and metal compounds are selected from the group consisting of palladium and palladium compounds, rhodium and rhodium compounds, platinum and platinum compounds and iridium and iridium compounds. The most preferred supported metal is palladium. The solid support for the metal or metal compound can be any particulate material which is stable under the process conditions, is not detrimental to the reaction and to which the metal or metal compound can be bound. The solid support material can be, for example, carbon, activated carbon, graphite, alumina, silica-alumina, diatomaceous earth or silica. The preferred solid support materials are activated carbon and alumina. Activated carbon is the most preferred support material. The physical form of the support material is that of a particulate powder. The available surface area of the solid support must be adequate to bind the desired level of catalyst. It is preferred that the solid support material have an intrinsic surface area within the range of 10 to 1500 m²/g. The method of binding of the metal or metal compound to the solid support is not considered critical to the described process. Any method of binding which retains the metal or metal compound in contact with the solid support under the process conditions is acceptable. In general, it has been found that the higher the level of metal or metal compound bound to the solid support, the more efficient the catalyst. Therefore, less total catalyst is required in the process for the same level of catalytic activity. A useful weight of metal or metal compound bound to solid support is within the range of 0.5 to 15 weight percent of the combined metal or metal compound and solid support material. A preferred weight of metal or metal compound bound to solid support is one to ten weight percent of the combined metal or metal compound and solid support material. The effective concentration of catalyst depends upon the amount and type of metal or metal compound bound to the solid support material, as well as the type of solid support material. In general, metal concentration, either as elemental metal or in the form of a metal compound, in the range of 25 to 4000 parts per million (ppm) metal, based on total initial weight of solids charged to the reactor, have been found useful. The initial weight of solids charged to the reactor include the weights of silicon, solid support material and metal or metal compound. A preferred concentration for supported metal is about 100 to 2000 ppm. Contact of the silicon and catalyst mixture with hydrogen chloride may be effected in standard type reactors for contacting solid and gaseous reactants. The reactor may be, for example, a fixed-bed reactor, a stirred-bed reactor or a fluidized-bed reactor. It is preferred that the reactor, containing the silicon and catalyst mixture, be purged with an inert gas, such as nitrogen or argon, prior to introduction of the hydrogen chloride. This purging is to remove oxygen and prevent oxidation of silicon and formation of other detrimental oxygenates. The required contact time for the hydrogen chloride to react with the silicon will depend upon such factors as the temperature at which the reaction is run and the type and concentration of catalyst employed. In general, contact times in the range of 0.1 to 100 seconds have been found useful. The described process can be run at a temperature of about 250°C. to 500°C. However, a preferred temperature for running the process is about 270°C. to 400°C. Recovery of the product silanes can be by standard means, for example, by condensation. ExamplesThe ability of selected metals, metal compounds and support materials to catalyze the reaction of hydrogen chloride with silicon to form tetrachlorosilane was evaluated in a series of test runs. The process was conducted in a fluidized-bed reactor of conventional design, similar to that described by Dotson U.S. Patent No. 3,133,109, issued May 12, 1964. For each test run, a mixture of ground metallurgical grade silicon metal (Elkem Metals Company, Alloy, West Virginia) and the potential catalytic material was formed by placing the materials in a glass vessel and shaking. The test mixture was added to the reactor and the reactor was purged with nitrogen gas for about 30 minutes. The reactor temperature, for each run, was maintained at the temperature specified in Tables 1 and 2. Hydrogen Chloride was fed to the reactor a rate of 8-10 g/h for a period of about 20 hours. Products were collected continuously throughout the 20-hour run, in a cold trap. The collected product was analyzed by gas liquid chromatography to determine the amounts and types of silanes produced. The weight difference of the reactor before and after each run was used as an indication of silicon conversion. Materials tested as unsupported catalysts and their concentrations in the ground silicon metal are listed in Table 1. The sources of materials tested as catalysts, as indicated in Table 1, are: Aldrich Chemical Company, Milwaukee, WI; ALFA Research Chemicals, Danvers, MA; and Belmont Metals, Inc., Brooklyn, NY. Unless indicated otherwise, under the heading Type, all materials were tested as powders in the form received. Screened particle size of the tested material is provided in parenthesis, when screening was conducted. The results of this series of runs are presented in Table 1 under the heading Product. Under the subheadings HSiCl₃ and SiCl₄ are listed the weight percent of these two products in relation to total recovered products. Under the heading Si-Conv is presented the percent of silicon metal consumed during the process as determined by the reduction in weight of silicon initially added to the reactor. The heading P.I. is a performance index calculated as the SiCl₄ value multiplied by the Si- Conv /100 value. The first line of data represents a baseline for a process in which no catalyst was present. The values presented for the baseline are the averaged values of four separate runs. All other values in Table 1 are the averaged values for two separate runs. Effect of Metal and Metal Compounds as Catalyst For Tetrachlorosilane Production Catalyst Temp. (°C) Product Type Source Conc. (ppm) HSiCl₃ SiCl₄ Si-Conv P.I. None--31587.112.0 93.011 SnBelmont 250 315 67.7 26.296.025 SnBelmont50031562.735.991.133 SnBelmont100031562.635.795.334 SnBelmont200031549.450.291.146 SnBelmont400031558.841.195.839 SnBelmont400035055.241.587.436 Sn (-325 mesh)Aldrich50031566.330.384.626 Sn (-100 mesh)Aldrich100031570.728.375.421 Sn(IV)ClAldrich100031561.638.190.835 SnCl₄·5H₂OAlfa100031548.251.166.034 Sn(II) OxideAldrich100031566.632.483.227 Sn(IV) OxideAldrich100031563.234.774.726 Ni(2µ)Aldrich200031563.629.991.927 NiAlfa400031576.620.782.317 AsAlfa50031573.825.493.924 AsAlfa200031578.120.286.317 PdAldrich50031586.911.993.211 PdAldrich100031569.827.884.624 PdAldrich200031573.125.890.623 Materials tested as supported catalysts, their supports and the initial concentration of metal or metal compound present in relation to total solids charged to the reactor are presented in Table 2. The sources of materials tested, as indicated in Table 2, are: Alfa Research Chemicals, Danvers, MA; Calgon Corporation, Pittsburgh, PA; Dow Corning Corporation (DC), Midland, MI; Degussa Corporation, S. Plainfield, NJ; Engelhard Corporation, Edison, NJ; and United Catalyst Inc. (UCI), Louisville, KY. The support materials tested are labelled in Table 2 as: activated carbon (Act. C), alumina, Silica-alumina (Si-Al), graphite and diatomaceous earth (d-earth). The results of this series of runs is presented in Table 2 under the heading Product. Under the subheadings HSiCl₃ and SiCl₄ are listed the weight percent of these two products in relation to total recovered products. Under the heading Si-Conv is presented the percent of silicon metal consumed during the process as determined by the reduction in weight of silicon initially added to the reactor. The heading P.I. is a performance index calculated as SiCl₄ multiplied by Si-Conv /100. The first line of data represents a baseline for a process in which no catalyst or support material was present. The values presented for the baseline are the average values of four separate runs. All other values are the average values of two separate runs.	A process for preparing silanes of formula HnSiCl4-n, where n is an integer from zero to four, the process comprising contacting silicon with hydrogen chloride in the presence of an effective concentration of a catalyst comprising a metal or metal compound selected from a group consisting of tin and tin compounds, nickel and nickel compounds, arsenic and arsenic compounds, palladium and palladium compounds and mixtures thereof, rhodium and rhodium compounds, platinum and platinum compounds, iridium and iridium compounds and aluminum and aluminum compounds on a solid support at a temperature of 250°C to 500°C. A process for preparing silanes of formula HnSiCl4-n, where n is an integer from zero to four, the process comprising contacting silicon with hydrogen chloride in the presence of an effective concentration of a catalyst selected from a group consisting of tin and tin compounds, nickel and nickel compounds, arsenic and arsenic compounds, palladium and palladium compounds and mixtures thereof at a temperature of 250 to 500°C.	DOW CORNING; DOW CORNING CORPORATION	HALM ROLAND LEE; NAASZ BRIAN MICHAEL; ZAPP REGIE HAROLD; HALM, ROLAND LEE; NAASZ, BRIAN MICHAEL; ZAPP, REGIE HAROLD
EP-0489443-B1	489,443	EP	B1	EN	19,940,831	1,992	20,100,220	new	C23C14	C23C14	G03G5, C23C14	C23C 14/24B, C23C 14/24A, C23C 14/26	Vacuum evaporation system	A vacuum evaporation container includinging a resistively heatable cylindrical crucible having at least one open end and having an axially aligned slot and a hollow cylindrical insert concentrically located within the cylindrical crucible, the insert having a slot aligned with the slot of the crucible, closed ends and an electrical conductivity less than the electrical conductivity of the electrically conductive cylindrical crucible. This vacuum evaporation container is employed in a vacuum deposition process.	BACKGROUND OF THE INVENTIONThis invention relates in general to a vacuum evaporation system and more specifically, to apparatus and processes for vacuum evaporating vaporizable materials. In the art of electrophotography an electrophotographic plate comprising a photoconductive layer on a conductive layer is imaged by first uniformly electrostatically charging the imaging surface of the photoconductive layer. The plate is then exposed to a pattern of activating electromagnetic radiation such as light, which selectively dissipates the charge in the illuminated areas of the photoconductive layer while leaving behind an electrostatic latent image in the non-illuminated area. This electrostatic latent image may then be developed to form a visible image by depositing finely divided electroscopic toner particles on the surface of the photoconductive layer. The resulting visible toner image can be transferred to a suitable receiving member such as paper. This imaging process may be repeated many times with reusable photoconductive layers. Numerous different types of electrophotographic imaging members for xerography, i.e. photoreceptors, can be used in the electrophotographic imaging process. Such electrophotographic imaging members may include inorganic materials, organic materials, and mixtures thereof. Electrophotographic imaging members may comprise contiguous layers in which at least one of the layers performs a charge generation function and another layer forms a charge carrier transport function or may comprise a single layer which performs both the generation and transport functions. The electrophotographic plate may be in the form of a plate, drum, flexible photoreceptor web, sheet, flexible belt and the like. The photoconductive layer or layers may be formed of various materials. If the photoconductive materials are vaporizable and do not decompose at vaporizing temperatures, they can often be deposited by vacuum deposition. Similarly, vaporizable materials may be vacuum deposited for various other applications such as solar cells, metallic layers for decorative packaging, capacitors, optical coatings on glass and the like. Electrophotographic imaging members based on amorphous selenium have been modified to improve panchromatic response, increase speed and to improve color copyability. These devices are typically based on alloys of selenium with tellurium and/or arsenic. These selenium electrophotographic imaging members may be fabricated as single layer devices comprising a selenium-tellurium, selenium-arsenic or selenium-tellurium-arsenic alloy layer which performs both charge generation and charge transport functions. The selenium electrophotographic imaging members may also comprise multiple layers such as, for example, a selenium alloy transport layer and a contiguous selenium alloy generator layer. A common technique for manufacturing photoreceptor plates involves vacuum deposition of a selenium alloy to form an electrophotographic imaging layer on a substrate. Tellurium is incorporated as an additive for the purpose of enhancing the spectral sensitivity of the photoconductor. Arsenic is incorporated as an additive for the purpose of improving wear characteristics, passivating against crystallization and improving electrical properties. Typically, the tellurium addition is incorporated as a thin selenium-tellurium alloy layer deposited over a selenium alloy base layer in order to achieve the benefits of the photogeneration characteristics of SeTe with the beneficial transport characteristics of SeAs alloys. Fractionation of the tellurium and/or arsenic composition during evaporation results in a concentration gradient in the deposited selenium alloy layer during vacuum evaporation. Thus, the term fractionation is used to describe inhomogeneities in the stoichiometry of vacuum deposited alloy thin films. Fractionation occurs as a result of differences in the partial vapor pressure of the molecular species present over the solid and liquid phases of binary, ternary and other multicomponent alloys. Alloy fractionation is a generic problem with chalcogenide alloys. A key element in the fabrication of doped photoreceptors is the control of fractionation of alloy components such as tellurium and/or arsenic during the evaporation of selenium alloy layers. Tellurium and/or arsenic fractionation control is particularly important because the local tellurium and/or arsenic concentration at the extreme top surface of the structure, denoted as top surface tellurium (TST) or top surface arsenic (TSA), directly affects xerographic sensitivity, charge acceptance, dark discharge, copy quality, photoreceptor wear and crystallization resistance. In single layer low arsenic selenium alloy photoreceptors, arsenic enrichment at the top surface due to fractionation can also cause severe reticulation of the evaporated film. In two layer or multilayer photoreceptors where low arsenic alloys may be incorporated as a base or transport layer, arsenic enrichment at the interface with the layer above can lead to severe residual cycle up problems. In single layer tellurium selenium alloy photoreceptors, tellurium enrichment at the top surface due to fractionation can cause undue sensitivity enhancement, poor charge acceptance and enhancement of dark discharge. In two layer or multilayer photoreceptors where tellurium alloys may be incorporated as a generator layer, tellurium enrichment at the upper surface of the tellurium alloy layer can result in similar undue sensitivity enhancement, poor charge acceptance, and enhancement of dark discharge. Another common technique for manufacturing photoreceptors involves vacuum deposition of organic and inorganic pigments to form a thin charge generation layer. This charge generation layer together with a thicker charge transport layer form an electrophotgraphic imaging layer on a substrate. A typical thickness of the charge generation layer is between about 0.05 micrometer and about 1 micrometer with about 0.1 micrometer to about 0.5 micrometer being preferred. The pigment material may comprise a selenum-tellurium alloy with a high concentration of tellurium for red sensitivity or may comprise an organic pigment such as phthalocyanine, perylene, or other polycyclic pigment that is thermally stable. These organic pigments sublime when heated in the vacuum to temperatures above about 400°C. Because they do not melt and make good thermal contact with the crucible, it is preferable that they are vacuum deposited out of an isothermal source. Furthermore, while these pigments are stable at elevated temperatures in an inert container in a vacuum in the presence of metals and other impurities they may decompose or react partially. Thus, it is preferable that the evaporation source be made out of an inert materials such as quartz. Two types of techniques are used in thermal evaporation and vacuum deposition of materials. Free evaporation directly from solid surfaces (sometimes referred to as Langmuir evaporation), is approximated by shallow open crucible sources and is the most commonly used technique. This type of free evaporation from open crucible sources promote fractionation of multi-component evaporant materials such as mixtures of selenium with arsenic and/or tellurium. In the other technique, called Knudsen's method, evaporation occurs as effusion from an isothermal enclosure or crucible with a small orifice. The evaporation surface inside the enclosure is large compared with the size of of the orifice and maintains an equilibrium pressure inside. The enclosed Knudsen type of source has two advantages: the enclosed source eliminates spatter due to localized vaporization by poorly conducting materials and gives a greater latitude in choosing temperature and pressure conditions that will permit a multicomponent material to be in equilibrium and evaporate congruently. When a multicomponent material is in equilibrium and evaporates congruently, the composition of the deposited coating is constant with time. Many vaporizable materials such as, for example, alloys of selenium, arsenic and/or tellurium can be evaporated congruently under the appropriate conditions. Tube crucibles with a constricted slit approximate a Knudsen cell and facilitate attainment of equilibrium and congruent evaporation of multicomponent materials. The geometry of a tube crucible having a constricted slit also permits easy fabrication and uniform heating by resistance with no cold or hot spots. Although excellent deposits may be achieved with tube crucibles having constricted slits or slots, loading of evaporants through the narrow slot opening is difficult, slow, tedious, and sometimes, impossible because of the relative size of the particles being loaded and the width of the slot in the Knudsen-type crucible. If the slit opening is widened to facilitate loading of the crucible, the performance of the crucible approaches that of an open crucible. On the other hand, abandonment of the simple tube geometry concept to fabricate compound crucibles with a removable cover to allow loading introduces difficulties in maintaining temperature uniformity within the crucible. It also renders loading more complex (particularly in planetary coating devices), difficult, expensive and time consuming. Further, after one or more coating runs, it may be necessary to clean the crucible of residue as the resulting debris can cause defects to occur in subsequently formed photoreceptor layers. Generally, because of the importance of maintaining a fixed distance between the crucibles and the substrates to be coated, and because of the massive electrical connections utilized between the electrically conductive crucibles and the power source, the crucibles are normally rigidity mounted in position and removal thereof is difficult and time consuming. Moreover, because the crucibles are normally semi-permanently mounted in the vacuum chamber, production is delayed for loading of the crucibles with the evaporant and for cleaning. Further, cleaning of the Knudsen-type crucibles is extremely difficult because of the small slot widths. INFORMATION DISCLOSURE STATEMENTUS-A 4,842,973 to Badesha et al., issued June 27, 1989, - A process is disclosed for fabricating an electrophotographic imaging member comprising providing in a vacuum chamber at least one first layer crucible, at least one second layer crucible, and a substrate. The substrate may comprise an electrically conductive material such as aluminum, titanium, nickel, stainless steel, and the like. See, for example, column 9, lines 19-22. US-A 3,582,611 to Matheson et al., issued June 1, 1971 - An apparatus is disclosed for evaporation and vacuum deposition of metal on an article to be coated. A variable resistance evaporation boat 6 has a cavity 7 on its upper surface as shown in Fig. 1. The ends of the boat have a lower resistivity than the center in order to reduce end heat loss. US-A 3,637,980 to Fox et al., issued January 25, 1972 - An evaporating boat is disclosed in which a trough is shown for receiving materials to be evaporated. US-A 3,845,739 issued to Erhart et al on November 5, 1974 - A planetary coating system is disclosed for vacuum coating a plurality of substrate bodies. US-A 3,861,353 issued to Erhart et al on January 21, 1975 - A planetary coating system is disclosed for vacuum coating a plurality of substrate bodies. Thus, there is a continuing need for an improved system for vacuum evaporating vaporizable materials. SUMMARY OF THE INVENTIONIt is, therefore, an object of the present invention to provide an improved vacuum evaporation containers which facilitate more rapid loading of material to be evaporated. It is another object of the present invention to provide improved vacuum evaporation containers which are inert with respect to the evaporant. It is yet another object of the present invention to provide improved vacuum evaporation containers which eliminates the need for frequent connecting and disconnecting of electrical cables. It is still another object of the present invention to provide improved vacuum evaporation containers which facilitates cleaning off-line. It is another object of the present invention to provide improved vacuum evaporation containers which facilitate rapid change of the type materials to be deposited. It is yet another object of the present invention to provide improved vacuum evaporation containers which permit the use of disposable evaporation container components. It is still another object of the present invention to provide improved vacuum evaporation containers which permit the use of harsh materials such as acids or solvents to clean vacuum evaporator containers without adverse effects. The foregoing objects and others are accomplished in accordance with this invention by providing a vacuum evaporation container comprising a resistively heatable cylindrical crucible having at least one open end and having an axially aligned slot and a hollow cylindrical insert concentrically located within the cylindrical crucible, the insert having a slot aligned with the slot of the crucible, closed ends and an electrical conductivity less than the electrical conductivity of the electrically conductive cylindrical crucible. This invention also includes a vacuum deposition process comprising providing a vacuum evaporation container comprising an electrically conductive cylindrical crucible having at least one open end and having an axially aligned slot and a hollow cylindrical insert concentrically located within the cylindrical crucible, the insert having a slot aligned with the slot of the crucible, closed ends and an electrical conductivity less than the electrical conductivity of the electrically conductive cylindrical crucible, inserting solid vaporizable material into the hollow cylindrical insert, placing a substrate to be coated adjacent to the vacuum evaporation container, and heating the cylindrical crucible in a partial vacuum to vaporize the vaporizable material and depositing the material as a coating on an adjacent substrate. BRIEF DESCRIPTION OF THE DRAWINGSA more complete understanding of the present invention can be obtained by reference to the accompanying drawings wherein: FIG. 1A is an isometric illustration of an open ended cylindrical crucible employed in the system of this invention. FIG. 1B is an isometric illustration of a closed end cylindrical insert employed in the system of this invention. FIG. 2 is a schematic cross-sectional view of a closed end cylindrical insert enclosed within an open ended cylindrical crucible employed in the system of this invention. These figures merely schematically illustrate the invention and are not intended to indicate relative size and dimensions of the device or components thereof. DETAILED DESCRIPTION OF THE DRAWINGS Referring to FIG. 1A, a hollow electrically conductive cylindrical crucible 10 is shown having open ends 12 and 14 and a narrow slit opening 16. In FIG. 1B, a hollow cylindrical boat insert 20 is illustrated having closed ends 22 and 24 and a wide slit opening 26. This wide slit opening facilitates rapid and clean loading of evaporant into the hollow cylindrical boat insert 20. Referring to FIG. 2, hollow cylindrical boat insert 20 is concentrically located within cylindrical crucible 10 with wide slit opening 26 aligned with narrow slit opening 16. Electrically conductive flanges 28 and 30, welded to each end of cylindrical crucible 10, contain holes 32 and 34 adapted to receive bolts (not shown) which secure power cables (not shown) to the flanges. The flanges are also provide support for the crucible and can be fastened by any suitable means to frame members of any suitable and conventional vacuum coating housing (not shown). An optional baffle 36 may positioned between the ends 22 and 24 of insert 20 and above the evaporant (not shown) to prevent line of sight exit of evaporated material through opening 16, but still allow easy loading as well as egress of vapors. The baffle may be of any suitable shape. Typical cross-sectional shapes include flat, inverted square U , inverted semicircle, and the like. Generally, hollow cylindrical boat insert 20 is as long as the coating widths required for each substrate to be coated. The narrow slit opening 16 of crucible 10 is preferably positioned parallel to the surface to be coated. Where the surface to be coated is the outer surface of drums, the axis of the drums are preferably positioned parallel to the axis of hollow electrically conductive cylindrical crucible 10. Similarly, the axis of rollers supporting web material to be coated are also preferably positioned parallel to the axis of hollow electrically conductive cylindrical crucible 10. If desired, hollow electrically conductive cylindrical crucible 10 may be relatively long and enclose a plurality of relatively short cylindrical boat inserts 20. Where drums are supported on mandrels parallel to and spaced from the long hollow crucible, the length of individual cylindrical boat inserts would normally be as long as the coating widths required for each drum. Similarly, where multiple segment strips across the width of wide belts are to be coated (the belt being subsequently sliced lengthwise to separate it into segment strips), the length of individual cylindrical boat inserts would normally be as long as the coating widths required for each segment strip. Although a space between the outer surface of cylindrical insert 20 and hollow electrically conductive cylindrical crucible 10 is shown in FIG. 2, any such space is preferably eliminated or at least minimized in order to maximize heat transfer between the outer surface of cylindrical insert 20 and hollow electrically conductive cylindrical crucible 10. The cylindrical insert 20 and hollow electrically conductive cylindrical crucible 10 combination may be used as a vacuum evaporation container in any suitable and conventional vacuum coating apparatus such as a planetary coater, an in-line coater, a web coater, coaters with stationary substrates, and the like. Typical planetary coaters are described in US-A 3,861,353 and US-A 3,845,739, the entire disclosures thereof being incorporated herein by reference. In operation, hollow boat cylindrical insert 20 is loaded with evaporant through wide slit opening 26. The hollow boat cylindrical insert 20 can be preloaded while a coating run is being made with another previously loaded hollow boat cylindrical insert 20 thereby minimizing the time expended to remove the empty inserts, cleaning the insert (if necessary), loading the insert with evaporant, and reinstalling the insert in the crucible. When the previous coating run is completed, the empty hollow boat cylindrical insert 20 may be slid out from either open end 12 or 14 of hollow electrically conductive cylindrical crucible 10 and the preloaded insert slid into either open end 12 or 14 of crucible 10. If desired, the preloaded insert may be pushed into one open end of crucible 10 to force out the empty inserts from the other open end of crucible 10. After sliding preloaded insert 20 into crucible 10 and positioning a substrate to be coated adjacent to crucible 10, a suitable partial vacuum is applied to a chamber housing crucible 10 and the substrate to be coated (not shown). Sufficient electric current is supplied to flanges 28 and 30 to heat crucible 10 and insert 20 and evaporate the evaporant. The crucible is heatable by electrical resistance heating. Any suitable electrically conductive heat resistant material may be utilized for the crucible. Generally, the resistance heatable crucibles have a resistance range of between about 10⁻² ohms and about 10⁻³ ohms. Typical electrically conductive heat resistant material include stainless steel, tantalum, tungsten, molybdenum, Hastelloy™, and the like. The specific resistivity selected depends upon the electrical power supply utilized. Any suitable means such as flanges fastened to the crucibles may be utilized to facilitate attachment of electrical connections. The flanges may have holes drilled therethrough to allow electrical terminals to be bolted thereon. The crucibles walls should be sufficiently thick to allow the crucible to be self supporting and resistant to distortion or warping during use at elevated temperatures. Typical wall thicknesses are from about 0.25 millimeter to about 1 millimeter. Thin walls are preferred to achieve high electrical resistance. The cross-section of the interior of the crucible may be of any suitable shape. Typical shapes include circles, ovals, squares, rectangles, triangles, pentagons, hexagons, octagons, and the like. The length of the crucible is preferably longer than the width of the substrate to be coated. The inner cross-sectional area selected for the crucible depends upon the intended use of the crucible. Thus, for example, when small amounts of evaporant is to be deposited, the inner cross-sectional area of the crucible should be correspondingly small. A typical inner cross-sectional areas for a crucible to be used to form selenium alloy coating having a thickness of about 50 micrometers on six cylindrical metal substrates having a circumference of about 200 centimeters is about 192 square centimeters. A typical inner cross-sectional area for a crucible to be used to form a charge generator layer having a thickness of about 0.2 micrometer on a web about 2 kilometers long is about 128 cm². In the above, it was assumed that the packing density of the evaporant was about 25 percent, the coating efficiency was about 50 percent and less than about 25 percent of the crucible volume was filled. The maximum size of the width of the crucible slot depends upon the interior volume of the crucible, the rate of the material to be deposited and the positive pressure to be achieved within the crucible during deposition. Thus, the smaller the internal volume of the crucible, the smaller the slot width to ensure that sufficient pressure is achieved during evaporation so that the evaporated material flows substantially uniformly through the narrow slot to the substrate to be coated. Depending upon the interior volume of the crucible, the slot width may vary from between about 5 millimeters and about 50 millimeters. The minimum width of the slot is determined by the need to avoid plugging of the slot during vacuum deposition of the coating. Generally, the ratio of the slot width to the interior cross-sectional area of the crucible ranges from between about 1:100 and about 1:5. A typical example of a crucible slot width to interior cross-sectional area for vacuum deposition of a material comprising organic pigment is a crucible having a slot width of about 13 millimeters and an interior cross-sectional area of about 71 square centimeters. Generally, the length of the crucible slot is slightly longer than the width of the area to be coated. Where the length of the crucible extends across the widths of multiple substrates, the slot may optionally contain transverse struts which enhance rigidity of the crucible and which function as masks to prevent deposition of evaporant adjacent the edges of each substrate being coated. The crucible utilized for this invention may be rigidly mounted in the vacuum deposition apparatus to ensure proper alignment with the substrate to be coated. The crucible need not be moved from the coating housing from one coating operation to another. This eliminates the need for frequent connecting and disconnecting of heavy electrical power cables which could result in changes in electrical resistivity at the point of connection from one coating run to another thereby affecting the quality and quantity of vacuum deposited coating. To permit expansion and contraction of the crucible when heated and cooled, one end may be mounted so that it is free to move on the axis of the crucible. Any suitable inert heat resistant material having an electrically conductivity less than that of the crucible may be employed in the boat insert. The boat insert may be electrically conductive but, in this case, its resistivity should be taken into account to determine the current needed to heat the crucible. Preferably, the hollow cylindrical insert is sufficiently electrically insulating so that less than about 1 percent of the electrical current flowing from one end of the crucible to the other end passes through the boat insert. The hollow cylindrical insert should be resistant to degradation at high vacuum deposition temperatures and be non-reactive with materials to be vacuum deposited. Typical heat resistant materials having an electrically conductivities less than that of electrically conductive crucibles include quartz glass, graphite, aluminum oxide, silicon carbide, tantalum carbide, ceramic, and the like. Generally, the insert materials do not react with the evaporant material and are unaffected by acids or strong solvents useful for the removal of coating material residue whereas acids or solvents are corrosive to many crucible materials. If desired, the inserts may be disposable. The insert walls should be sufficiently thick to allow the insert to be self supporting and resistant distortion or warping during use at elevated temperature. Typical insert wall thicknesses are from about 1 millimeter and about 10 millimeters. Generally, the ends of the crucibles are aligned with areas of the drum webs that are to be free of uncoated material. Thus, each end of an insert is preferably aligned with the corresponding edge of a substrate that is to remain uncoated. The length of the insert may be longer than, the same as, or shorter than the length of the crucible. A plurality of inserts may be inserted into a single crucible. Preferably, the insert has a length (combined length where multiple inserts are involved) shorter than the length of the crucible so that the insert or inserts can be more centrally positioned in the crucible where heating is more uniform. Inserts of various different lengths may be utilized in the same crucible. Thus, a permanently mounted crucible can be used to apply coatings of different widths thereby accommodating different substrates having different widths either during the same coating run or in sequential runs. Preferably, the end walls of the inserts should be shaped to substantially close each open end of the crucible. Such closures serve to maintain pressure within the crucible. The width of the slot employed for the insert may be quite large and, for example, equal the diameter of an insert having a circular cross-section. The length of the slot in the insert may be as small as the width of the slot for large volume crucibles where the crucible slot is wide enough to facilitate easy loading of the crucible with the specific material to be vacuum deposited. However, if the width of the slot of the crucible is too small for convenient loading of the material to be evaporated, the width of the slot of the insert should be larger than the slot of the crucible and be of sufficient width to facilitate easy loading of the material to be vacuum deposited. Also, the width of the insert slot should be larger than the largest particle size of the material to be vacuum deposited even though the width of the crucible slot is smaller than the largest particle size of the material to be vacuum deposited. Typical slot widths are between about 2.5 centimeters and about 25 centimeters. In typical evaporation runs for depositing alloys, alloys of Arsenic and selenium could be vacuum evaporated congruently, that is, the composition of the deposit could be maintained constant with time by employing narrow crucible openings of less than 10 millimeter and preferable less than 5 millimeter for a 50 millimeter diameter crucible. Generally, it is preferred that the cylindrical insert fit snugly in the interior of the crucible to maximize transfer of heat energy from the crucible to the insert and prevent vapors from exiting out the ends. Thus, it is preferred that the external cross-sectional shape of the insert have the same shape as the cross-sectional shape of the crucible. This ensures that the external surface of the insert will be substantially paralleled to the adjacent interior surface of the crucible in a direction axial of both the insert and crucible. If desired, one or more baffles may be mounted within the interior of the insert to block any line of sight path between the surface of the material to be vacuum deposited and the slot opening of the crucible. Typical baffles include baffles extending from one end of the insert to the other end, the baffles having a cross-section shape like an inverted U with 90° corners. The cross-sectional shape of the baffle may have any other suitable configuration such as flat, arcuate, angular, and the like. Since matching sets of inserts may be utilized to facilitate loading of one set of inserts with material to be vacuumed deposited while another set of inserts is simultaneously being used in a crucible for a coating operation, loaded inserts can be inserted into crucibles immediately after removal of spent inserts. Moreover, by using one or more extra sets of inserts, some of the sets of inserts may be cleaned while other inserts are being used for loading operations and still other sets of inserts are employed in coating operations. Where the crucibles are open at each end, fresh inserts can be inserted in one end of the crucible thereby pushing the spent inserts out the other end. Alternatively, the spent inserts may be pushed out of one end of a crucible by inserting a push rod into the other end of the crucible and freshly loaded inserts may be inserted into the same end of the crucible from which the spend inserts were removed. Still other loading and unloading procedures are apparent in view of these teachings. Any suitable material may be vacuum deposited with the evaporation container of this invention. The materials may be organic or inorganic. Typical inorganic materials for vacuum deposition include selenium, selenium arsenic alloys, selenium arsenic tellurium alloys, selenium tellurium alloys, halogen doped selenium alloys, and the like. Photoconductive chalcogenide alloy including binary, tertiary, quaternary, and the like alloys may be employed to form a vacuum deposited photoconductive layer. Typical photoconductive alloys of selenium include selenium-tellurium, selenium-arsenic, selenium-tellurium-arsenic, selenium-tellurium-chlorine, selenium-arsenic-chlorine, selenium-tellurium-arsenic-chlorine alloys, and the like. Preferred photoconductive alloys include alloys of selenium with tellurium, arsenic, or tellurium and arsenic with or without a halogen dopant. As employed herein, a selenium alloy is defined as an intermetallic compound of selenium with other elemental additives where the ratios of constituents are inconsistent with stoichiometric compositions. The photoconductive alloys of selenium may be applied to a coated or uncoated substrate alone as the only photoconductive layer or it may be used in conjunction with one or more other layers such as a selenium or selenium alloy transport layer and/or a protective overcoat layer. Generally, the selenium-tellurium alloy may comprise between about 5 percent by weight and about 40 percent by weight tellurium and a halogen selected from the group consisting of up to about 70 parts per million by weight of chlorine and up to about 140 parts per million by weight of iodine all based on the total weight of the alloy with the remainder being selenium. The selenium-arsenic alloy may, for example, comprise between about 0.01 percent by weight and about 50 percent by weight arsenic and a halogen selected from the group consisting of up to about 200 parts per million by weight of chlorine and up to about 1000 parts per million by weight of iodine all based on the total weight of the alloy with the remainder being selenium. The selenium-tellurium-arsenic alloy may comprise between about 5 percent by weight and about 40 percent by weight tellurium, between about 0.1 percent by weight and about 5 percent by weight arsenic and a halogen selected from the group consisting of up to about 200 parts per million by weight of chlorine and up to about 1000 parts per million by weight of iodine all based on the total weight of the alloy with the remainder being selenium. The expressions alloy of selenium and selenium alloy are intended to include halogen doped alloys as well as alloys not doped with halogen. When employed as a photoconductive layer in an electrophotographic imaging member, the thickness of the photoconductive selenium alloy layer is generally between about 0.1 micrometer and about 400 micrometers thick. Selenium-tellurium and selenium-tellurium-arsenic alloy photoconductive layers are frequently employed as a charge generation layer in combination with a charge transport layer. The charge transport layer is usually positioned between a supporting substrate and the charge generating selenium alloy photoconductive layer. Generally, a selenium-tellurium alloy may comprise from about 60 percent by weight to about 95 percent by weight selenium and from about 5 percent by weight to about 40 percent by weight tellurium based on the total weight of the alloy. The selenium-tellurium alloy may also comprise other components such as less than about 35 percent by weight arsenic to minimize crystallization of the selenium and less than about 1000 parts per million by weight halogen. In a preferred embodiment, the photoconductive charge generating selenium alloy layer comprises between about 5 percent by weight and about 25 percent by weight tellurium, between about 0.1 percent by weight and about 4 percent by weight arsenic, and a halogen selected from the group consisting of up to about 100 parts per million by weight of chlorine and up to about 300 parts per million by weight of iodine with the remainder being selenium. Compositions for optimum results are dictated by the application. It is desirable, in general, to achieve uniformly homogeneous compositions within the evaporated layers, i.e. to evaporate the alloy materials without significant fractionation. Elevated levels of tellurium lead to excessive photoreceptor light sensitivity and high dark decay and correspondingly reduced levels of tellurium result in low light sensitivity and loss of copy quality. Elevated levels of arsenic in some applications, above about 4 percent by weight, can lead to high dark decay, to problems in cycling stability and to reticulation of the photoreceptor surface. The resistance of amorphous selenium photoreceptors to thermal crystallization and surface wear begins to degrade as the concentration of arsenic drops below about 1 percent by weight. As the chlorine content rises above about 70 parts per million by weight chlorine, the photoreceptor begins to exhibit excessive dark decay. The inorganic particles employed in the process of this invention may, in general, be in either shot (bead) particle or pellet particle form. However, the particles may also be in chunk form, if so desired. Generally, to prepare selenium alloy shot (bead) particles, the components of selenium alloys are combined by melting the selenium and additives together by any suitable conventional technique. The molten selenium alloy is then shotted by any suitable method. Shotting is usually effected by quenching molten droplets of the alloy in a coolant such as water to form large particles of alloy in the form of shot or beads. Shotting processes for forming alloy beads are well known and described, for example, in US-A 4,414,179, the entire disclosure of this patent being incorporated herein by reference. The alloy beads may have an average size of, for example, between about 300 micrometers and about 3,000 micrometers. Pellet particles may be prepared from shot particles by grinding shot particles into a powder and thereafter compressing the powder into relatively large pellets. Pelletizing of the amorphous shotted alloy is frequently utilized as a means of controlling fractionation. Where selenium alloy pellets are to be employed, the alloy beads, or combination of the alloy beads and minor amount of dust particles may be rapidly ground in a conventional high speed grinder or attritor to form alloy particles having an average particle size of less than about 200 micrometers. Any suitable grinding device may be utilized to pulverize the bead particles to form the fine alloy particles having an average particle size of less than about 200 micrometers. Typical grinders include hammer mills, jet pulverizers, disk mills, and the like. Depending upon the efficiency of the grinding device employed, grinding alloy beads to form alloy particles having an average particle size of less than about 200 micrometers can normally be accomplished in less than about 5 minutes. Longer grinding times may be employed, if desired. One method of preparing selenium alloys for evaporation is to grind selenium alloy shot (beads) and compress the ground material into pellet agglomerates, typically 150-300 mg. in weight and having an average diameter of about 6 millimeters (6,000 micrometers). The pellets are evaporated from the containers of this invention in a vacuum coater using a time/temperature profile designed to minimize the fractionation of the alloy during evaporation. The pellets may be of any suitable shape. Typical shapes include cylinders, spheres, cubes, tablets, and the like. Compression of the alloy particles into pellets may be accomplished with any suitable device such as, for example, a simple punch tableting press, a multi punch rotary tableting press, and the like. Typical organic materials for vacuum deposition include phthalocyanines including metal free phthalocyanine described in US-A 3,357,989, metal phthalocyanines such as vanadyl phthalocyanine and copper phthalocyanine, titanyl phthalocyanine and chloroindium phthalocyanine, dibromoanthanthrone, perylene pigments, Monastral violet and Monastral Red Y, Vat orange 1 and Vat orange 3 trade names for dibromo anthanthrone pigments, benzimidazole perylene, polynuclear aromatic quinones available from Allied Chemical Corporation under the tradename Indofast Double Scarlet, Indofast Violet Lake B, Indofast Brilliant Scarlet and Indofast Orange, and the like. Other suitable vaporizable materials known in the art may also be utilized, if desired. Generally, the temperatures employed for vacuum deposition should be sufficient to vaporize or sublime the material being vacuum deposited. The partial vacuum applied can vary within a wide range depending on the specific materials to be deposited. Typical applied vacuums range from between about about 1,33 Pa and about 1,33 10⁻⁴ Pa (10⁻² and about 10⁻⁶ torr). Thus, for example, chamber pressure during evaporation of selenium alloys may be on the order of about 4 x 10⁻⁵ torr. Depending upon the specific material utilized and the type of vacuum applied, the typical coating temperatures employed are between about 200°C and about 800°C. Evaporation is normally completed in about 15 to 25 minutes with a molten selenium alloy temperature ranging from about 250°C to about 500°C. Other times and temperatures and pressures outside these ranges may be used as well understood by those skilled in the art. It is generally desirable that the substrate temperature be maintained in the range of from about 50°C. to about 70°C during deposition of a selenium alloy layer. Additional details for the preparation of selenium layers are disclosed, for example, in US-A 4,842,973 and US-A 4,297,424, the entire disclosures of these patents being incorporated herein by reference. Evaporation of organic pigments by sublimation is typically accomplished at temperatures between about 400°C and about 600°C. Deposition on a moving web is performed at rates of at least about 5 meters/minute to about 100 meters/minute with higher rates preferable for reasons of economy. The higher rates will, of course, require higher temperatures of evaporation. To ensure that the polymeric web substrate is not heated above its softening point, the web is wrapped on a cooling cylinder above the crucible. Additional details for the deposition of organic charge generation layers are disclosed, for example, in US-A 4,555,463 and US-A 4,587,189, the disclosures of these patents being incorporated herein in their entirety. The substrate to be coated may be opaque or substantially transparent and may comprise numerous suitable materials having the required mechanical properties. The entire substrate may comprise a single layer material or it may comprise multiple layers. The surface of the substrate may be electrically insulating or electrically conductive. Any suitable electrically conductive material may be employed. Typical electrically conductive materials include, for example, aluminum, titanium, nickel, chromium, brass, stainless steel, copper, zinc, silver, tin, and the like. The electrically conductive material may vary in thickness over substantially wide ranges depending on the desired use. Accordingly, the conductive material may comprise a layer ranging in thickness, for example, from about 50 Angstrom units to many centimeters. Typical electrically insulating non-conducting substrate materials include polyesters, polycarbonates, polyamides, polyurethanes, and the like. The coated or uncoated substrate may be flexible or rigid and may have any number of configurations such as, for example, a plate, a cylindrical drum, a scroll, an endless flexible belt, and the like. For electrophotoconductive members, the outer surface of the supporting substrate preferably comprises a metal oxide such as aluminum oxide, nickel oxide, titanium oxide, and the like. If desired, conventional relative movement may be effected between the surface of the substrate to be coated and the crucible slot. Thus, for example, drum shaped substrates may be rotated adjacent a crucible slot to achieve vapor deposition of coating material around the entire circumference of the drum. In some cases, intermediate adhesive layers between the substrate and subsequently applied layers may be desirable to improve adhesion. If such adhesive layers are utilized, they preferably have a dry thickness between about 0.1 micrometer to about 5 micrometers if utilized in an electrophotoconductive member. Typical adhesive layers include film-forming polymers such as polyester, polyvinylbutyral, polyvinylpyrolidone, polycarbonate, polyurethane, polymethylmethacrylate, and the like and mixtures thereof. A principal advantage of this invention is that it enables operating conditions that minimize differential evaporation of a two component material, sometimes referred to as fractionation, and large particle ejection or spatter of the evaporant material. Another advantage is that inert material which is not suitable for resistance heating maybe used to hold the evaporant material. Still another advantage is that the vacuum evaporator containers of this invention may be easily cleaned with harsh materials such as acids or solvents without any adverse effects. Other advantages include ease of loading of the evaporant. A number of examples are set forth hereinbelow and are illustrative of different compositions and conditions that can be utilized in practicing the invention. All proportions are by weight unless otherwise indicated. It will be apparent, however, that the invention can be practiced with many types of compositions and can have many different uses in accordance with the disclosure above and as pointed out hereinafter. EXAMPLE IA photoreceptor drum was coated using the vacuum evaporation container of this invention. An aluminum drum was mounted on rotatable shaft. The axis of the drum was positioned parallel to the axis of a cylindrical stainless steel crucible. The drum had a length of about 40 centimeters and a diameter of about 24 centimeters. The cylindrical crucible of stainless steel had a circular cross-section, an internal diameter of about 5 centimeters, a wall thickness of about 0.5 millimeter, a length of about 60 centimeters, and an axially aligned narrow slot along the top of the cylindrical crucible. The crucible slot had a width of about 5 millimeters and a slot length of about 45 centimeters. The drum was positioned so that its outer surface was about two centimeters from the crucible. A cylindrical insert machined from a carbon (graphite) rods (available from Pure Carbon Corp of Pennsylvania), having a circular cross-section, an external diameter of about 4.98 centimeters, a wall thickness of about 2.5 millimeters, and an axially aligned wide slot on the top of the cylindrical crucible was loaded with 190 grams of selenium-arsenic-iodine pellets. The insert slot had a width of about 15 millimeters and a length of 38 centimeters. The insert also had circular shaped ends, each end having a diameter of about 4.98 centimeters. The selenium-arsenic-iodine pellets were formed from beads prepared by water quenching droplets of a molten alloy comprising about 63.7 atomic percent selenium, about 36 atomic percent arsenic and about 0.3 atomic percent iodine, based on the total weight of the beads. Electrophotographic imaging members were prepared by vacuum evaporating the selenium-arsenic-iodine alloy pellets at a temperature of 385°C to 410°C with the aluminum drum substrate held at 180°C, at an evaporation pressure between about 5,3 10⁻² Pa and 2,7 10⁻³ Pa (4 x 10⁻⁴ torr and 2 x 10⁻⁵ torr). This resulted in a film 60 micrometers thick and 38 centimeters wide and comprising about 36.5 atomic percent arsenic, 0.37 atomic percent iodine and 73.1 atomic percent selenium. This composition was obtained by X-ray energy dispersion analysis based on the total weight of the final coating layer onto the aluminum substrates. A top surface analysis by means of an electron probe gave 37 atomic percent arsenic, indicating excellent uniformity. EXAMPLE IIA polyester film supplied from a roll can be vacuum coated with an electrically conductive titanium layer so that the layer has a thickness of about 200 Angstroms. The exposed surface of the titanium layer should be oxidized by exposure to oxygen in the ambient atmosphere. A siloxane hole blocking layer can be formed on the oxidized titanium layer by applying a 0.22 percent (0.001 mole) solution of 3-aminopropyl triethoxylsilane with a gravure applicator. The deposited coating can be dried at 135°C in a forced air oven to form a layer having a thickness of about 450 Angstroms. A coating of polyester resin (49000, available from the E. I. du Pont de Nemours & Co.) can next be applied with a gravure applicator to the siloxane coated base. The polyester resin coating can be dried to form a film having a thickness of about 0.05 micrometer. This coated film web about 45 centimeters wide can then be placed in a roll vacuum coater. The film can be moved across a crucible positioned about 10 centimeters from the top of a cylindrical stainless steel crucible. The cylindrical crucible can be identical to that described in Example I. A cylindrical insert fabricated from a quartz glass tube having a circular cross-section, an external diameter of about 4.98 centimeters, a wall thickness of about 2 millimeters, and an axially aligned wide slot on the top of the cylindrical crucible can next be loaded with about 50 grams of benzimidazole perylene pellets. The perylene can be formed by the condensation of perylene dianhidride with o-phenylene diamine as described in US Patent No. 4,587,189 and compacted into pellets about 13 millimeters in diameter and about 5 millimeters thick. The insert slot can have a width of about 40 millimeters and a length of about 40 centimeters. The insert can also have circular shaped ends enclosing the cylinder. Electrophotographic imaging members can be prepared by vacuum evaporating the pigment pellets to form a charge generator layer or film at a crucible temperature of about 550°C and an evaporation pressure between about 5.3 10⁻² Pa and 2.7 10⁻³ Pa (4 x 10⁻⁴ torr and 2 x 10⁻⁵ torr). The speed of the web can be controlled to give a thickness of deposited film to be about 0.2 micrometers. A charge transport layer can then be formed on the charge generator layer by applying a solution of a polycarbonate resin and N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine dissolved in methylene chloride to ultimately provide a 40 percent by weight loading of N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine, respectively, in the transport layer after drying. Sufficient transport layer material can be coated on top of the generator layer so that after drying at temperature of about 135°C, a transport layer having thickness of about 24 micrometer is formed. An optional anti curl backing coating can be also applied.	A vacuum evaporation container comprising resistively heatable cylindrical crucible having at least one open end and having an axially aligned slot and at least one hollow cylindrical insert concentrically located within said cylindrical crucible, said insert having a slot aligned with said slot of said crucible, closed ends and an electrical conductivity less than the electrical conductivity of said electrically conductive cylindrical crucible. A vacuum evaporation container according to Claim 1 wherein a plurality of cylindrical inserts in a row are concentrically located within said cylindrical crucible. A vacuum evaporation container according to Claim 1 wherein said cylindrical crucible is resistively heatable to between about 200°C and about 800°C. A vacuum evaporation container according to Claim 1 wherein said cylindrical crucible has a wall thicknesses between about 0.25 millimeter and about 1 millimeter. A vacuum evaporation container according to Claim 1 wherein the ratio of the width of said crucible slot to the interior cross-sectional area of said crucible ranges from between about 1:100 and about 1:5. A vacuum evaporation container according to Claim 1 wherein said insert has a wall thicknesses between about 1 millimeter and about 10 millimeters. A vacuum evaporation container according to Claim 1 wherein said insert has a slot width between about 2.5 centimeters and about 25 centimeters. A vacuum evaporation container according to Claim 1 wherein the external cross-sectional shape of said insert has the same general shape as the cross-sectional shape of said crucible. A vacuum evaporation container according to Claim 1 wherein said insert contains a baffle mounted within the interior of said insert to block any line of sight path between the surface of material to be vacuum deposited and said slot of said crucible. A vacuum evaporation container according to Claim 1 wherein said crucible is open at each end. A vacuum evaporation container according to Claim 1 wherein the width of said slot of said insert is wider than the width of said slot of said crucible. A vacuum deposition process comprising providing a vacuum evaporation container comprising resistively heatable cylindrical crucible having at least one open end and having an axially aligned slot and at least one hollow cylindrical insert concentrically located within said cylindrical crucible, said insert having a slot aligned with said slot of said crucible, closed ends and an electrical conductivity less than the electrical conductivity of said resistively heatable cylindrical crucible, inserting particles of solid vaporizable material into said hollow cylindrical insert, placing a substrate to be coated adjacent to said vacuum evaporation container, and heating said cylindrical crucible in a partial vacuum to vaporize said vaporizable material and depositing said material as a coating on an adjacent substrate. A vacuum deposition process according to Claim 12 wherein a plurality of cylindrical inserts are concentrically located within said cylindrical crucible. A vacuum deposition process according to Claim 12 wherein the external cross-sectional shape of said insert has the same general shape as the cross-sectional shape of said crucible. A vacuum deposition process according to Claim 12 including removing said insert from said open end, inserting solid particles of vaporizable material into said hollow cylindrical insert, and sliding said insert containing said solid vaporizable material into said open end prior to heating said cylindrical crucible in a partial vacuum to vaporize said vaporizable material. A vacuum deposition process according to Claim 15 including inserting fresh solid particles of vaporizable material into a second hollow cylindrical insert while said first insert containing said solid vaporizable material is heated in said partial vacuum to vaporize said vaporizable material. A vacuum deposition process according to Claim 12 including heating said cylindrical crucible by passing an electric current through said crucible from one end to the other. A vacuum deposition process according to Claim 17 wherein the bulk resistivity of said electrically conductive cylindrical crucible is between about 10⁻² ohms and about 10³ ohms and said insert is sufficiently electrically insulating so that less than about 1 percent of said electrical current flowing from one end of said crucible to the other passes through said insert. A vacuum deposition process according to Claim 12 wherein the width of said slot of said crucible is smaller than the largest particle size of said solid particles of vaporizable material and the the width of said slot of said insert is larger than the largest particle size of said solid particles of vaporizable material. A vacuum deposition process comprising providing a vacuum evaporation container comprising at least one resistively heatable conductive cylindrical crucible having at least one open end and having an axially aligned slot and a first hollow cylindrical insert concentrically located within said cylindrical crucible, said first hollow cylindrical insert having a slot aligned with said slot of said crucible, closed ends and an electrical conductivity less than the electrical conductivity of said electrically conductive cylindrical crucible, inserting particles of a first solid vaporizable material into said first hollow cylindrical insert, placing a first substrate to be coated adjacent to said vacuum evaporation container, said first substrate having an area to be coated that has a width substantially the same as the length of said slot of said first hollow cylindrical insert, heating said cylindrical crucible in a partial vacuum to vaporize said first vaporizable material, depositing said first vaporizable material as a coating on said first substrate, removing said first substrate, removing said first hollow cylindrical insert from said crucible, sliding a second hollow cylindrical insert containing a second solid vaporizable material into said crucible, said second hollow cylindrical insert having a slot length different from the slot length of said first hollow cylindrical insert, aligning said slot of said second hollow cylindrical insert with said slot of said crucible, placing a second substrate to be coated adjacent to said vacuum evaporation container, said second substrate having an area to be coated that has a width substantially the same as the length of said slot of said second hollow cylindrical insert, heating said cylindrical crucible in a partial vacuum to vaporize said second vaporizable material, and depositing said second vaporizable material as a coating on said second hollow cylindrical substrate.	XEROX CORP; XEROX CORPORATION	MELNYK ANDREW R; SWALES MICHAEL G; TENEY DONALD; MELNYK, ANDREW R.; SWALES, MICHAEL G.; TENEY, DONALD
EP-0489444-B1	489,444	EP	B1	EN	19,990,407	1,992	20,100,220	new	H04B10	H04J14	H04J14, H04B10	H04B 10/148, H04J 14/02M	Method for transmission and receipt of coherent light signals	The invention relates to a method for transmission and receipt of coherent light signals. Each subscriber is provided with an optical heterodyne detection circuit. An oscillation light of an optical local oscillator (3) is divided to a local oscillation light (4) for the heterodyne detection and a transmitting light (20) for data communication. A channel for those lights is selected from vacant communication channels. The transmitting light (20) may be obtained from a transmission light oscillator which is controlled by a control unit common to the optical local oscillator.	This invention relates to a method for transmission and receipt of coherent light signals used in optical fiber communications, and more particularly to, a method for transmission and receipt of coherent light signals in which a wavelength of the signal lights is precisely controlled to be selected.Optical fiber communication systems have been developed quickly as communication systems having excellent characteristics of high speed modulation and long distance communications. Especially, a coherent optical communication system, in which optical frequency modulation or optical phase modulation is carried out in a transmitting apparatus and the optical signals are detected by optical heterodyne detection in a receiving apparatus, has been attractive among such optical fiber communication systems for its high receiving sensibility in high density frequency division multiplexing which contribute to a large capacity communication as well as a long distance communication. The high density frequency division multiplexing communication method is expected to realize extremely fine motion picture communications, in which it is possible to provide many subscribers with communication services by a relatively small number of stations and a small scale of transmission facilities.In the coherent optical communication between subscribers and the station by using the high density frequency division multiplexing method, a communication method with a network topology of double star type in which each subscriber is allocated with a predetermined wavelength of optical signals has been reported. In such communication method, it is possible to transmit different kinds of information to different subscribers simultaneously, although it is impossible in a network of tree type topology adopted in CATV now in use, however, a number of wavelength channels corresponding to a number of subscribers are required, so that usage efficiency of wavelengths is not high. In order to improve the usage efficiency, there is a communication method in which a vacant wavelength channel available for communication is selected to be used as a channel in case of each talking occasion without allocating a specific wavelength to each subscriber. Such a communication method is called a Demand Assign frequency division multiplexing method already open to public. This communication method has an advantage in that the number of wavelength channels required in the communication is less than the number of subscribers, so that the usage efficiency of wavelengths increases and station facilities are not required to be large in number and scale.According to the conventional method for transmission and receipt of coherent light signals, however, there is a disadvantage in that there is no study and report on means in a subscriber for setting a wavelength of a transmitting light source, and adjusting the wavelength to an absolute wavelength for a reference wavelength or a selected wavelength of the station in bilateral communications. In the Demand Assign wavelength division multiplexing communication method, it is required to select a wavelength for communication in each call, so that each subscriber is required to prepare a receiver and a transmitter of wavelength selecting type. A receiver of wavelength selecting type for unilateral communications has been described in detail in Japanese Patent Publication No. KOKAI 1-77325. In this receiver of wavelength selecting type, it is possible to select a desired wavelength channel by controlling a current supplied to a local oscillating light source to be one of memorized currents. However, as explained above, there is no disclosure about transmitter or receiver for bilateral communications.EP-A2-0 354 567 relates to a transmission/receipt device of a bidirectional transmission system for coherent light. A local laser oscillator and means for converting a wavelength of the local light source are provided so that a wavelength corresponding to a signal light transmitted from a subscriber to a station is different from a wavelength corresponding to the local light. In particular, however, the wavelength converting means are very difficult to be embodied. Thus, the decrease of a local light output, the enlargement of an apparatus and the increase of costs are resulted.EP-A2-0 298598 discloses an optical communication system with a stabilized group of frequencies. It discloses a wavelength internal control in a transmission system and a receiving wavelength control in a heterodyne system.Accordingly, it is an object of the invention to provide a method for transmission and receipt of coherent light signals in which it is possible in a subscriber to set a wavelength of a local oscillating light source to an absolute wavelength and a selected wavelength of a station.It is a further object of the invention to provide a method for transmission and receipt of coherent light signals in which an absolute wavelength for a local oscillating light source and a transmitting light source is stabilized in a bilateral communication system.It is a still further object of the invention to provide a method for transmission and receipt of coherent light signals in which the setting of a wavelength is easily carried out in a bilateral communication system.The objects are solved with the features of the claims. The invention will be explained in more detail in conjunction with appended drawings wherein: Fig. 1 is a block diagram of a transmitting and receiving apparatus used in a method for transmission and receipt of coherent light signals in a first preferred embodiment according to the invention;Fig. 2 is an explanatory view explaining wavelength allocation of lights for communication in the method for transmission and receipt of coherent light signals in the first preferred embodiment according to the invention;Fig. 3 is an explanatory view explaining signal format structures of a common signalling channel in the method for transmission and receipt of coherent light signals in the first preferred embodiment according to the invention;Fig. 4 is a block diagram of a transmitting and receiving circuit in a station in the method for transmission and receipt of coherent light signals in the first preferred embodiment according to the invention;Fig. 5 is a flow chart of transmitting operation from a subscriber in the method for transmission and receipt of coherent light signals in the first preferred embodiment according to the invention;Fig. 6 is a flow chart of receiving operation by a subscriber in the method for transmission and receipt of coherent light signals in the first preferred embodiment according to the invention;Fig. 7 is a block diagram of a transmitting and receiving device used in a method for transmission and receipt of coherent light signals in a second preferred embodiment according to the invention:Fig. 8A and 8B are explanatory views explaining wavelength allocation of lights for communication in the method for transmission and receipt of coherent light signals in the second preferred embodiment according to the invention;Fig. 9A is an explanatory view illustrating transmitting a light through an optical wavelength standard used in the transmitting and receiving apparatus in Fig. 7;Fig. 9B is a graph showing a relation between frequency and intensity of lights in the optical wavelength standard in Fig. 8A;Fig. 10 is a flow chart of transmitting operation from a subscriber in the method for transmission and receipt of coherent light signals in the second preferred embodiment according to the invention;Fig. 11 is a flow chart of receiving operation by a subscriber in the method for transmission and receipt of coherent light signals in the second preferred embodiment according to the invention;Fig. 12A is a block diagram of an optical wavelength standard in a transmitting and receiving circuit in a third preferred embodiment according to the invention; andFig. 12B is a graph showing a relation between the frequency and the output intensity in the optical wavelength standard in Fig. 12A.Fig. 1 shows a transmitting and receiving apparatus used in a method for transmission and receipt of coherent light signals in a first preferred embodiment according to the invention. The transmitting and receiving apparatus includes a coherent receiving circuit 1, a local optical oscillator 3, a wavelength control circuit 5, a frequency discriminator 6, a channel discriminator 7, and an external modulator 14 of lithium niobate. The coherent receiving circuit 1 includes a photodetector 8, an amplifier 9 and a demodulator 19.In operation, a receiving light 2 (second light signal) transmitted from a station is combined with an oscillating light 4b (local light signal) supplied by a local optical oscillator 3 to be supplied to the photodetector 8 where heterodyne detection is carried out to generate an intermediate signal. The intermediate signal is amplified by the amplifier 9, and then demodulated by the demodulator 19.The wavelength control circuit 5 controls the local optical oscillator 3 to generate an oscillating light 4 corresponding to a wavelength of a received channel which is discriminated by the channel discriminator 7. In more detail, the wavelength control circuit 5 controls the local optical oscillator 3 to oscillate with a predetermined wavelength by setting currents for temperature control and for oscillation control to be values determined in accordance with data of relations of temperatures and currents vs. oscillating wavelengths of the local optical oscillator 3 stored in the memory 10.In this oscillation control, the wavelength control circuit 5 sweeps wavelength of the oscillating light of the local optical oscillator 3 in a narrow range to pull the intermediate frequency signal into a predetermined range of frequencies in accordance with a frequency discriminating signal supplied from the frequency discriminator 6. At the same time, the channel discriminator 7 discriminates a channel from others by detecting a pilot signal having a specific frequency band of 10 MHz included in each channel signal light. If the channel received is not a desired one, then the wavelength control circuit 5 receives a signal from the channel discriminator 7 to detect difference of wavelengths between the tuned channel and the desired one to correct a current supplied to the local optical oscillator 3. Such a control is carried out by a microprocessor included in the wavelength control circuit 5.On the other hand, the transmitting signal 12 is supplied to the external modulator 14 to modulate a part of the oscillating light (first light signal 4a) supplied from the local optical oscillator 3 and intensity modulation is carried out in the external modulator 14, and the modulated signal light 20 is transmitted to the station through an optical fiber transmission line 20.Fig. 2 shows wavelength allocation of lights for communication. Wavelengths f 1 to f 10 are allocated to receiving lights (down line signals) for subscribers, while wavelengths f 12 to f 22 are allocated to transmitting lights (up line signals). Each wavelength pair f i and f i + 12 (i = 1,2, ···, 10) is used for one bilateral communication between two subscribers by control of the station. Among the wavelength pairs, the wavelength pair f 11 and f 12 is used for a common signaling channel by which line control signals are transmitted from a subscriber of a caller to the station and from the station to a subscriber of a callee to set up a bilateral communication between the subscribers of the caller and callee.Fig. 3 shows time allocation and signal format structure of common signals in the common signaling channel in case of one hundred subscribers. Time division multiplexing access (TDMA) is adopted in transmitting control signals, so that each subscriber is allocated with a specific period (100 µm in Fig. 3) having an interval of 10 ms to communicate with the station. Each period for one subscriber in the down line from the station is divided to three regions, first one for channel discrimination (8 bits), second one for control signal (32 bits) and third one for guard time (72 bits). As for the up line, a subscriber can use the guard time to avoid interferences with other subscribers. The period is divided to two regions, first one for channel discrimination (8 bits) and second one for control signal (32 bits). When a subscriber of a caller sends a call request signal to the station for requesting a call to a subscriber of a callee, the station selects one wavelength pair from the aforementioned pairs and sends the control signal for selecting a wavelength to the subscriber of the caller and informs the subscriber of the callee of the call request.Fig. 4 shows a transmitting and receiving apparatus in the station. The transmitting and receiving apparatus includes a transmitter row 40, a receiver row 41, a line control unit 42, a wavelength control system 43, a combining circuit 44, and a divider 45. Wavelengths f 1 to f 11 of transmitting lights supplied from the transmitter row 40 are stabilized to be absolute wavelengths by the wavelength control system 48. Such a stabilization to the absolute wavelengths is described on page 896 of Journal of Lightwave Technology, vol. 3, 1990, titled A Coherent Optical FDM CATV Distribution System by S. Yamazaki, et al. On the other hand, receiving lights supplied from subscribers are supplied through the divider 45 to receivers of the receiver row 41 each corresponding to a specific wavelength selected from up line wavelengths f 12 to f 22. CW (continuous wave) optical signals are supplied from the transmitter row 40 to receiving circuits of the receiver row 41 as local oscillating lights, so that intermediate signals are generated in the receiver row 41 to be supplied to the line control unit 42. The line control unit 42 controls signals of the transmitter and receiver rows 40 and 41 to carry out operation set out below.Fig. 5 is a flow chart of requesting a call from a subscriber in the transmitting and receiving apparatus shown in Fig. 1. At non-communication state, the receiving circuit 1 is kept waiting a call from other subscribers by receiving the common signaling channel f 11 from the station by tuning the local optical oscillator 3 to the frequency f 12. When the subscriber requests a call to one of the other subscribers, the oscillating light is modulated to include a subscriber number of a callee. The request signal is transmitted to the station by use of the common signaling channel of f 1 2. The station selects a channel having frequencies f 1 and f 1 + 1 2 from vacant channels, and the selected channel is transmitted to the subscriber of the caller. Simultaneously, the subscriber of the callee is requested to be connected to the station using wavelength (fj, f j+ 12) as shown in Fig. 6. At the subscriber (caller), the local optical oscillator 3 is controlled to oscillate with the frequency f 1+ 12 by the wavelength control circuit 5. As a result, a communication line is set up to use the selected channel between the subscribers of the caller and callee by control of the station. As understood from Fig. 2, the frequency f i is for the down line, and the frequency f i +1 2 is for the up line. Thus, data communication starts between the two subscribers, and when it finishes, the same operation restarts.Fig. 6 is a flow chart of receiving a call request from a subscriber in the transmitting and receiving device shown in Fig. 1. At non-communication state, the station and subscribers remain at the waiting state. When the station receives a call request from one of the subscribers by using the up line frequency f 12 of the common signaling channel, the station selects a channel having down and up line frequencies f i and f i+ 12 from vacant channels. The selected channel is transmitted to the subscriber of a callee by using the down line frequency f 11 of the common signaling channel. In the subscriber of the callee, the local optical oscillator 3 is controlled to oscillate with the frequency f 1+ 12 by the wavelength control circuit 5. In the same manner as explained in Fig. 5, the communication starts between the two subscribers of the caller and callee by control of the station.Fig. 7 shows a transmitting and receiving apparatus used in a method for transmission and receipt of coherent light signals in a second preferred embodiment according to the invention. The transmitting and receiving apparatus includes a coherent receiving circuit 1, a wavelength control circuit 5, a frequency discriminator 6, a channel discriminator 7, a memory 10, a transmitting light source 21, a detecting circuit 22, an optical wavelength standard 26, a photodetector 27, and a temperature stabilizing system 28. The coherent receiving circuit 1 includes a photodetector 8, an amplifier 9, a demodulator 19 and a local optical oscillator 3. The detecting circuit 22 includes a photodetector 23, an amplifier 24 and a frequency discriminator 25.In this second preferred embodiment, non-correlated wavelengths f i and f j are selected for down and up line signals as shown in Fig. 8A (i = 1, 2, ··· , 11, and j = 12, 13, ··· , 22). For this purpose, the local optical oscillator 3 oscillates to provide lights having wavelengths f 1 to f11, to f and the transmitting light source 21 provides lights having wavelengths f 11 to f 22 as shown in Fig. 8B. Fig. 9A shows operation of the optical wavelength standard 26 which includes a Fabry-Perot Interferometer 29. The free spectrum range of the Fabry-Perot interferometer 29 is set to meet the wavelengths of up line signals f 11 to f 22, as shown in Fig. 9B. At the waiting state, the temperature around the optical wavelength standard 26 is stabilized by the temperature stabilizing system 28 so that the transmission peaks are equal to wavelengths of the transmitting lights. At the communication state, the temperature stabilizing system 28 takes a hold state, however, the wavelengths of the transmission peaks remain stabilized with a few MHz changes for a few hours.In this second preferred embodiment, TDMA is adopted in transmitting control signals as like in the first preferred embodiment, and the signal format structure of the common signaling channels are the same as those shown in Fig. 3. In addition, the structure of the transmitting and receiving circuit of the station is the same as that in Fig. 4, except that local optical oscillators are additionally provided for the receiver row.Figs. 10 and 11 are flow charts of transmitting and receiving operations in the transmitting and receiving apparatus shown in Fig. 7, respectively. The operations are the same as those in Figs. 5 and 6 respectively, except that some steps are added for setting wavelength of the channel f j used for a transmitting light. In the step of fine tuning of the oscillating light, the transmission outputs of the optical wavelength standard 26 change periodically while sweeping of wavelengths, so that it can be judged whether the channel is the desired one by counting the number of the transmission peaks. On the other hand, the station also judges whether the channel is the desired one. When the desired wavelength is selected, the wavelength of transmitting lights is stabilized by the wavelength control circuit 5.Operation of Fig. 10 is summarized as set out below. When a call request is made in one of subscribers, the call request is transmitted from the transmitting light source 4 emitting the light of the wavelength f 12 to the station. Then, a channel having the wavelength f i and f j is selected from vacant channels in the station. This selected channel is transmitted from the station back to the subscriber by use of the light of the wavelength f 11, so that the local optical oscillator 3 is controlled to be pulled into the f i channel by the wavelength control circuit 5. At the same time, the transmitting light source 21 is controlled to oscillate with the wavelength f j by the wavelength control circuit 5. In this control, a frequency signal is supplied from the detecting circuit 22 to the wavelength control circuit 5, and a transmission peak signal is supplied to be counted in the wavelength control circuit 5 from the photodetector 27 thereto. Thus, the setting of the wavelength f j is completed in the transmitting light source 21.Fig. 11 shows operation in which one of subscribers receives a call request from the other subscriber. This operation is self-explanatory with reference to the flow-chart, and also to the operation of Fig. 10.Fig. 12A shows an optical wavelength standard in a transmitting and receiving circuit in a third preferred embodiment according to the invention. The optical wavelength standard includes a wavelength plate 30, a polarizing divider 31, photodetectors 32 and 36, an adder 33, a subtractor 34 and a divider 35.In the optical wavelength standard, a light 37 is supplied to the wavelength plate 30 in the direction of 45° to the plate plain, and then is transmitted therethrough to the polarizing divider 31 where the light 37 is divided to two lights to be supplied to the photodetectors 32 and 36, respectively. Outputs of the photodetectors 32 and 36 are processed arithmetically by the adder 33, the subtractor 34 and the divider 35, and an output 38 having periodic characteristic can be obtained, as shown in Fig. 12B. Stabilization of the wavelength can be realized by targeting the wavelengths to the cross points of zero level with a relatively simple control system as compared with a Fabry-Ferot interferometer having transmission peaks. Such an optical wavelength standard is described in Japanese Patent Application No. 1-226863.In the preferred embodiments thus explained above, wavelengths of both down and up line signals are controlled, however, it is possible to adopt a system in which wavelengths of only down line signals are controlled. At the waiting state, the wavelength of the transmitting light is synchronized with the common signaling channel f 1 1 in the second preferred embodiment, however, it is possible to set the beat frequency of the detecting circuit 22 so that the wavelength thereof is synchronized with the common signaling channel f 1 2. The transmitting light source may remain at the waiting state, or may be built up at each time when the light transmission begins to search the wavelength of the common signaling channel. Control of periods of the wavelengths may be carried out by a system having a periodical transmission or reflective characteristic such as a Mach-Zender interferometer. It is possible to separate a swept signal light from the transmitting line by using an optical switch to avoid interference to transmitting lights from other subscribers.	A method for transmission and receipt of coherent light signals, comprising the steps of: a) providing a station and subscribers connected to each other to transmit and receive coherent light signals using wavelength division multiplexing by optical fibers;b) providing an oscillation light (4) having a first predetermined wavelength in one of said subscribers;c) transmitting a first light signal (4a) from said one of said subscribers to said station;d) receiving a second light signal (2) having a second predetermined wavelength transmitted from said station in said one of said subscribers;e) combining a local light signal (4b) and said second light signal (2) to provide an intermediate light signal which is converted to an intermediate electric signal, said intermediate electric signal being demodulated to provide data transmitted from said station to said one of said subscribers; and characterized by the step of: f) dividing said oscillation light (4) having said first predetermined wavelength into said first light signal (4a) and said local light signal (4b), both of said first light signal and said local light signal having said first predetermined wavelength.A method for transmission and receipt of coherent light signals, according to claim 1, wherein: said first and second light signals are of a common signaling channel.A method for transmission and receipt of coherent light signals, according to claim 1, wherein: said first and second light signals are of a common signaling channel to set up a line connection between said one of said subscribers and a designated subscriber of said subscribers, and said first and second light signals are controlled to have first and second predetermined wavelengths of a communication channel selected from vacant communication channels, respectively.A method for transmission and receipt of coherent light signals, according to claim 2, wherein: a wavelength of said common signaling channel is a reference wavelength to control said first and second predetermined wavelengths. A method for transmission and receipt of coherent light signals, comprising the steps of: a) providing a station and subscribers connected to each other to transmit and receive coherent light signals of wavelength division multiplexing by optical fibers;b) providing an oscillation light signal (local light) having a wavelength of a channel (f1...f11) in one of said subscribers;c) transmitting a light signal (upline light signal) having a wavelength of a channel (f12...f22) from said one of said subscribers to said station;d) receiving a light signal (downline light signal) having a predetermined wavelength transmitted from said station in said one of said subscribers; characterized in that e) said oscillation light signal is divided into two signals of said wavelength one being used for the detection in said subscriber, the other being used for the transmission from the subscriber to said station;f) a beat frequency between oscillation light (local light) and a common signaling channel (f11) is detected so that a local light will be near or at said common signaling channel wavelength (f11) at non-communicating state;g) simultaneously, a beat frequency of a local light and a upline light signal (transmitting light signal) is detected to be controlled at non-communication state, so that a wavelength of the upline light signal is coincided to a upline signal, wavelength of the common signaling channel (f12); andh) thereafter, wavelengths of the upline light signal and the local light are changed (f22, f3) to provide the communication station in accordance with a communication request via the common signaling channel (f11,f12).A method for transmission and receipt of coherent light signals, according to claim 5, wherein: a wavelength of a common signaling channel is a reference wavelength to control said wavelengths of said oscillation light and said transmitting light signal.A method for transmission and receipt of coherent light signals, according to claim 5, wherein: said beat frequency is controlled to be a predetermined value between said oscillation light signal and said first light signal, whereby a line connection is set up between said one of said subscribers and a designated subscriber of said subscribers.A method for transmission and receipt of coherent light signals, according to any of claims 5 to 7, wherein: at least one of said oscillation light signal and said transmitting light signal is used for correction of a reference wavelength at non-communication state, and a wavelength of said first light signal is set based on said reference wavelength at communication state. A method for transmission and receipt of coherent light signals, according to any of claims 5 to 8, further comprising the step of: supplying said transmitting light signal to a transmission member having a predetermined wavelength property to provide transmission peaks equal to a wavelength division of communication channels, said transmitting light signal being swept in wavelength to be set to one of said communication channels by counting said transmission peaks. An apparatus for carrying out the method of any of claims 1 to 4, comprising: a) a coherent receiving circuit (1) with a photodetector (8), an amplifier (9) and a demodulator (19), wherein the photodetector (8) is connected to the amplifier (9) and the amplifier is connected to the demodulator (19),b) a frequency discriminator (6) and a channel discriminator (7) connected in parallel between the amplifier (9) and a wavelength control circuit (5),c) a memory (10) connected to the wavelength control circuit (5), andd) a local optical oscillator (3) controlled by the wavelength control circuit (5) and connected both to an external modulator (14) and the photodetector (8).An apparatus for carrying out the method of any of claims 5 to 9, comprising: a) a coherent receiving circuit (1) comprising a photodetector (8), a local optical oscillator (3), an amplifier (9), and a demodulator (19), wherein the local optical oscillator (3) is connected to the photodetector (8), the photodetector (8) is connected to the amplifier (9), and the amplifier (9) is connected to the demodulator (19),b) a frequency discriminator (6) and a channel discriminator (7) connected in parallel between the amplifier (9) and a wavelength control circuit (5),c) a memory (10) connected to the wavelength control circuit (5),d) a transmitting light source (21) connected to the local optical oscillator (3) and the wavelength control circuit (5),e) a detecting circuit (22) with a photodetector (23), an amplifier (24) and a frequency discriminator (25), wherein the photodetector (23) is connected to the local optical oscillator (3) and the amplifier (24), the amplifier (24) is connected to the frequency discriminator (25), and the frequency discriminator (25) is connected to the wavelength control circuit (5),f) an optical wavelength standard (26) connected to a photodetector (27) being connected to the wavelength control circuit (5), andg) a temperature stabilizing system (28) connected between the wavelength control circuit (5) and the optical wavelength standard (26).	NIPPON ELECTRIC CO; NEC CORPORATION	SHIKADA MINORU; SHIKADA, MINORU; Shikada, Minoru, c/o NEC Corporation
EP-0489447-B1	489,447	EP	B1	EN	19,951,220	1,992	20,100,220	new	E21B47	E21B49, E21B21	E21B21, E21B47, E21B49	E21B 49/00D, E21B 47/06, E21B 21/08	A method for the esimation of pore pressure within a subterranean formation	A method for the estimation of pore pressure within a subterranean formation containing fluid during the drilling of a bore hole 6. The bore hole is drilled using a drill string 4 consisting of a drill bit 5 fitted to its lower end, and using drilling mud pumped from the surface through the drill string and finally evacuated. The method is characterised by, whilst the drill bit is level with the formation and whilst the drill string is being raised to the surface for a distance at least equalling the drill pipe length, a) the monitoring of the change in value of an initial parameter such as mud level in a mud tank to detect the influx of the fluid from the formation into the bore hole; b) the monitoring of the change in value of a second parameter such as the apparent drill string weight whereby the second parameter characterises the force applied at the surface to retrieve the drill string; c) the correlation of the values of the first and second parameters in order to detect an increase in one of the parameters, which would correspond to an increase of the other parameter, and then the determination of the increase in value of the second parameter; and d) the estimation of the pore pressure of the formation from the increase in value of the second parameter as determined in step c).	The present invention relates to a method for the estimation of interstitial pressure within a subterranean formation containing fluid. The method is applied during the drilling of a bore hole through the said formation. The bore hole is drilled using a drill string comprising a number of drill pipes connected end to end with a drill bit fitted to its lower end, drilling mud being pumped through the said drill string and drill bits back to the surface. The drill string is suspended from the surface using suspension gear such as a hook. Drill pipes are added or removed depending on whether the drill bit is being raised or lowered in the bore hole. To either add or remove pipes, the drill string is periodically wedged in position to allow it to be unhooked from the suspension gear. When the drill bit needs to be retrieved during drilling (e.g. for replacement because it is worn) the drill string must be extracted and disassembled, element by element (with each element normally composed of a string of three pipes). Then, on recommencing drilling, the drill string is reassembled element by element, lowering the drill bit step by step into the bore hole. Some subterranean formations are porous, containing fluid such as water, gas, or crude oil within the pores. The fluid within the rock is at a certain pressure termed the pore pressure. When the drill bit of the drill string penetrates such a formation, the fluid tends to flow from the formation into the bore hole for as long as the formation is sufficiently permeable to allow such flow. If the pore pressure is high, the fluid contained in the formation may violently well from the bore hole thus creating a blow-out, which can be extremely dangerous for both the equipment and the drillers if the blow-out is not controlled in time. Drilling fluid, or drilling mud, is therefore used which fills the bore hole and applies a hydrostatic pressure to the bore hole at the level of the formation. The level of hydrostatic pressure depends on the drilling mud density and the depth at which the formation is situated. The drilling mud density is regulated at the surface by modifying its concentration using a weighting agent such as barite so that the hydrostatic pressure is always maintained higher than the pore pressure of the fluid within the formation. The fluid is thus maintained within the formation. However, the formation must not be damaged and the fluid held within must not be polluted. Thus the drilling mud density must not be too high. In addition, a filtrate reducing agent such as bentonite is added to the drilling mud, forming a relatively impermeable layer, called a mud cake, along the bore hole wall. The cake mainly forms across the porous formations and prevents the drilling mud from penetrating the formations. The mud cake also strengthens the bore hole walls. Thus, the importance of knowing, or at least having a good estimate of, the pore pressures within the formations being drilled or having been drilled is evident. When raising the drill string within the bore hole towards the surface the drilling mud may be subject to a piston effect if the rate of withdrawal is excessive. This effect will lower the drilling mud's hydrostatic pressure within the part of the bore hole below the drill bit and, if this hydrostatic pressure becomes lower than the pore pressure of the fluid contained in a formation, this fluid may enter the bore hole. It is because of this that a bore hole erupts most often when withdrawal of the drill string commences. Conversely, during the drill string's descent within the bore hole, an increase in the hydrostatic pressure is produced. If the descent is too quick, the resulting increase in pressure may cause the formation to fracture. Consequently the drillers control the trip velocities (speeds of descent and ascent) of the drill string so as to prevent any increase or decrease in the hydrostatic pressure. Theoretical models have been developed to determine the optimal speed of descent or ascent of the drill string (considering that time is lost if the rate is too slow) and therefore to determine the change in resultant pressure. The models use different parameters such as the geometry of the bored hole and the drill bit, together with the drilling mud's properties and especially its viscosity. To exemplify this point, one such model is described in article number 11412 of the IADC/SPE, entitled Surge and Swab modelling for dynamic pressures and safe trip velocities (1983) by Manohar Lal. These models enable the calculation of the changes in pressure resulting from drill string trips, based on parameters which undergo little or no change during boring. They do not allow the estimation of the pore pressure of a formation from variables measured during boring operations. Systems have also been invented to control drill string trip velocities. Such systems are described by, for example, patent numbers US-A 3,942,594 or US-A 3,866,468. Because of its importance, much work has been dedicated to detecting the influx of formation fluid into the bore hole. Without doubt the most widely used method concerns the measurement of the level of drilling mud in the tank in which it is stored after leaving the bore hole, when the drill string is being raised, and before being reinjected into the bore hole. The volume occupied by the drill string materials withdrawn from the bore hole is calculated using reference tables, and added to the volume of drilling mud in the mud tank. The value is compared to previous values and any influx of fluid from the underground formation which may have occurred is thus determined. This operation is carried out regularly after lifting out a drill string stand (usually consisting of 5 to 10 elements, with each element measuring approximately 30 metres). The level of drilling mud in the mud tank may be correlated with another influx indicator such as the flow rate of mud at the bore hole outlet. These techniques may be illustrated using, for example, Patent Nos US-A 3,646,808 and US-A 3,729,986, and the published Patent Application No GB-A 2,032,981. However, none of the methods quoted allow an estimation of the pore pressure of the fluid contained within a subterranean formation and using the measurements made during boring which is an object of the present invention. This invention proposes a method of achieving this. Thus, according to the present invention there is provided a method for estimating, during a drilling operation, the approximate range within which the pore pressure in an underground formation is to be expected, using a drill string comprising a plurality of drill pipes connected together with a drill bit at the lower end thereof, there being present within the drill pipe and hole a drilling fluid the density of which is such that the resulting fluid hydrostatic pressure is slightly greater than the pore pressure, to prevent formation fluids entering the hole, in which method any changes in the value of a first parameter, related to the flow of drilling fluid from the hole, are monitored to detect an influx of fluid from the formation, and any changes in the value of a second parameter, comprising the apparent weight (P) of the string on a hook (q) when suspended by hoisting gear, are monitored to characterise a force applied at the surface to support the string, which method is characterised in that the hook load is observed while the bit is level with the formation, and while the string and bit is being raised, and the first and second parameters are correlated and the change in the value of the second parameter is determined, from which there are drawn conclusions as to the pore pressure in the formation adjacent the bit, and in thatif on raising the string and the bit the piston effect of the bit in the hole causes the pressure in the hole to be lowered from above to below the pore pressure, there will result an increase in hook load, and there will also be a fluid influx into the hole from the formation which will be registered by monitoring the first parameter, then the pore pressure will be in the range delimited by the hydrostatic pressure in the hole and a value resulting from applying to that hydrostatic pressure the reduction caused by the bit, the hydrostatic pressure being calculable from the fluid density and the depth of the formation, and the reduction (dp) of the hydrostatic pressure being derivable by dividing the change in apparent weight (dP) of the string and bit by the maximum surface area (S) of the bit perpendicular to the bit's longitudinal axis. It will be understood that the mud flow parameter provides an indication of when there occurs an influx of formation fluid, at which point there may be ascertained the associated hook load change (because of the piston effect of the drill string), and from this, and a knowledge of the effective cross-sectional area of the piston and the hydrostatic pressure obtaining at the depth indicated by the string length, there may be determined an approximate value - an estimation or indication - of the pore pressure at that point. Conveniently, the first parameter is either the outlet flow rate of the drilling mud or the mud volume within the mud tank on the surface. The change in pressure dp (due to a pistoning effect caused by the drill string being raised) is also conveniently determined, in the bore hole, at the drill bit depth by measuring the increase in apparent weight dP of the drill string when an influx of fluid has been detected at the surface, and using the maximum (sectional) surface area S of a cross-section of the drill bit, according to the formula dp=dP/S . The formation's estimated pore pressure thus lies between the hydrostatic pressure of the drilling mud at the drill bit's depth and the same hydrostatic pressure reduced by the said change in pressure, dp. This range of pressures is sufficient for an acceptable estimate of the pore pressure. The rate of advance of the drill bit is conveniently recorded so as to detect porous formations and then correlated with two other parameters - the volume of drilling mud in the mud tank and the apparent weight of the drill string. Also, it is useful to record the weight values of the drill bit as a function of depth at least when passing down through the porous formations and when the drill bit is not touching the bottom of the bore hole. The values recorded are then compared with the values measured during the retrieval of the drill string to determine any change in weight. Other characteristics and advantages of the invention will be given more clearly in the description which follows of one, non-limiting, example of the method, with reference to the accompanying drawing in which: Figure 1 is a schematic representation of a vertical section of a drilling rig and associated bore hole; Figure 2 shows the drill bit passing through a subterranean porous formation; Figure 3 shows one example of a recording of the apparent weight (in Kilonewtons) of the drill string suspended by a hoist hook, with time, and the volume of drilling mud (in cubic metres) in the mud tank; and Figure 4 shows the same data records, apparent weight at the hoist hook and the volume of drilling mud in the mud tank, this time corrected for the drill bit depth. The derrick shown in Figure 1 comprises of a tower 1 rising above the ground 2 and equipped with a hoist 3 from which the drill string 4 is suspended. The drill string 4 is formed from pipes screwed together end to end and having at its lower end a drill bit 5 to drill the bore hole 6. The hoist 3 consists of a crown block 7 with the axle fixed in position at the top of the tower 1, a lower, vertically free-moving travelling block 8 attached to which is a hook 9, and a cable 10 joining the two blocks 7 and 8 and forming, from the crown block 7 both a fixed cable line 10a anchored to a fixed/securing point 11, and a live mobile line 10b which winds around the cable drum of a winch 12. When drilling is not taking place, as shown, the drill string 4 may be suspended from the hook 9 using a rotary swivel 13 connected to a mud pump 15 via a flexible hose 14. The pump 15 is used to inject drilling mud into the bore hole 6, via the hollow drill string 4, from the mud tank 16. The mud tank 16 may also be used to receive excess mud from the bore hole 6. By operating the hoist 3 using the winch 12, the drill string 4 may be lifted, with the pipes being successively withdrawn from the bore hole 6 and unscrewed so as to extract the drill bit 5, or to lower the drill string 4, with the successive screwing together of the tubes making up the drill string 4 and to lower the drill bit 5 to the bottom of the bore hole. These trip operations require the drill string 4 to be unhooked from the hoist 3; the drill string 4 is held by blocking it using wedges 17 inserted in a conical recess 18 within a bed 19 mounted on a platform 20, and through which the pipes pass. When drilling, the drill string 4 is rotated by a square rod or kelly 21 fitted to its upper end. In-between operations, this rod is placed in a sleeve 22 sunk into the ground Changes in height h of the travelling block 8 during the lifting operations of the drill string 4 are measured using a sensor 23. In this example it consists of a pivoting angle transmitter coupled to the most rapid spinning pulley within the crown block 7 (i.e. the pulley around which the live line 10b is wound). This sensor constantly monitors the rate and direction of rotation of this pulley, from which the value and sense of linear displacement of the cable connecting the two blocks 7 and 8 can be easily determined, thus giving h. An alternative type of sensor, using laser optics and based on radar principles, may also be used to determine h. Besides height h, the load applied to the hook 9 of the travelling block 8 is measured; this corresponds to the apparent weight P of the drill string 4, which varies with the number of pipes forming it, the friction experienced by the drill string along the length of the bore hole wall, and the density of the drilling mud. This measurement is obtained using a newton-type force meter 24 inserted in-line on the fixed cable 10a of the cable 10 and which measures its tension. By multiplying the value obtained from this sensor by the number of cables connecting block 7 to block 8, the load at the hook of block 8 is obtained. Sensors 23 and 24 are linked by lines 25 and 26 to a computer 27 which processes the measurement signals and sends them to a recorder 28. In addition, a sensor 29, linked to the computer 27 via a line 30, measures the level of the drilling mud in the mud tank 16. Sensor 29 consists generally of a float whose displacement is measured, and is both commercially available and presently used on drilling platforms. A sensor 31 detects the presence or absence of the kelly 21 in the sleeve 22. This sensor is connected to the computer 27 via line 32. The measurement instruments described above enable the data conversion of the parameters measured with respect to time and the depth of the drill bit 5 in the bore hole 6. One such data conversion is described in patent number US 4,852,665. Most of the drilling platforms also consist of a means of measuring the flow rate of injected drilling mud into the bore hole (usually associated with the pumping means) and the flow rate of the drilling mud leaving the bore hole and returning to the mud tank 16. Figure 2 is an enlargement of the drill bit 5 fitted to the drill string 4 and being raised in the bore hole 6. The drill bit 5 is seen traversing a porous formation 34, such as sand, containing fluid (a liquid or a gas) under a given pressure called the pore pressure. The formation 34 is surrounded by an impermeable formation 36 above and an impermeable formation 38 below. The drilling mud 16 in contact with the porous formation 34 forms a relatively impermeable mud cake 40 producing a slight protuberance within the bore hole, thus reducing the bore hole diameter. When the drill bit 5 passes through such a porous formation, the reduction in bore hole diameter at this point causes a pistoning effect and therefore a reduction dp in hydrostatic pressure p of the drilling mud just below the drill bit 5. This leads to an influx of formation fluid into the bore hole, as indicated by arrows 42. It may be noted that this fluid influx may also occur even when the drill string is withdrawn very slowly. Also, the inventors have noted that this decrease in pressure dp corresponds with an increase dP of the apparent weight of the drill string (the suspended weight at the hook measured using sensor 24 (fig. 1)). Using the principle described in this invention, the change in hydrostatic pressure dp is determined by dividing the change in apparent weight dP by the maximum surface area (schematically represented by S in figure 2) of the drill bit cross-section perpendicular to the drill bit's longitudinal axis. dp = dP/S When the drill bit does not have a uniform section, the largest cross-sectional area is used. An increase in apparent weight may not necessarily correspond to the piston phenomenon illustrated in figure 2, thus, the influx of fluid in the bore hole must be detected, which is accompanied by an increase in mud volume within the mud tank and an increase in mud flow rate leaving the bore hole. An influx of fluid may then be detected by the level detector 29 (fig 1) and/or by the flowmeter (not shown) positioned on the drilling mud outlet conduit outside the bore hole. By correlating the values measured for the first parameter and indicating an influx of fluid with the values measured for a second parameter characteristic of the force applied at the surface to lift the drill string, the change in hydrostatic pressure dp at the depth of the drill bit being considered is obtained. The formation's pore pressure producing the fluid may then be estimated as its value lies between the drilling mud hydrostatic pressure and the hydrostatic pressure reduced by the change in pressure dp. Knowing the depth x of the drill bit and the density ρ of the drilling mud, the hydrostatic pressure is given by: p = x g ρ where g is the acceleration due to gravity. If the bore hole is contorted, the depth x must of course be corrected to account for the deviation with respect to the vertical. For a reasonably thick porous formation 34, the pore pressure may be determined along several drill string stands withdrawn from the bore hole. This may then provide an overall measurement for the stands considered or provide a mean value for the individual measurements obtained for each stand withdrawn. The pore pressure, or more simply the change in apparent weight, may also be determined by averaging the measurements taken during several withdrawals of the drill string. To measure the changes in apparent weight at the hoist's hook, the reduction or the slope of the successive weight measurements on withdrawing the drill string may be firstly determined. This weight will obviously decrease regularly (stepwise) as the drill string stands of equal lengths are pulled up to the surface. The increase in apparent weight is then measured with respect to this regular decrease in weight. Another, perhaps complementary, method may be used during drilling; for example at each stage when the bore hole is drilled by the length of a drill string rod stand, the drill string may be slightly lifted in order that the drill bit no longer touches the bottom of the bore hole, and the weight at the hook may be measured and recorded when the drill bit is at the level of the formation. The said weight is compared with that previously recorded during drilling when the drill bit was at the same depth in the bore hole. The measurements of the changes in weight and drilling mud volume within the mud tank may be made and recorded over time, but it would be better if the values were converted with respect to the drill bit depth inside the bore hole. This conversion may be carried out using the method described in patent number US 4,852,665. Drillers know that the rate of advance of the drill bit during drilling is higher through porous formations than through non-porous formations. Thus it is of interest to map the porous formations during drilling by recording the speed of advancement of the drill bit and by pinpointing the zones where this advancement rate is higher. The method for measuring the rate of advance described in patent number US 4,843,875 may be used in this case. This porous formation depth information may then be correlated with the measurements of the changes in apparent weight and drilling mud volume. Figures 3 and 4 represent the volume of drilling mud in the surface mud tank (figs. 3(a) and 4(a)) measured in cubic metres, and the apparent weight P (in kilonewtons) of the drill string suspended from the hoist hook (figs. 3(b) and 4(b)). The measurements in both figures 3 and 4 are expressed, respectively, with time (in seconds) and depth (in metres) of the drill bit in the bore hole. In figures 3(a) and 4(a) a regular decrease in the volume of drilling mud in the mud tank at the surface, from approximately 9 m³ to 8 m³ may be noted between 24,000 seconds and 26,200 seconds (fig. 3(a)), corresponding to a drill bit depth of between 950m and 670m (fig 4(a)). This decrease simply corresponds to the regular shortening of the drill string length in the bore hole due to the pipes being removed. This decrease in material is balanced by an equivalent volume of drilling mud, which may be translated by a regular lowering of the level of drilling mud in the mud tank. To implement this invention, it is not necessary to calculate the volume of the drill string withdrawn from the bore hole, but rather follow the decline of the curve in figure 3(a) or 4(a) to detect an increase with respect to the usual decrease; this increase indicates the influx of formation fluid into the bore hole. In figures 3(a) and 4(a) two successive influxes A and B can be observed. These influxes are correlated with recordings of force or weight P at the hook (figs. 3(b) and 4(b)). An increase in weight dP is clearly highlighted, indicated by C and D, with respect to the regular decrease in weight as shown by the straight line E. This regular decrease in weight, easily seen on the recording with respect to depth (fig. 4), is due to the decrease in length of the drill string suspended by the hook, as the pipes are removed at the surface. In figure 3(b), the events C and D can be seen as consisting of two peaks each. This is in fact because to the increase in weight was not expected and the rate of lifting the drill string was not smooth, but rather very strongly braked at a given moment (for t = 26,450 and t = 27,100). To determine the increase in weight dP, the average value of the maximum weight P may, for example, be taken as there is a lot of noise associated with the recording as seen in figures 3 and 4. In these figures, the increase in weight dP equals approximately 240kN. The change in hydrostatic pressure dp at the drill bit depth being considered is easily determined by dividing the value dP by the drill bit's cross-sectional area S. Knowing dp, the formation's pore pressure is estimated from the drilling mud's hydrostatic pressure at the drill bit's depth.	A method for estimating, during a drilling operation, the approximate range within which the pore pressure in an underground formation (34) is to be expected, using a drill string (4) comprising a plurality of drill pipes connected together with a drill bit (5) at the lower end thereof, there being present within the drill pipe (4) and hole (6) a drilling fluid the density of which is such that the resulting fluid hydrostatic pressure is slightly greater than the pore pressure, to prevent formation fluids entering the hole (6), in which method any changes in the value of a first parameter, related to the flow of drilling fluid from the hole (6), are monitored (29) to detect an influx of fluid (42) from the formation (34), and any changes in the value of a second parameter, comprising the apparent weight (P) of the string (4) on a hook (q) when suspended by hoisting gear (7,8,9), are monitored (23) to characterise a force applied at the surface to support the string (4), which method is characterised in thatthe hook load is observed while the bit (5) is level with the formation (34), and while the string (4) and bit (5) is being raised, and the first and second parameters are correlated and the change in the value of the second parameter is determined, from which there are drawn conclusions as to the pore pressure in the formation adjacent the bit (5), and in thatif on raising the string (4) and the bit (5) the piston effect of the bit (5) in the hole (6) causes the pressure in the hole (6) to be lowered from above to below the pore pressure, there will result an increase in hook load, and there will also be a fluid influx into the hole (6) from the formation (34) which will be registered by monitoring the first parameter, then the pore pressure will be in the range delimited by the hydrostatic pressure in the hole (6) and a value resulting from applying to that hydrostatic pressure the reduction caused by the bit (5), the hydrostatic pressure being calculable from the fluid density and the depth of the formation (34), and the reduction (dp) of the hydrostatic pressure being derivable by dividing the change in apparent weight (dP) of the string (4) and bit (5) by the maximum surface area (S) of the bit (5) perpendicular to the bit's longitudinal axis. A method as claimed in claim 1, wherein changes in the first and second parameters are monitored during the removal or addition of more than one drill pipe. A method as claimed either of claims 1 and 2, wherein the pore pressure is estimated from more than one retrieval of the drill string (4). A method as claimed any of the preceding claims, wherein the first parameter is the flow rate of drilling fluid leaving the bore hole (6). A method as claimed any of claims 1 to 3, wherein the drilling fluid is mud stored at the surface in a mud tank (16), the first parameter being a measure of the level of mud in the tank. A method as claimed in claim 5, wherein the first parameter is corrected to account for the volume of drill string withdrawn from the bore hole (6). A method as claimed in any of the preceding claims, wherein the apparent weight (P) is measured during drilling when the drill bit (5) is not in contact with the bottom of the bore hole (6) and is compared with the apparent weight (P) at the same depth when retrieving the drill string (4) A method as claimed in any of the preceding claims, wherein the change in the second parameter is determined for the piston effect when retrieving the drill string (4) from a given depth. A method as claimed in claim 8, wherein the hydrostatic pressure of the mud is calculated at said given depth. A method as claimed in any of the preceding claims, wherein advancement of the drill bit (5) during drilling is measured and correlated with values of the first and second parameters.	SCHLUMBERGER SERVICES PETROL; SERVICES PETROLIERS SCHLUMBERGER	BURGESS TREVOR MICHAEL; KERBART YVES; MCCANN DOMINIC PATRICK JOSEPH; BURGESS, TREVOR MICHAEL; KERBART, YVES; MCCANN, DOMINIC PATRICK JOSEPH
EP-0489450-B1	489,450	EP	B1	EN	19,960,710	1,992	20,100,220	new	E06B9	E06B9	E05F1, E06B9	E06B 9/40, E05F 1/08, E06B 9/58, E06B 9/78, E06B 9/54, E06B 9/68, E06B 9/90	A closure for a door or window opening	A closure, such as an insect screen, for a door or window opening having guide tracks (12,14) at opposite sides, a retractor assembly (16) mounted at a third side of the frame, a flexible screen (10) wound at one of its ends to the retractor, a header bar (18) secured to the other end of the flexible screen, said header bar being guided by said guide tracks for movement perpendicular thereto. A pair of wheels (62), one mounted at each end of the header bar (18) are operatively associated with one of the guide tracks (22) and a brake and preferably also a drive mechanism are provided on the header bar (16), the brake being effective simultaneous to stop rotation of both of the wheels (62) and thereby to arrest movement of the header bar at any location along the length of the guide tracks, and the drive means being arranged to urge the header bar to the closed position of the screen (10).	The present invention relates to a closure for a door or window opening. The invention is concerned principally, although not exclusively, with an insect screen form of such closure. Conventionally, insect screens are mounted either to be lifted out bodily from the door or window, or, particularly in the case of doors, are mounted as hinged doors. As far as window insect screens are concerned, these are commonly made in a manner rather similar to roller blinds which can be retracted, e.g. by a spring loaded roller, or by a bead chain driven roller. US-A-1887646 shows such a insect proof screen which is primarily for a window or may be used, according to Figure 11 and 12 of that patent, as a door screen. WO-88-06671 discloses a flexible screen which is collapsed and is not wound up by retraction. It includes a motorized header element for extending and retracting an accordion type shade along a pair of rectilinear and curvilinear mounted side tracks and for effecting an environmental seal in the plane formed between the shade and the surface which it covers. The invention is adapted to both and automatic and manual operation and contains with its automatic/motorized drive system means for recharging its battery power source. However, it is very much of an accordion pleat arrangement which is a very different type from that of US-A-1887646. It is an object of the present invention to provide improved and alternative structures to that disclosed in these documents. It is now proposed, according to the invention, to provide a closure for a door or window opening, said closure comprising a rectangular frame having a guide track on each of two opposite sides, a spring loaded retractor roller mounted at a third side of the frame, a flexible screen position with one of its ends on said third side of the screen and being retractable by said retractor roller towards said third side, a header bar secured to the other end of the flexible screen, said header bar being guided by said guide tracks for movement perpendicular thereto, a pair of wheels one mounted at each end of the header bar, each wheel being operatively associated with one of said guide tracks and with means for synchronizing the movement of opposite ends of the header bar, and drive means adapted to rotate the wheels of said pair in a direction to move said header bar towards a closed position of said closure. With such a structure, the drive means are adapted to rotate the wheels in a direction to move the header bar towards the closed position of the closure. The drive means may comprise at least one torsion spring mounted in said header bar, said torsion spring being operatively connected to said wheels. While the wheels could be separately driven, they are desirably connected to a common drive shaft and said at least one torsion spring acts on the common drive shaft. Brake means may be provided to lock the screen at any desired location along the length of the guide tracks. This can be advantageous particularly when it is used in combination with a sliding door arrangement which can be opened and adjusted for passage therethrough. While the closure is primarily intended to act as an insect screen, such that the material of the flexible screen is of a mesh type, it is contemplated that the flexible screen could be imperforate and opaque to provide a shutter like closure. The wheels may take various forms. For example, it could be simple wheels, e.g. with a rubber tyre on their periphery which runs on the guide track. An alternative possibility is having a wheel around which is wrapped a cord as disclosed, for example, in DE-A-3526745. However, according to a preferred construction, the wheels are each in the form of a toothed pinion and the guide tracks each have associated therewith a toothed rack, each rack being engaged by a separate one of said pinions. In order easily to mount the closure in a particular installation, the pinions are advantageously mounted in an adjustable bearings, permitting the teeth of the pinion to be disengaged from the teeth of the rack. While it is contemplated that the wheels could be braked separately, advantageously they are connected to a common shaft and the brake means acts on the common shaft. With such a structure, the brake means may comprise a laterally displaceable brake shoe, engageable with said common shaft, or a sleeve attached thereto, a wedge shaped actuating member carried by said header bar adjacent said brake shoe and a handle manually displaceable axially of said header bar, connected to said actuating member to cause the actuating member to move therewith and thereby cause the brake shoe to be urged against the common shaft or sleeve. The flexible screen is attached at said one of its ends to a retractor roller and said retractor roller preferably includes at least one further torsion spring effective to cause the retractor roller to rotate to wind the screen in an opening direction into said retractor roller and said at least one torsion spring which is mounted on said header bar has a greater strength than that of said at least one further torsion spring on the retractor roller. Where the wheels are each in the form of a toothed pinion and the guide tracks each have associated therewith a toothed rack, each rack being engaged by a separate one of said pinions. Preferably as indicated above, the pinions are mounted on adjustable bearings, permitting the teeth of the pinions to disengage from the teeth of the rack, and further fixed teeth are provided and positioned to be engaged by the teeth of the pinions when they are disengaged from the teeth of the rack, to prevent rotation of the pinions. In this way the positioning of the teeth on the rack can be adjusted to suit a particular requirement despite the fact that there are drive means tending to rotate the pinions. Preferably the retractor roller is mounted for rotation in bearings associated with each of said two opposite sides, and a stepped annular shell is associated with each end of the retractor bar, and a fixed abutment is carried by the guide track to cooperate with individual steps of the confronting shell carried by the retractor roller, a coil compression spring urges said shell towards the fixed abutment, the steps on the two shells are inter-engaged with the associated fixed abutment and provide an adjustment of the axial length of the roller to suit a particular door or window opening. In order further to seal the door or window opening against the passage of insects, preferably the header bar has associated therewith an elongate brush projecting laterally away from the side of the header bar to which the screen is attached, this brush engaging the jamb of the door or window. In order further to ensure that the insect screen is sealed with reference to the guide tracks, the screen preferably has associated with its opposite edges, guide edges engageable with the guide tracks. In order that the present invention may more readily be understood, the following description is given, merely by way of example, reference being made to the accompanying drawings in which:- Figure 1 is a perspective view of one embodiment of the closure of the invention shown mounted as an insect screen covering a door opening; Figure 2 is a front elevation, partly in section, of the screen assembly shown in Figure 1; Figure 3 is an enlarged fragmentary sectional view showing the mounting of the retractor roller; Figure 4 is an enlarged fragmentary sectional view through the upper end part of the header bar as viewed in the direction of the retraction roller of the closure showing the pinion teeth engaged with the rack teeth; Figure 5 is a similar view to Figure 4 but showing the pinion teeth engaged with further teeth on the header bar; Figure 6 is a detailed cross-sectional view through the header bar at the location of the brake operating handle; Figure 7 is a view taken along the line VII-VII of Figure 6; Figures 8 and 9 are schematic side elevations and cross-sections through the header bar illustrating the driving of the common shaft; and Figure 10 is a section through the header bar perpendicular to that of Figure 9 illustrating the mounting of the lower end of the drive spring. Referring first to Figure 1, the screen 10, shown as an insect screen, is mounted to close a door opening in the form of a rectangular frame having an upper and a lower guide track 12,14 and a third side shown closed by a box 16. The left side of the screen 10 is secured to a vertical header bar 18 having upper and lower wheels (not shown in Figure 1) in the form of pinions which engage in racks 20,22 carried on the upper and lower tracks 12,14. The wheels are in fact carried by a common drive shaft and this can be braked by operation of a control handle 24 which is axially slidable on the header bar 18. The free side of the header bar 18 which is remote from the screen 10 is provided with a brush seal 26 to engage the jamb of the door opening when the screen is in the closed position. Mounted within the box 16 is a retractor roller 28 (Figure 2) to which the other edge of the screen 10 is attached. In order to tension the screen 10 a retractor torsion spring 30 is mounted within the roller 28, in a conventional manner and surrounds an upper support shaft 32. A similar lower support shaft 32 is provided at the bottom. At each end of the support shaft there is provided a bearing arrangement indicated by the general reference 34. and illustrated in more detail in Figure 3. Connected to the upper track 12 is a housing member 36, having a generally cylindrically shaped housing portion 38 in which is rotatably mounted a bearing member 40, having an upper stepped shell 42, provided with two ramp-like stepped surfaces 44, displaced 180° from one another. A fixed abutment 46 is provided on each of two diametrically opposite sides of the interior of the housing portion 38 and projects downwardly. The bearing member is urged axially upwardly by a coil compression spring 48 (shown in a compressed state) and is keyed to the shaft 32 for axial sliding movement relative thereto. In use the housing member 36 is secured to the rail and in order to allow for the variation in the spacing between the upper and lower tracks to suit the minute details of a particular doorway, the rotational position of the shell 42 is chosen so that its appropriate steps 44 engage the abutments 46 to hold the shell firmly against any further rotation. It is contemplated that instead of having an abutment 46 a second similar shell 42 could be provided and in this instance it would be advantageous for the steps to be undercut so that they engage fully. It will be seen that surrounding the lower part of the upper shaft 32 is a torsion spring engaging member 50, also shown in Figure 2, this engaging the end of the torsion spring 30. If reference is still made to Figure 2 it will be seen that a pip 52 is provided to the upper and lower ends of the screen 10 at one or more spaced intervals along the edges of the screen to act as guides for the screen on the tracks 12,14. As mentioned earlier, the header bar 18 has at its upper and lower ends a wheel, and in the embodiment illustrated this wheel is in the form of a pinion 54 having peripheral teeth 56 (Figures 4 and 5). In Figure 4 the teeth are shown engaged with the teeth 58 of the upper rack 20. A similar assembly is, of course, provided at the bottom. The pinion 54 is mounted for rotation in an eccentric bearing 60 mounted in an upper cap part 62 of the header bar. The eccentric bearing 60 may be rotated so that the pinion 54 is moved out of engagement with the teeth 58 and into engagement with further teeth 64 on the cap 62 as shown in Figure 5. These further teeth 64 prevent the pinion 54 from rotating, while not engaged with the rack 20. Associated with the cap 62 is a projection 66 which engages within the upper track 12 to guide the end of the header bar along the track. Because there are toothed pinions provided at each end, the guiding of the header bar is such as to ensure that the axis of the header bar 18 is always vertical, that is perpendicular to the direction of the tracks 12,14. If reference is now made to Figures 6 and 7, it can be seen that the header bar 18 has a part tubular cross-section portion 68, and a recessed rear portion 70. Within the part tubular portion is mounted a common shaft 72 which carries the upper and lower wheels (pinions 54). This is a splined shaft on which is mounted a brake drum sleeve 74 which may optionally be engaged by a brake shoe 76 having a wedge like rear face 78. The operating handle 24 has a hollow body 79 which encompasses the part tubular portion 68 of the header bar and has a key portion 80 which extends through a rectangular aperture 82 in the header bar 18. Mounted within the recess 70 is a rear operating member 84 which is located in the recess 70 and is engaged by the key 80 so that the front operating handle 24 and the rear operating member 84 can be caused to move longitudinally of the holding bar 18 together. Facing the wedge like ramp 78 of the brake shoe 76 is a complementary ramp surfaces 86. Thus, upon operation in an upward direction of the front operating member 24 (or the rear operating member 24) the two ramp surfaces 78,86 are more fully engaged thereby to urge the brake shoe 76 against the brake sleeve 74. As illustrated in Figure 7, this in fact urges the brake drum 74, and with it the common shaft 72, to the right. A displacement d is thus brought about and the resilience of the common shaft 72 is used to assist in this braking action. If reference is made to Figures 8, 9 and 10, it can be seen that a portion of the common shaft 72 is surrounded by an upper drive housing 88, around which is disposed a torsion drive spring 90, the drive housing being engaged by the drive spring 90 through engagement in one of the splines 75 (Figure 6) therein, a retainer spring 92 holding the drive housing 88 in place. A projection 94 on a lower spring housing 96 engages in the opening 69 of the part tubular portion 68, to prevent the lower housing 96 from rotating to provide the reaction force for the spring 90. The spring 90 is wound in a direction to cause the common shaft 72 and therefore the pinions 54 to rotate in a direction to close the screen. The force produced by the drive spring 90 is greater than that produced by the recoil spring 30, which is simply used to take up slack in the screen when the header bar is moved towards the opening position. By operation of the handle 24, or the rear operating member 84, the screen can be locked anywhere along the length of the tracks 12,14. In this manner the header bar can simply be moved against the jamb of a sliding door which is in a partly opened position and the bar can be locked on its own. In this circumstance the screen could move in a track parallel to and adjacent the sliding door and the angled brush 26 is used to block the passage for insects.	A closure for a door or window opening, said closure comprising a rectangular frame having a guide track (12,14) on each of two opposite sides, a spring loaded retractor roller (28) mounted at a third side (16) of the frame, a flexible screen (10) positioned with one of its ends on said third side of the screen and being retractable by said retractor roller (28) towards said third side (16), a header bar (18) secured to the other end of the flexible screen (10), said header bar being guided by said guide tracks (12,14) for movement perpendicular thereto, a pair of wheels (54) one mounted at each end of the header bar (18), each wheel (54 ) being operatively associated with one of said guide tracks (12,14) and with means (72) for synchronizing the movement of opposite ends of the header bar, and drive means (90) adapted to rotate the wheels of said pair in a direction to move said header bar towards a closed position of said closure. A closure according to claim 1, wherein the wheels (54) are each in the form of a toothed pinion and wherein the guide tracks (12,14) each have associated therewith a toothed rack (20,22), each rack being engaged by a separate one of said pinions. A closure according to claim 2, wherein the pinions are mounted on adjustable bearings (60), permitting the teeth of the pinions to be disengaged from the teeth of the rack. A closure according to claim 3, wherein further fixed teeth (64) are provided and positioned to be engaged by the teeth of the pinions, when they are disengaged from the teeth of the rack, to prevent rotation of the pinions. A closure according to any preceding claim, wherein both of the wheels are connected to a common shaft (72) and wherein brake means (74-82) acts on the common shaft. A closure according to claim 5, wherein said brake means comprise a laterally displaceable brake shoe (76), engageable with said common shaft (72), or a sleeve (74) attached thereto, a wedge shaped actuating member (78) carried by said header bar (18) adjacent said brake shoe (76) and a handle (24) manually displaceable axially of said header bar, connected to said actuating member (78) to cause the actuating member to move therewith and thereby cause the brake shoe to be urged against the common shaft or sleeve. A closure according to any preceding claim, wherein the drive means (90) comprise at least one torsion spring mounted in said header bar, said torsion spring being operatively connected to said wheels. A closure according to claim 7, wherein both of the wheels are connected to a common drive shaft and wherein said at least one torsion spring acts on the common shaft. A closure according to any preceding claim, wherein said retractor roller includes at least one further torsion spring (30) effective to cause said retractor roller to rotate to wind the screen in an opening direction onto said retractor roller, and wherein said at least one torsion spring (90) mounted on said header bar has, a greater strength than that of said at least one further torsion spring (30) on the retractor roller. A closure according to any preceding claim, wherein the retractor roller (28) is mounted for rotation in bearings (34) associated with each of said two opposite sides, and wherein a stepped annular shell (42) is associated with each end of the retractor bar, and a fixed abutment (46) is carried by the guide track to cooperate with individual steps (44) of the confronting shell carried by the retractor roller, a compression spring (48) urges said shell towards the fixed abutment, the steps (44) on the two shells are inter-engaged with the associated fixed abutment and provide an adjustment of the axial length of the roller to suit a particular door or window opening. A closure according to any preceding claim, wherein the header bar has associated therewith an elongate brush (26) projecting laterally away from the side of the header bar to which the screen is attached. A closure according to any preceding claim, wherein the screen has associated with its opposite edges guide elements (52) engageable in the guide tracks. A closure according to any preceding claim, wherein the screen is in the form of an insect screen.	HUNTER DOUGLAS IND BV; HUNTER DOUGLAS INDUSTRIES B.V.	LONTHO ROY RAYMOND; OSKAM HERMAN; LONTHO, ROY RAYMOND; OSKAM, HERMAN
EP-0489451-B1	489,451	EP	B1	EN	19,950,201	1,992	20,100,220	new	B60T8	null	B60T8	B60T 8/50, B60T 8/42A6, B60T 8/1761D	Antilock brake system with motor current control	The period of an initial apply motor current in each apply phase of an antilock brake control cycle in an antilock braking system having a motor (30) driven pressure modulator (18) is adaptively controlled following a sensed recovery from an incipient wheel lockup condition to establish substantially a steady state condition relationship between current and pressure before motor current is ramped to ramp brake pressure. The period of the initial apply motor current is made a function of the amount of pressure decrease during a prior release phase portion of the antilock brake control cycle to account for the greater increase in brake pressure to the initial reapply value.	This invention relates to an antilock brake system and method for controlling vehicle wheel brakes as, for example, shown in US Patent No 4,881,784. When the brakes of a vehicle are applied, a tyre torque is generated between the wheel and the road surface that is dependent upon various parameters which include the road surface condition and the amount of slip between the wheel and the road surface. This tyre torque increases as slip increases until a critical value of slip is surpassed. Beyond the critical value of slip, the tyre torque decreases and the wheel rapidly approaches lockup. Therefore, to achieve stable braking, an antilock brake system seeks to operate wheel slip at or near the critical slip value. An antilock brake system achieves this objective by detecting an incipient wheel lock condition. Upon detecting an incipient wheel lock condition, the antilock brake system releases pressure at the wheel brake to allow recovery from the incipient wheel lock condition. Upon recovery, brake pressure is reapplied. Criteria used to indicate an incipient wheel lock condition includes excessive wheel deceleration and/or excessive wheel slip. One known antilock brake system uses a (motor driven) pressure modulator in which a DC torque motor drives a piston in a cylinder whose volume is modulated to control the hydraulic brake pressure at the wheel brake. In this system, because of the relationship between motor current, motor torque and motor load represented by the hydraulic brake pressure on the head of the piston, the value of motor current is used as a representation of brake pressure and is controlled to provide control of the brake pressure. In one such system, when an incipient wheel lock condition is sensed, the value of motor current at this time is stored as a representation of the brake pressure producing the maximum braking force coexisting with the critical slip between the wheel and the road surface and the motor current is controlled to quickly retract the piston to release brake pressure to allow recovery from the incipient wheel lock condition. When a recovery from the incipient wheel lock condition is sensed, the motor current is controlled to extend the piston to reapply brake pressure. In reapplying the brake pressure, the pressure is quickly established substantially at the brake pressure producing the maximum braking force by quickly establishing the motor current at a significant fraction of the motor current stored at the time an incipient wheel lock condition was sensed. Thereafter, brake pressure is ramped at a controlled rate which may be a function of wheel slip and acceleration by ramping the motor current in direction applying brake pressure until an incipient wheel lock condition is again sensed after which the cycle is repeated. In the foregoing form of motor driven pressure modulator, the following dynamic relationships exist: (a) when the brake pressure load on the DC torque motor is equal to the motor torque, the DC torque motor does not rotate, the piston remains stationary, and the motor current is a measure of the brake pressure and (b) when the brake pressure load on the DC torque motor is less than the motor torque, the DC torque motor accelerates and rotates at some speed while extending the piston to increase brake pressure. In this latter situation, the speed of the DC torque motor is unknown and the motor current is not a true indicator of brake pressure. Accordingly, when a recovery condition from an incipient wheel lockup condition is sensed and motor current is controlled to the significant fraction of the previously stored motor current representing the brake pressure producing the maximum braking force, the motor begins to accelerate to reapply brake pressure. During this period, the relationship between the motor current and brake pressure is unknown so that the value of brake pressure is unknown during this period. If the motor current were then to be ramped without a known or predicted relationship between current and pressure, the desired control of brake pressure may not result from the control of the motor ramping current. Accordingly, it would not be desirable to begin ramping the motor current until the motor speed in response to the initial reapply current has decreased so that a predictable relationship exists between the motor current and pressure. Thereafter, the motor current may be ramped such as described in our copending patent application EP-A-0.459.548. In general, this invention provides for adaptively controlling the period of the initial apply current corresponding to the desired initial apply pressure following a sensed recovery from an incipient wheel lockup condition to establish substantially a steady state condition relationship between current and pressure before the current ramping portion of the reapply cycle is initiated. This provides for a predictable relationship between motor current and brake pressure so as to enable intelligent control of brake pressure during the reapply portion of the antilock brake control cycle and further prevents an unnecessary delay before ramping of brake pressure is initiated. A method of controlling brake pressure in accordance with the present invention is characterised by the features specified in the characterising portion of claim 1. In accordance with a principal aspect of this invention, the initial current apply period following a sensed recovery of an incipient wheel lockup condition is made a function of the amount of pressure increase from the pressure at the end of the release phase to the desired initial apply pressure. In one aspect of the invention, the amount of pressure increase is represented by the pressure decrease during the release phase portion of the antilock brake cycle. In general, the lower the pressure is released during the release phase, the longer the duration of the initial reapply current. This accounts for the greater increase in brake pressure to the initial reapply value and therefore the longer period required for the DC torque motor to accelerate and move the piston to achieve a condition where the brake pressure load on the DC torque motor is substantially equal to the motor torque, a condition whereat the motor speed is substantially zero. In accordance with another aspect of this invention, the duration of the application of the initial apply current having a value determined to establish a brake pressure producing substantially the maximum braking force is controlled as a function of the brake pressure when recovery from an incipient wheel lock condition is first sensed and a value related to the pressure represented by the motor current stored when the incipient wheel lockup condition was first sensed. This difference provides an estimate of the time required for the DC torque motor to again re-establish the pressure at a pressure having a predetermined relationship to the pressure existing when the incipient wheel lockup condition was first sensed. When motor current is controlled to quickly release brake pressure, the relationship between motor current and brake pressure is unpredictable so that when recovery from an incipient wheel lockup condition is first sensed, the brake pressure and the steady state motor current corresponding thereto are unknown. In accordance with another aspect of this invention, the brake pressure existing when recovery from an incipient wheel lockup condition is first sensed and the motor current corresponding thereto is estimated. Based on this estimated pressure, the duration of the initial period of application of the motor current to establish the initial reapply brake pressure is controlled based upon the relationship between the estimated pressure and a value related to the desired initial reapply pressure. In another aspect of this invention, the current corresponding to the brake pressure existing when recovery from an incipient wheel lockup condition is first sensed is estimated by decaying the value of motor current existing when the incipient wheel lockup condition was first sensed in a manner that substantially tracks the actual wheel brake pressure during the release portion of the antilock brake cycle. For example, the motor current may be decayed in a manner to match a predetermined pressure decay while the motor is controlled to release brake pressure. Accordingly, the estimated pressure represented by the decayed current provides a reference to establish the duration of the initial reapply period. The present invention will now be described, by way of example, with reference to the following description of a preferred embodiment, and the accompanying drawings, in which:- Figure 1 is a diagram of a braking apparatus including a (motor driven) pressure modulator for limiting the brake pressure for antilock brake control; Figure 2 is a diagram of the electronic controller of Figure 1 for controlling the current to the DC torque motor of the pressure modulator of Figure 1; and Figures 3-6 are flow diagrams illustrating the operation of the electronic controller of Figure 1 in accordance with the principles of this invention. An antilock brake system for a wheel of a motor vehicle is illustrated in Figure 1. In general, the wheel includes a brake unit 10 operated by hydraulic pressure provided by a master cylinder 12 and a hydraulic boost unit 14 operated by the vehicle operator. The hydraulic fluid under pressure from the master cylinder 12 is provided to the brake unit 10 via brake lines 16 and a pressure modulator 18. The brake unit 10 is illustrated as a disc brake system that includes a caliper 20 located at a rotor 22. The wheel includes a wheel speed sensing assembly comprised of an exciter ring 24 rotated with the wheel and an electromagnetic sensor 26 which monitors the rotation of the exciter ring to provide a signal having a frequency proportional to the speed of the wheel. The wheel speed signal from the electromagnetic sensor 26 is provided to an electronic controller 28. The pressure modulator 18 is controlled by the electronic controller 28 to limit the brake pressure applied to the brake unit 10 to prevent wheel lockup. The pressure modulator 18 is illustrated in an inactive position where it is transparent to the braking apparatus. This is the modulator home position during normal vehicle braking. In general, when the electronic controller 28 senses a braking condition whereat the wheel is approaching an incipient wheel lock, the pressure modulator 18 is controlled to regulate the braking pressure to the brake unit 10 to maintain the braking of the wheel in a stable braking region. The pressure modulator 18 includes a DC torque motor 30 whose output shaft drives a gear train 32 which, in turn, rotates a linear ballscrew actuator 34. The linear ballscrew actuator 34 contains a linearly stationary ballscrew which, when rotated, linearly positions a nut 36. The nut 36 terminates in a piston 38 such that as the linear ballscrew rotates, the piston 38 is either extended or retracted depending upon the direction of the rotation of the DC torque motor 30. The pressure modulator 18 includes a housing 40 in which a cylinder 42 is formed. The piston 38 is reciprocally received within the cylinder 42. The cylinder 42 forms a portion of the fluid path between the master cylinder 12 and the brake unit 10. Included within this fluid path is a (normally closed) ball check valve 44 which, when closed, isolates the master cylinder 12 from the brake unit 10. The ball check valve 44 is operated to an open position by the piston 38 when it is positioned in an extended position within the cylinder 42 as illustrated in Figure 1. When the ball check valve 44 is opened, fluid communication is provided between the master cylinder 12 and the brake unit 10. This position is the normal inactive position of the pressure modulator 18 so that normal braking of the wheel of the vehicle is provided upon actuation of the brakes by the vehicle operator. However, when the DC torque motor 30 is operated by the electronic controller 28 to modulate the braking pressure in the brake unit 10, the piston 38 is retracted, allowing the ball check valve 44 to seat and isolate the master cylinder 12 from the brake unit 10 as long as the pressure in the cylinder 42 is less than the pressure from the master cylinder 12. Further retraction of the piston 38 functions to increase the volume in the cylinder 42 thereby decreasing the pressure applied to the brake unit 10. By controlling the DC torque motor 30, a pressure at the brake unit 10 can therefore be modulated to controlled values less than the master cylinder 12 pressure output until such time that the piston 38 again unseats the ball check valve 44 or until the pressure generated by the pressure modulator 18 at the brake unit 10 exceeds the fluid pressure output of the master cylinder 12. When this latter condition exists, the ball check valve 44 is opened by the differential fluid pressure which limits the pressure of the brake unit 10 at the master cylinder 12 pressure. In this manner, the pressure at the brake unit 10 can never exceed the operator established pressure. Referring to Figure 2, the electronic controller 28 of Figure 1 is illustrated and generally takes the form of a digital computer based controller. The controller includes a microprocessor 46 that is standard in form and includes the standard elements such as a central processing unit which executes an operating program permanently stored in a read-only memory which further stores tables and constants utilized in controlling the pressure modulator 18, an analogue-to-digital converter, a random access memory and input/output circuitry utilized to provide motor control signals to a motor driver interface circuit 48. The input/output circuit further includes input ports for receiving the wheel speed signal from the output of an interface and squaring circuit 53 having an input from the electromagnetic sensor 26. The motor driver interface circuit 48 receives an enable signal, a motor current command signal Ic and a forward/reverse direction signal from the microprocessor 46 and controls an H-switch driver 50 to establish the commanded motor current Ic in the required forward or reverse direction. The current to the DC torque motor 30 is controlled to the commanded value via a closed loop that responds to the actual motor current represented by the voltage across a sense resistor 52. In response to the direction and motor current command, the motor driver interface circuit 48 energizes the upper and lower forward gates via the upper gate signal UGF and lower gate signal LGF to control the DC torque motor 30 in the forward direction to apply brake pressure and energizes the upper and lower reverse gates via the signals UGR and LGR to control the DC torque motor 30 in the reverse direction to retract the piston 38 to reduce pressure at the brake unit 10. The microprocessor 46 may take the form of a Motorola single chip microcomputer MC-68HC11. The motor driver interface circuit 48 and H-switch circuit 50 may take the form of the driver illustrated in US patent no. 4,835,695. When the speed of the DC torque motor 30 is low as current is controlled in the forward direction to apply pressure to the brake unit 10, the motor current is a measure of the torque and therefore the brake pressure. However, when the motor current is controlled in the reverse direction to release brake pressure or when the DC torque motor 30 is rotating in the forward direction, the motor current sensed by the sense resistor 52 is not a true indicator of brake pressure. During a typical antilock brake control cycle established by the braking apparatus of Figures 1 and 2, when an incipient wheel lock condition is sensed, the motor current is controlled to quickly retract the piston 38 to release brake pressure to allow recovery from the incipient wheel lock condition. This reversal is accomplished by commanding a reverse motor direction and setting the command current Ic at a reverse current value Ir. The motor driver interface circuit 48 responds to these commands by energizing the upper and lower reverse H-switch gate switches to drive the DC torque motor 30 in reverse direction at the commanded current level. As indicated, this current is not representative of the brake pressure existing at the brake unit 10 while the brake pressure is being released. When recovery from the incipient wheel lock condition is sensed, brake pressure is reapplied at a value related to the pressure existing at the time an incipient wheel lock condition was first sensed and thereafter ramped by commanding a forward motor direction and setting the command current Ic at a forward apply current value Ia, first at an initial value that is related to the motor current value when an incipient wheel lock condition was first sensed and thereafter that is ramped in an increasing direction to ramp the brake pressure. The motor driver interface circuit 48 responds to these commands by energizing the upper and lower H-switch gate switches to drive the DC torque motor 30 in a forward direction at the commanded level. Brake pressure is ramped by ramping the value of the apply current value Ia. This ramp function is continued until an incipient wheel lock condition is again sensed after which the cycle is repeated. In operation of the pressure modulator 18, when an incipient wheel lockup condition is sensed, the motor current value IREF is stored as a measure of the value of brake pressure PREF producing the maximum braking effort between the tyre and road surface. The brake pressure is then rapidly released by controlling the motor current in reverse direction. When recovery from the incipient wheel lockup condition is sensed in response to the decreased brake pressure, the motor current is reapplied to a predetermined significant fraction KFRAC of the stored current value IREF representing the brake pressure PREF so as to quickly re-establish the brake pressure at a value substantially producing the maximum braking effort between the tyre and road surface. Reapplication of the apply current to re-establish the braking pressure first functions to reverse the motor movement and induce motor movement in the pressure apply direction. The DC torque motor 30 then rotates in the forward direction until such time that the brake pressure load substantially equals the motor torque represented by the applied motor current at which time the brake pressure is equal to KFRACPREF. A period of time is required for the DC torque motor 30 to stop rotation in the reverse direction and to reaccelerate and apply brake pressure at the commanded brake pressure level. Until such time that the motor movement has re-established the brake pressure at the significant fraction KFRAC of the value PREF, it is not desirable to begin ramping the motor current to provide controlled increase in the brake pressure. This is because until such time that a steady state condition is established following application of the initial current value, motor current as a measure of brake pressure is not valid so that a predictable relationship between motor current and pressure is not established. Accordingly, the duration of the initial time period that the initial apply current is applied is adaptively controlled so as to assure that the DC torque motor 30 has achieved substantially a steady state condition before the current is ramped to ramp the brake pressure while at the same time preventing an unnecessary delay before ramping of brake pressure is initiated. Since the time required for the DC torque motor 30 to re-establish the pressure corresponding to the applied current is dependent upon the amount of increase in brake pressure required, the duration of the initial apply period is made dependent upon the amount of pressure increase. In this embodiment, the amount of pressure increase is represented by the pressure decrease during the pressure release phase of the braking cycle, the greater the pressure decrease, the greater the required increase in brake pressure to achieve the initial apply brake pressure which is dependent upon the initial pressure at the beginning of the pressure release phase. In order to provide an estimate of the brake pressure when recovery from the incipient wheel lockup condition was first sensed, this invention provides for decaying a motor current value IEST of the stored motor current from the initial value IREF while the brake pressure is being released in a manner so as to mimic the actual decrease in brake pressure. Therefore, when a recovery condition is first sensed, the decayed value of motor current represents an estimate of the actual brake pressure PEST existing at the brake unit 10. The duration of the initial apply period is then made dependent upon the pressure drop during the release of brake pressure which is the difference between this decayed value IEST estimating the brake pressure PEST at the time recovery from an incipient lockup condition is sensed and the value IREF representing the brake pressure PREF at the time the incipient wheel lockup condition was first sensed. The initial apply period is such that a substantially steady state condition of the DC torque motor 30 is established before ramping brake pressure is initiated based on a predictable relationship between motor current and brake pressure while at the same time an unnecessarily lengthy delay before the ramping of the brake pressure is initiated is avoided. During the ramping of the brake pressure, the predictable relationship is maintained due to the low ramp rate and therefore motor speed, which relationship may be assured by motor speed control as described in our copending patent application EP-A-0.459.548. The operation of the electronic controller 28 in controlling the DC torque motor 30 in accordance with this invention is illustrated in Figures 3-6. The read-only memory of the microprocessor 46 contains the instructions necessary to implement the algorithm as diagrammed in those figures. Referring first to Figure 3, when power is first applied to the braking apparatus from a vehicle battery 54 (Figure 1) such as when a conventional vehicle ignition switch (not illustrated) is rotated to its on position, the computer program is initiated at a point 56 and then provides for system initialization at step 58 which entails clearing registers, initializing various RAM variables to calibrated values and other functions. When the initialization routine is completed, the program then proceeds to perform antilock brake control functions as required. These antilock brake control functions are performed by executing a control cycle in response to each of repeated control cycle interrupts which are generated at predetermined fixed time intervals such as 5 milliseconds. Upon the occurrence of a control cycle interrupt, the digital computer begins executing the functions embodied in the control cycle. First, at step 60, wheel speed sensor information is read and wheel speed is computed for each of the wheels. Thereafter, the routine determines the individual wheel accelerations at step 62 and the individual wheel slip values at step 64. From the computed values of wheel acceleration and wheel slip, the program determines at step 66 whether or not those parameters represent the need for antilock brake pressure modulation for any wheel. If antilock brake control of wheel brake pressure is not required, the program proceeds to perform background tasks at step 68. These tasks may include diagnostic functions as well as other functions. However, if step 66 determines that a need for antilock brake pressure modulation for any wheel is required, the program proceeds to a step 70 where antilock brake control functions are executed. Once those functions are executed, the program proceeds to the step 68 previously described. The foregoing steps 60 through 70 are repeated once for each control cycle. Thus, when a control cycle interrupt occurs, a new cycle begins at step 60 and the functions represented by steps 60 through 70 are again repeated as previously described. Repeated executions of step 70 when antilock brake control is required establishes the general brake cycle as previously described wherein when the wheel slip and acceleration conditions represent an incipient wheel lockup condition, a pressure release mode is indicated and brake pressure is released to allow the wheel to recover from the incipient wheel lockup condition and when wheel acceleration and slip conditions represent a recovered condition, an apply mode is indicated and wheel pressure is reapplied and ramped until another incipient wheel lockup condition is sensed at which time the release mode is indicated and the cycle is repeated. Referring to Figure 4, there is illustrated the antilock brake control functions executed once for each braking channel where each channel includes a pressure modulator 18. Where the four wheels of the vehicle are controlled independently, this requires the routine of Figure 4 to be executed four times, once for each wheel with its related parameters. In another arrangement, the rear brakes may be controlled by a single pressure modulator such that the routine of Figure 4 then is executed once for each front wheel and once for the combined rear wheels. The antilock brake control routine of step 70 of Figure 3 is entered at step 72 and then proceeds to a step 74 that selects the required brake mode. In general, the selection is made from a number of apply modes, such as 3, each having a related rate of increase in brake pressure as a function of wheel acceleration and wheel slip and one or more release modes also as a function of wheel acceleration and wheel slip. For example, the apply modes may provide for higher rates of increase in brake pressure with increasing values of wheel acceleration and with decreasing values of wheel slip. The release modes may provide for full release with high wheel slip and high wheel acceleration values and step-down release with lower wheel slip and wheel acceleration values. In this embodiment, the particular apply or release brake mode is determined via a ROM stored lookup table storing the various apply and release brake modes as a function of wheel acceleration and wheel slip. The stored brake modes established a threshold between pressure apply and pressure release as a function of wheel acceleration and wheel slip. An incipient wheel lockup condition is indicated when the lookup table first indicates one of the brake release modes whereas a recovered condition is indicated when the lookup table first indicates one of the brake apply modes. Step 76 then determines whether the brake mode determined at step 74 is one of the apply modes. If not, indicating one of the release modes in response to an incipient wheel lockup condition, the program proceeds to a step 78 which executes a brake release mode routine. In general, repeated executions of the brake release mode 78 provide control of the DC torque motor 30 of the respective wheel in reverse direction to retract the piston 38 to reduce the brake pressure to allow wheel recovery from the incipient wheel lockup condition. A wheel recovery condition resulting from repeated executions of the brake release mode 78 is detected at step 74 when the lookup table first indicates one of the pressure apply modes for the wheel acceleration and wheel slip conditions. When this condition is determined at step 76, the program proceeds to a step 80 where the apply current Ia for reapplying brake pressure is determined. In the preferred mode, when step 74 first indicates an apply mode, a large bump current in the forward direction is commanded to the DC torque motor 30 to stop the rotation of the DC torque motor in the reverse direction and to initiate rotation of the DC torque motor in the forward direction. Thereafter, the motor current is set to the significant fraction KFRAC of the value IREF, the motor current at the time the prior incipient lockup condition was first sensed as indicated when the prior brake release mode was first indicated by step 74. As previously described, the period of application of this current in accordance with this invention is a function of the amount of increase in brake pressure from the release pressure to the initial apply brake pressure represented by the current value KFRACIREF. Following expiration of this initial time period at which time the predictable relationship between motor current and brake pressure exists so that motor current is a measure of the brake pressure, the motor current is ramped with repeated executions of the step 80 at a controlled rate to increase the brake pressure at the brake unit 10 until an incipient wheel lock condition is again sensed by step 74 determining a release mode via the lookup table in response to the wheel acceleration and slip values. Referring to Figure 5, there is illustrated the routine embodied in the brake release routine 78 of Figure 4 for estimating the pressure at the brake unit 10 as the pressure is being released in response to a brake release mode being indicated at step 74. This estimation is required since during release, motor current is not a measure of brake pressure. This routine is entered at step 82 and proceeds to a step 84 where a motor current value IEST is decayed exponentially in accordance with the expression IESTKEST where KEST is a fraction less than 1 establishing the rate of decrease in the estimated pressure. IEST has an initial value equal to the motor current value IREF when a release mode is first indicated by step 74. Further, the fraction KEST is a calibration constant stored in ROM and which, in conjunction with the repetition rate of the control cycle, is a predetermined value determined to decay the value of IEST to mimic the actual rate of pressure decease at the brake unit 10 during pressure release. Therefore, the value of IEST is the current corresponding to the pressure at the brake unit 10 during the brake release phase of the brake pressure cycle and which, when applied to the DC torque motor 30 in the pressure apply direction, would establish that brake pressure under steady state conditions. Following step 84, the program proceeds to a step 86 where the program commands the release current Ir in reverse direction to the DC torque motor 30. As long as step 74 indicates a brake release mode, step 78 is repeatedly executed to continually release the brake pressure via step 86 and to continually estimate the value of the brake pressure via step 84. Release of brake pressure in response to repeated execution of the steps 72 through 78 results in the wheel recovering from the incipient lock condition. This recovered condition is detected at step 72 when the lookup table indicates a pressure apply mode for the wheel acceleration and wheel slip conditions. When step 74 indicates that step 72 has determined a pressure apply mode, step 84 is no longer executed so that the decayed value of IEST represents the estimated brake pressure PEST at the end of the release phase of the braking cycle. The program then proceeds to the step 80 where the brake apply routine establishes the apply motor current Ia for applying brake pressure. In the preferred mode, the routine 80 first establishes the apply motor current Ia at an initial high bump current value Ib for a time Tb. As indicated, this current functions to stop the reverse motion of the DC torque motor 30 and initiate forward movement of the DC torque motor 30 to reapply brake pressure. Following expiration of time Tb, the routine 80 establishes the initial apply current Ia at the value KFRACIREF previously described to quickly establish the brake pressure at a value substantially producing the maximum braking effort. The initial apply current is commanded to the DC torque motor 30 for an initial period Tinit which is determined to establish substantially a steady state condition of the DC torque motor 30. At this condition, the predictable current/pressure relationship is established to provide for intelligent control of the subsequent ramping of the brake pressure. The value of this initial period is made dependent upon the required increase in brake pressure to the desired initial apply pressure corresponding to the initial apply current by making the period proportional to the pressure drop during the release phase of the pressure cycle which is represented by the difference between the estimated pressure PEST represented by the decayed current value IEST when the recovery condition was first sensed and the pressure PREF represented by IREF. In another embodiment, the initial period is made proportional to the required pressure increase to the initial apply current by making the period proportional to the difference between the decayed current value IEST and the initial reapply current KFRACIREF. Referring to Figure 6, the routine embodied in the brake apply routine of step 80 of Figure 4 is entered at step 88 and proceeds to determine via step 90 if the application of the initial apply pressure has been completed. If not, the program proceeds to step 92 to determine whether or not the bump current previously referred to has been completed. If not, a step 94 initializes the value Tinit of the initial apply period in accordance with the expression Koff + KG(IREF - IEST) , where Koff is an offset value and Kg is a gain constant. As previously indicated, this time is determined to establish a steady state condition of the DC torque motor 30 whereat the current and pressure relationships are predictable. Thereafter, at step 96, the apply current value Ia to the DC torque motor 30 is set to the bump current value Ib for a time period Tb which may be the period of a single control cycle. Thereafter, the program commands the apply current Ia in the forward direction at step 98. Returning to step 92, when the bump current is completed upon expiration of the time Tb, the program determines at step 100 whether or not the initial period time is equal to the computed time Tinit set at step 94. If the initial period has not expired, the initial period is incremented at step 102 after which the apply current Ia is set to the initial apply current value KFRACIREF at step 104. It is recalled that IREF is the motor current value at the time the incipient wheel lockup condition was last sensed and is a measure of the brake pressure PREF producing substantially the peak tyre torque between the tyre and the road surface. When step 100 determines that the initial time period Tinit has expired, the initial apply is indicated as complete at step 106 such as by setting an appropriate flag to enable ramping of the brake pressure. This is provided at step 108 after the initial apply has been completed as sensed at step 90 by ramping the value of the apply current Ia at a rate that may, for example, be based upon the particular apply mode sensed at step 74. Thereafter at step 110, the value of IEST and IREF are set equal to the apply current Ia. Thus when an incipient lockup condition is first sensed at step 74, IREF and the initial value of IEST each represent the peak pressure PREF during the apply phase. These values are then used as previously described to estimate the brake pressure at the end of the resulting release phase and the initial apply current and period Tinit to be used in the subsequent pressure apply phase. Thereafter, the program commands the motor current at the value Ia in the forward direction at step 98.	A method of controlling the brake pressure applied to the brake unit (10) of a wheel in a braking apparatus having a pressure modulator (18) including a motor (30) for generating a motor torque in response to motor current to control the value of the applied brake pressure, the method comprising the steps of sensing (74) an incipient wheel lockup condition; controlling (78) the motor current to release brake pressure when an incipient wheel lockup condition is sensed to allow wheel recovery from the incipient wheel lockup condition; and sensing (74) recovery from the incipient wheel lockup condition; characterised by controlling motor current (80,90, 100,102,104,98), when recovery is sensed, to an initial current value corresponding to a desired initial apply pressure value for an initial apply time, said initial apply time being established by a predetermined relationship to the brake pressure increase from the released brake pressure to the desired initial apply pressure, the initial apply time established by the predetermined relationship enabling the motor to achieve a condition whereat a predictable relationship exists between the motor current and brake pressure. A method as claimed in claim 1, wherein the desired initial apply pressure value has a predetermined relationship to the brake pressure when an incipient wheel lockup condition is first sensed and further includes the step of determining an amount of released brake pressure when the motor current is controlled to release brake pressure, the brake pressure increase from the released brake pressure to the desired initial apply pressure being represented by the determined amount of pressure decrease. A method as claimed in claim 1, including storing the value PREF of the brake pressure as represented by the value IREF of motor current the time an incipient wheel lockup condition is first sensed; and estimating the brake pressure PEST at the time recovery from the incipient wheel lockup condition is first sensed; wherein the step of controlling motor current, when a recovery is sensed, comprises controlling the motor current to an initial current value corresponding to a desired initial apply pressure value for an initial time that is a predetermined function of the difference between PREF and PEST, the initial time established by the predetermined function enabling the motor to achieve a condition whereat a predictable relationship exists between the motor current and brake pressure. A method as claimed in claim 3, wherein the step of estimating the brake pressure PEST includes (A) establishing an initial current value IEST equal to the stored value IREF and (B) decaying the value of IEST from the initial current value while motor current is controlled to release brake pressure so as to mimic the released brake pressure, the decayed value of IEST at the time recovery from the incipient wheel lockup condition is first sensed comprising the estimated brake pressure PEST. A method as claimed in claim 1, including storing a value IREF of motor current at the time an incipient wheel lockup condition is first sensed as a measure of the brake pressure at the time an incipient wheel lockup condition is first sensed; establishing an initial current value IEST equal to the stored value IREF; and decaying the value of IEST from the initial current value while motor current is controlled to release brake pressure so as to mimic the released brake pressure, the decayed value of IEST at the time recovery from the incipient wheel lockup condition is first sensed comprising an estimate of the brake pressure at the time recovery from the incipient wheel lockup condition is first sensed; wherein the step of controlling motor current, when a recovery is sensed, comprises controlling the motor current to an initial current value corresponding to a desired initial apply brake pressure value for an initial time that is a predetermined function of the difference between IREF and the decayed value of IEST at the time recovery from the incipient wheel lockup condition is first sensed, the initial time established by the predetermined function enabling the motor to achieve a condition whereat a predictable relationship exists between the motor current and brake pressure.	DELCO ELECTRONICS CORP; GEN MOTORS CORP; DELCO ELECTRONICS CORPORATION; GENERAL MOTORS CORPORATION	HOGAN MARTIN ANDREW; LEE ALAN JAMES; LEPPEK KEVIN GERARD; SPADAFORA PETER JOHN; HOGAN, MARTIN ANDREW; LEE, ALAN JAMES; LEPPEK, KEVIN GERARD; SPADAFORA, PETER JOHN
EP-0489453-B1	489,453	EP	B1	EN	19,941,026	1,992	20,100,220	new	F16D55	B22D19, F16D55	F16D55, B22D19, F16D65	B22D 19/14, F16D 55/226, R16D200:260B2, R16D55:00D4	Disc brake	A disc brake comprises a caliper housing 10 having a body member 12 and an arm member 14 connected to one another by a bridge 16. A leading side of the arm member 14, that is the side which the rotor of a disc brake reaches first during normal rotation thereof, is more rigid than a trailing side thereof. A set of stiffening fibres 28, 30 is provided in each of first and second bridge portions 22, 24 of the bridge 16 to produce the difference in rigidities between the leading and trailing sides of the caliper housing 10, wherein the first bridge portion 22 comprises a greater density of fibres 28 than the second bridge portion 24. This difference in rigidities reduces uneven wear of the brake pad and, as a consequence, reduces brake squeal and noise.	The present invention relates to a disc brake for use in a motor vehicle, and in particular to a brake caliper housing. It is known in motor vehicles to provide a disc brake assembly which comprises a rotor, inner and outer brake pads, and a caliper housing having a cylindrical recess containing a piston for urging the inner brake pad into braking engagement with one side of the rotor and an arm member for urging the outer brake pad into braking engagement with the other side of the rotor by reactive force on actuation of the piston. The brake assembly includes a bridge coupling the caliper housing to the arm member. The bridge usually comprises two limbs which are substantially identical and symmetrical, and which in use apply the urging force, through the arm member, to the outer brake pad to cause it to come into braking engagement with the rotor. This type of disc brake assembly is commonly referred to as the floating caliper type. In use, it has been found that such an arrangement causes uneven wear of the lining on the brake pad between its leading and trailing sides. This in turn can lead to sticking of the brake pad, and vibration which generates brake squeal or noise. A prior art disc brake caliper is disclosed in EP-A-405,778. JP-A-61-88,956 discloses a disc brake caliper formed from a composite aluminium casting which is strengthened by a cast iron insert embedded in each portion of the bridge of the caliper, thereby to strengthen the stress-concentrating part of the caliper. DE-A-29 50 660 discloses a brake caliper in which the caliper bridge is formed from a material having a high modulus of elasticity and is wholly or partly encased by a material of lower density and a lower modulus of elasticity. The present invention seeks to provide an improved disc brake. According to an aspect of the present invention, there is provided a disc brake for a motor vehicle comprising a rotor; inner and outer brake pads disposed on opposite sides of the rotor and movable into braking engagement therewith; a piston for urging the inner brake pad against the rotor; and a caliper housing comprising a body member having a cylinder positioned on one side of the rotor and containing the piston, an arm member positioned on the other side of the rotor and cooperating with the outer brake pad, and a bridge extending between the body member and the arm member across the plane of the rotor, the bridge comprising a plurality of bridge portions each being connected at a first longitudinal extent thereof to the body member and at a second longitudinal extent thereof to the second member; characterised by stiffening means operative on one or more of the bridge portions so as to cause the rigidity of the bridge to be stiffer at a leading side of the arm member than at a trailing side thereof. The manner in which the outer brake pad is urged onto the rotor can thereby be altered to prevent or reduce uneven wear thereof. By 'leading side' of the arm member is meant the side of the arm member which is located upstream with respect to the normal direction of rotation of the rotor (that is the direction in which the rotor rotates when the vehicle is travelling in the forward direction). By 'trailing side' of the arm member is meant the side of the arm member located downstream with respect to the normal direction of rotation of the rotor. The invention can be used with disc brakes of the fixed, floating and sliding types. The invention also extends to a disc brake caliper. Advantageously, the stiffening means is embedded in one or more of the bridge portions. In a preferred embodiment, the stiffening means comprises stiffening fibres. The stiffening fibres may extend into the arm member and/or the body member. The stiffening fibres may be made of ceramics or carbon, or of any other suitable material. The caliper housing may be made of steel, aluminium or any other suitable material. An embodiment of the present invention is described below, by way of illustration only, with reference to the accompanying drawing, in which: Figure 1 is a side elevational view of an embodiment of disc brake assembly and brake caliper housing; and Figure 2 is a plan view of the brake caliper housing of Figure 1. Referring to Figure 1, the disc brake assembly 10 comprises a brake caliper housing 11 formed of a body member 12, an arm member 14, and a bridge 16 connected at one end to the body member 12 and at the other end to the arm member 14. The body member 12 has a generally cylindrical recess 13 therein which slideably receives a piston 15 to which is pressed an inner brake pad 17. The inner face 20 of the arm member 14 supports an outer brake pad 19 which faces the inner brake pad 17. A brake rotor 21, connected to a wheel (not shown) of a vehicle, lies between the inner and outer brake pads 17,19. Hydraulic, or other, actuation of the piston 15 causes the inner brake pad 17 to be urged against one side of the rotor 21 and, by reactive force, causes the caliper housing 11 to float, thereby bringing the outer brake pad 19 into engagement with the other side of the rotor 21, as is well known in the art. The bridge 16 comprises first and second bridge portions 22, 24 (better seen in Figure 2) which extend along the longitudinal direction of the bridge 16, and are each connected at a first longitudinal extent to the body member 12 and at a second longitudinal extent to the arm member 14. The two bridge portions 22,24 are also connected to one another at either end. A plurality of stiffening fibres 28, 30 are embedded within the caliper housing 11 and extend from within the body member 12, along the bridge 16 into the arm member 14. As can be seen better in Figure 2, there are two different sets of fibres, each embedded in a respective bridge portion 22, 24 of the bridge 16. The first set 22 of stiffening fibres is located in the leading side of the caliper housing 11, relative to the direction in which the rotor 21 rotates when the vehicle is travelling forwardly (and shown by the arrow). The second set of stiffening fibres are located in the trailing side of the caliper housing 11. There is a greater number and density of fibres in the first set of fibres 22 than in the second set 24 to cause the leading side of the caliper housing 11 to be stiffer than the trailing side. It has been found that this reduces uneven wear of the brake pads and, as a consequence, reduces brake noise and wear. Other arrangements of fibres may be provided to give the same effect, for example, there may be fibres in only the first bridge portion 22, or there may be different types of fibres in the first and second bridge portions 22, 24. Alternatively, the fibres in the first bridge portion 22 may be thicker than the fibres in the second bridge portion. The fibres may be pre-stressed to increase the overall rigidity of the bridge 16 and of the connection between the bridge and the two members 12, 14. Selective pre-stressing of the fibres can be used to increase the rigidity of the leading side of the bridge relative to the trailing side. The fibres are conveniently embedded in the caliper housing 11 by placing them in the caliper housing mould prior to casting.	A disc brake for a motor vehicle comprising a rotor (21); inner and outer brake pads (17,19) disposed on opposite sides of the rotor and movable into braking engagement therewith; a piston (15) for urging the inner brake pad (17) against the rotor; and a caliper housing (11) comprising a body member (12) having a cylinder (13) positioned on one side of the rotor and containing the piston, an arm member (14) positioned on the other side of the rotor and cooperating with the outer brake pad (19), and a bridge (16) extending between the body member and the arm member across the plane of the rotor, the bridge comprising a plurality of bridge portions (22,24) each being connected at a first longitudinal extent thereof to the body member and at a second longitudinal extent thereof to the arm member; characterised by stiffening fibres (28) in the arm member and one or more of the bridge portions causing the bridge to be stiffer at a leading side of the arm member than at a trailing side thereof. A disc brake according to claim 1, wherein the stiffening fibres (28) extend into the body member. A disc brake according to claim 1 or 2, wherein the stiffening fibres (28) are made of ceramics or carbon. A disc brake according to any one of claims 1 to 3, wherein the stiffening fibres (28) are pre-stressed. A disc brake according to any one of claims 1 to 4, wherein each bridge portion (22,24) comprises stiffening fibres (28), different densities of fibres being provided in each bridge portion. A disc brake according to any one of claims 1 to 4, wherein each bridge portion (22,28) comprises stiffening fibres (28), the cross-sectional areas of the fibres differing from bridge portion to bridge portion. A disc brake according to any preceding claim, wherein the bridge (11) comprises two bridge portions (22,24). A disc brake according to claim 7, wherein the bridge portions (22,24) are separated from one another for at least part of the longitudinal extent of the bridge.	ACG FRANCE	PANTALE DAVID; PANTALE, DAVID
EP-0489455-B1	489,455	EP	B1	EN	19,950,322	1,992	20,100,220	new	B60B17	null	B60B17, B60B9	B60B 17/00C2B	A rail vehicle wheel	A rail vehicle wheel comprises a wheel centre (1), a flanged tyre (2), a rubber ring (3) between the wheel centre and the tyre, and a pressure ring (4). The rubber ring consists of an annular, axial body (3') and at each side thereof a flange (3''), which forms an angle of for example 60° with the wheel axis.	Technical FieldThis invention relates to a rail vehicle wheel, comprising a wheel centre, a flanged tyre, and a rubber filling, which is disposed between the wheel centre, the tyre and a pressure ring. Background of the InventionConventional examples of the above type of rail vehicle wheels are so called V-wheels (shown for example in SE-A-315 915 or CH-A-320 175), in which one or two rubber rings forming a very open V with each other is/are arranged between the wheel centre and the tyre. The angle between each rubber ring and the axis of the wheel may typically be between slightly less than 30° and slightly more than 60°. The rubber rings are primarily exposed to pressure under operation, and the resiliency of the wheel is relatively low. The primary purpose of the wheel is to be sound-dampening. Due to the characteristic of the rubber material the resiliency in the axial direction, where the rubber is exposed to shear, is considerable, which is a drawback. In another design a number of rubber elements are arranged in circumferential rings between the wheel centre and the tyre and are operating in shear, which provides a good resiliency. A wheel of this design is, however, relatively complicated and expensive, especially if high loads are to be handled. GB-A-895 520 shows a rail vehicle wheel according to the preamble of claim 1. The rail vehicle wheel comprises a wheel centre, a flanged tyre and a rubber filling in a generally U-shaped, annular compartment between the wheel centre, the tyre and a pressure ring, which ring is mounted to a side of the wheel centre for holding the rubber ring in position. The rubber filling consists of two separate, substantially Z-formed rings being under pressure when mounted. Generally speaking, the object of the invention is to accomplish a wheel having the simple and comparatively cheap design of the conventional V-wheel but having a greater resiliency in the radial direction (and better stiffness in the axial direction). It is also imperative that a new wheel has the ability to carry great loads. All of the above objectives cannot be reached in the already known way of increasing the angle between each rubber ring and the wheel axis, so that the ring is more exposed to shear than to pressure under operation. Not even by combining the two rubber rings into one and increasing the angle as above stated it is possible to reach the objectives. The InventionThe object of the invention is achieved by the subject-matter as defined in claim 1. In order to attain all of the desired objectives, a rubber filling in a wheel of the above stated kind consists of a rubber ring having an annular, axial body, which does not completely fill the space afforded to it in the compartment, and, integrally with the axial body, at each side thereof a thinner flange, which forms an obtuse angle, preferably of 60°, with the wheel axis, and in that the rubber ring is slightly prestressed when mounted. The rubber ring flanges - by being exposed at operation to a combination of shear (to a larger extent) and pressure (to a lesser extent) - will give the wheel a resiliency of for example 0.5 - 1 mm or more but also a satisfactory stiffness in the axial direction. If the wheel is exposed to higher loads, the annular body will be exposed to pressure giving the wheel a progressive spring characteristic. In the conventional V-wheel the rubber rings are virtually only active in the vicinity of the contact point between the wheel and the rail, whereas in the present design the rubber flanges will be active practically around the whole wheel at rotation. In the conventional V-wheel the screw joints attaching the pressure ring to the wheel centre and thus keeping all parts together are placed radially inside the rubber rings. Also in the present design the pressure ring is attached to the wheel centre by a number of screw joints evenly distributed around the wheel, but here the screw of each screw joint extends through a hole in the annular body of the rubber ring, whereby a two-fold purpose is accomplished: undesired circumferential movements of the rubber ring are prevented and a very space-effective design is obtained. A further security against undesired mutual movements between rubber and metal (slip and creep) also in radial direction is according to the invention obtained in that surfaces of the wheel centre, tyre and/or pressure ring intended to cooperate with the rubber ring flanges are provided with annular grooves. A further feature of the wheel according to the invention is that the substantially axial surface of the wheel centre in contact with the annular body of the rubber ring is slightly tapered. In this way a certain compensation for the axial force from the contact of the wheel flange with the rail on which the wheel rolls is obtained and also a guiding for the rubber ring at the mounting. Brief Description of the DrawingThe invention will be described in further detail below reference being made to the accompanying drawing, in which Fig. 1 is a side view of a wheel according to the invention, Figs. 2 and 3 are cross-sectional views (to a larger scale) through this wheel along the lines II-II and III-III in Fig. 1, and Fig. 4 is a corresponding cross-sectional view through a rubber ring before mounting. Detailed Description of a Preferred EmbodimentA rail vehicle wheel according to the invention consists primarily of a wheel centre 1, a flanged tyre 2, a rubber ring 3, and a pressure ring 4. The rubber ring 3 has a substantial annular body 3', from which two thinner flanges 3'' extend towards the wheel tread (when fitted). The pressure ring 4, which has a press fit in relation to the wheel centre 1, is mounted to the wheel centre by means of screw joints, preferably evenly distributed around the wheel as shown in Fig. 1. Each screw joint consists of a stud or screw 5, which is initially securely fastened to the wheel centre 1, and a nut 6. The stud 5, which extends through the annular body 3' of the rubber ring 3, is comparatively slender, and the engagement between the nut 6 and the pressure ring 4 is over conical surfaces; these factors enhance flexibility and decrease the requirement on fine tolerances. As appears from Figs. 2 and 3, there are annular grooves in the metal surfaces of the wheel centre 1, the tyre 2 and the pressure ring 4 in contact with the rubber ring 3, whereas the corresponding surfaces of the rubber ring are even, as appears in Fig. 4, which shows the rubber ring before mounting. At mounting, the rubber will be pressed into these grooves increasing the contact surface between rubber and metal, so that mutual slip and creep will be diminished. It also appears from Fig. 4 that the annular body 3' of the rubber ring 3 may have annular recesses, so that even after the compression occurring at mounting, which may be in the region of 10-20 %, the space provided by the metal parts in this region is not completely filled with rubber. Likewise the diameter of the studs 5 is less than the diameter of the corresponding holes in the rubber ring 3. In this way a pressure increase in this area is obviated. Rubber has the ability to withstand twice as high forces under pressure as under shear. By choosing the angle between the wheel axis and each rubber flange 3'' at 60°, the geometry automatically leads to maximum twice as high forces in the annular body 3' exposed to pressure as in the flanges 3'' exposed to shear. By the geometry of the rubber ring 3 having a rather wide annular body 3', the tyre 2 has a big cross-sectional area inside the flanges 3'', so that the tyre - even after substantial wear - has great strength and stiffness with increased safety and advantageous pressure distribution in the rubber as result. The mounting of the wheel is simple: the rubber ring 3 is first mounted on the tyre 2, whereupon the assembly is placed on the wheel centre 1 with the pre-mounted studs 5 extending through the holes in the rubber ring 3, and as the last step the pressure ring 4 is mounted and attached (to contact against an abutment in the wheel centre 1) by the nuts 6, so that the desired prestress in the rubber is obtained and rubber material is pressed into the grooves in the metal parts. In the shown case there are three grooves at the inner side of each rubber ring flange 3'' and one at the outer side; these numbers may vary. The rubber ring 3 is completely symmetrical before mounting, as appears from Fig. 4. However, it appears from Figs. 2 and 3 that the substantially axial surface of the wheel centre 1 in contact with the annular body 3' of the rubber ring 3 has a certain inclination or taper, which has the twofold purpose of simplifying the mounting (by accomplishing a guiding) and providing a certain lateral force compensation for the lateral force emanating from the cooperation between the wheel flange (on the tyre 2) and the rail on which the wheel runs. By the fact that the studs 5 extend through the rubber ring 3, the latter will effectively be prevented from undesired rotational movements, while at the same time a very space-effective design is obtained. An even improved safety against rotational movements may be attained by initially cementing the rubber ring 3 to the tyre 2. In a conventional V-wheel design, where two rubber rings are arranged between a wheel centre and a tyre in a V-configuration and where the angle that each ring forms with the wheel axis is much smaller than in the present design, say 30° or less, the rubber is primarily exposed to pressure, which gives the wheel only a small resiliency in the radial direction and greater and undesired resiliency in the axial direction, where the rubber is more exposed to shear. In the present design only the rubber in the rubber ring flanges 3'' is active in normal operation of the wheel, as the annular body 3' does not completely fill the space afforded to it. Due to the fact that the rubber in the flanges 3'' mainly operates in shear, where the material is more resilient, a greater elasticity in the radial direction is obtained than in the conventional design and a greater stiffness in the axial direction. Only when the wheel is exposed to greater loads, the rubber ring body 3' will start to cooperate more actively under pressure and give the wheel a progressive spring characteristic. In the conventional V-wheel design, the rubber rings are compressed only in the vicinity of the contact point between the wheel and the rail and are practically idling during the remainder of each rotational turn, whereas in the present design the shear forces act (in different directions) on practically the whole rubber flanges 3'', which leads to a more even distribution of the loads and stresses. In the shown and described design the rubber flanges 3'' are directed towards the tyre 2; the rubber ring may also be arranged with the flanges directed towards the wheel centre.	A rail vehicle wheel, comprising a wheel centre (1), a flanged tyre (2) and a rubber filling (3) in a generally U-shaped, annular compartment between the wheel centre, the tyre (2) and a pressure ring (4) which ring is mounted to a side of the wheel centre (1) for holding the rubber filling (3) in position, characterized in that the rubber filling consists of a rubber ring (3) having an annular, axial body (3'), which does not completely fill the space afforded to it in the compartment, and, integrally with the axial body (3'), at each side thereof a thinner flange (3''), which forms an obtuse angle, preferably of 60°, with the wheel axis, and in that the rubber ring (3) is slightly prestressed when mounted. A wheel according to claim 1, where the pressure ring (4) is attached to the wheel centre (1) by a number of screw joints (5, 6) evenly distributed around the wheel, characterized in that a screw (5) of each screw joint (5, 6) extends through a hole in the annular body (3') of the rubber ring (3). A wheel according to claim 1 or 2, characterized in that surfaces of the wheel centre (1), tyre (2) and/or pressure ring (4) intended to cooperate with the rubber ring flanges (3'') are provided with annular grooves. A wheel according to any of the preceding claims, characterized in that the substantially axial surface of the wheel centre (1) in contact with the annular body (3') of the rubber ring (3) is slightly tapered.	WABCO HOLDINGS SAB; SAB WABCO HOLDINGS B.V.	EMILSSON FRED SOEREN; EMILSSON, FRED SOEREN; Emilsson, Fred Sören
EP-0489456-B1	489,456	EP	B1	EN	19,950,621	1,992	20,100,220	new	F16K35	F16K7	F16K7, F16K35	F16K 7/07, F16K 35/14	Dispensing devices with multiple-way tap	A device (10) for dispensing water from at least one delivery outlet (25) comprises first means (19) for manually controlling the delivery from said outlet (25) of water flowing from first sources (22) and second means (13) for manually controlling the delivery from said outlet (25) of water flowing from second sources (15). At least said first means (19) are operatively connected to cutoff means (30, 31) inhibiting delivery from the second means (13) when the first means (19) are made to deliver water from their respective sources (22).	This invention refers to a water selecting/dispensing device which can be positioned on the edge of a wash-basin or the like. The general scope of this invention is to provide a dispensing device whereby it is possible to select in a reciprocally exclusionary fashion the delivery between at least one source of treated water and mixable sources of hot and cold water, while avoiding possible mixings between the treated water and the hot and cold water. This scope is achieved according to the invention by providing a device as claimed in claim 1. U.S.-A-2 463 737 discloses a selective valve assembly for gasoline in which a latching mechanism is associated with the valves of the assembly so that only one valve may be open at a time. However, such an assembly is for use in connection with gasoline tank trucks and the like. The innovatory principles of this invention and its advantages with respect to the known technique will be more clearly evident from the following description of possible exemplificative and non-restrictive embodiments applying such principles, with reference to the accompanying drawings, in which: figure 1 shows a schematic partially cutaway side view of a first tap made according to this invention; figure 2 shows a view of the tap of figure 1 operated; figure 3 shows a partially cutaway front view of the device of figure 1; figure 4 shows a schematic partially cutaway sectional side view of a second tap made according to this invention; figure 5 shows a view of the tap of figure 4 operated; figure 6 shows a schematic partially cutaway sectional side view of a third tap made according to this invention; figure 7 shows a view of the tap of figure 6 operated; figure 8 shows a cross-section viewed along the line VIII-VIII of figure 6; figure 9 shows a schematic partially cutaway sectional side view of another tap made according to this invention; figure 10 shows a schematic partially cutaway side view of a selector applicable to the taps mentioned previously; figure 11 shows a cross-section viewed along the line XI-XI of figure 10. figure 12 shows a schematic partially cutaway side view of a further tap made according to this invention; With reference to the figures, a tap made according to the invention is shown in figures 1, 2, 3 and is generically indicated by reference 10. Said tap comprises a body 11 secured from below to a surface 12, for example the edge of a wash-basin. The body 11 comprises a housing designed to receive a single-control mixer cartridge 13, of known technique (for example of the type with ceramic disks, well-known by any technician expert in the field). The cartridge has a control pin 21 connected, by means of a casing element 50, to an operating lever 14. Said lever controls the delivery and adjusts the mixing of the water flowing from two inlets 15, 16 (figure 2) typically for hot water and cold water, respectively. The water is turned on by slanting the lever 14 downward, in the plane of the drawing, (as shown by the broken line in 26), while the mixing is regulated by rotating the lever around the axis of the pin 21. The outlet of the cartridge 13 is connected, by means of a duct 17, to a first delivery pipe 18. In the opposite position with respect to the cartridge 13, the body 11 has a housing for a known screw-type tap 19, which is made to rotate by means of a lever 20 protruding radially from a casing element 27 keyed onto the pin 28 controlling the screw. The screw tap 19 has an inlet duct 22 connected to a source of treated water, for example purified. The outlet of the screw tap is connected, by means of a duct 23, to a delivery pipe 24 advantageously disposed concentric to the pipe 18. The pipes 18 and 24 then lead into a delivery outlet 25. The pipes 18 and 24, which are integral with each other, are preferably connected to the body 11 in a rotatable fashion with respect to their axis, so as to enable the outlet 25 to be oriented in a horizontal plane. The casing element 27 has a cam-shaped surface which acts on the head 30 of a pin 31 in order to push it, against the action of a spring 32, when the screw tap is turned on by shifting the lever 20 (as clearly shown in figure 2). As can be more clearly seen in figure 3, at its other end the pin 31 supports a C -shaped element 33 which constitutes a movable hearing surface for the edge of the casing element 50 integral with the lever 14. When the lever 20 is in the closed position, the element 33 is in the retracted position shown in figure 1, and the lever 14 can be freely shifted to operate the mixer 13. As shown in figure 2, when the lever 20 is rotated, the screw tap 19 opens and the cam surface 29 simultaneously pushes the pin 31, so that the element 33 comes to rest against the edge of the casing 50, thus preventing the lever 14 from shifting and consequently opening the mixer. Advantageously, whenever the tap 19 is closed and the mixer 13 is open, the subsequent opening of the tap 19 forces the element 33 to close the mixer. The extension of the C-shaped element 33 ensures interference with the casing 50 belonging to the lever 26. Said lever has also been rotated around the axis 21 in order to vary the mixing ratio between the sources 15 and 16. It is clear, at this point, how the device 10 operates. By operating the lever 14, water flowing from the ducts 15 and 16 can be delivered from the outlet 25 mixed to any desired degree. Likewise, by operating the lever 20, water flowing from the duct 22 can be delivered from the outlet 25. Once the delivery one of the two flows of water has begun, the presence of the mechanical stop, consisting of the pin 31 and the element 33, prevents the other from simultaneously being delivered. This arrangement, together with the fact that the paths of the two different flows of water are completely separate, prevents any possibility whatsoever of them becoming mixed together. In this way, the properties of the treated water (for example its purity) can in no way be altered by the water coming from the other ducts. The impossibility of even small quantities of liquid contained in the ducts of the delivery outlet becoming mixed is useful whenever the sources consist of liquids other than simply water, such as for example, soft drinks. Figures 4 and 5 show a second embodiment of a tap according to the inspiring principles of this invention. This second embodiment 110 is substantially similar in structure to the previous embodiment 10 and maintains the same numbering as the latter preceded by the digit one, for the parts which remain substantially unchanged, and for which reference should be made to the foregoing description. The second embodiment is thus composed of a body 111 with housings designed to receive a mixing cartridge 113, operated by a lever 114 to mix and control the delivery of water flowing from ducts 115 and 116 (for example, hot and cold water ducts, respectively), and a screw-type tap 119, operated by a lever 120 to regulate the incoming flow of treated water (refrigerated, purified, etc.) from a duct 122. Unlike the previous embodiment, the outlet ducts 117 and 123, from the mixer 113 and from the screw tap 119, respectively, pass through a chamber 150 within which is slidingly and tightly housed a piston 151, which moves against the action of a spring 152 to alternatively close the duct 117 or the duct 123 which penetrate into the chamber 150 on opposites sides of the piston 151. As shown in figure 4, the spring 152 exerts pressure on the piston to close the duct 117. When the screw tap 119 is opened the water flowing from the duct 122 can then flow through the ducts 123 and 124 towards a delivery outlet, not shown since it is essentially similar to the delivery outlet 25 of figure 1. Conversely, when the mixer 113 is turned on the water flowing from it, as shown in figure 5, forces the piston 151 to slide against the action of the spring, so as to open the duct 117 in the direction of the duct 118, which also communicates with the delivery outlet. The sliding movement of the piston simultaneously closes the duct 123, so that when the tap 119 is operated it prevents delivery of the corresponding water. In this way a hydraulic lock is obtained which prevents the water flowing from the ducts 115, 116 (advantageously normal mains water) from being accidentally mixed with the treated water flowing from the duct 122. Figures 6-8 show a third embodiment applying the innovatory principles claimed herein. This embodiment, which is generically indicated by reference 210, comprises a body 211 with a housing designed to receive a mixing cartridge 213, operated by a lever 214 for mixing and controlling the delivery of water flowing from ducts 215 and 216 (for example, cold and hot water, respectively, from a water supply system), the mixed flow passes through ducts 217 and 224 and is then delivered from a delivery outlet, not shown, identical to the delivery outlet 25 of figure 1. Disposed at the opposite end of the body 211 are a selector 260 and a delivery tap 261. The selector 260 comprises a first fixed disk 262 having (as is more clearly shown in figure 8) a plurality of holes disposed along a circumference concentric to the disk. For example, there can be three holes, indicated in the figures by references 263, 264, 265, communicating by means of ducts 266, 267, 268 with their respective pipes 269, 270, 271 which supply treated water. The treated water can be, for example, purified and refrigerated water, purified water, and water containing carbon dioxide. Disposed matching with one face of the disk 262 is a second disk 272 coaxial with the first and free to rotate around their common axis. The rotation of the disk 272 is is controlled by an external ring nut 273 connected to it by means of a screw 274 sliding within a circumferentially extended slot 275, as can be clearly seen in figure 7. The disk 272 is traversed by a hole 276 which, on rotation of the disk is shifted to selectively match with one of the plurality of holes on the fixed disk 262. In this way, the selected duct (269, 270 or 271) communicates, through a chamber 277, with a duct 278 coaxial to the disks and ending in a chamber 279 connected to a duct 218 leading to the delivery outlet. Fitted to slide axially to the duct 278 is a hollow shaft 280 provided at one end with a plug 281 which intercepts the flow through the duct 278. Sliding within the hollow shaft 280 is a shaft 282 which is divided at one end to simultaneously control a plug 283 which is actuated to close the inlet of the mixer 213 connected, through the duct 285, to the duct 215 and (as shown in figure 7) a plug 284 which is actuated to close the inlet of the mixer 213 connected, through a duct 286, to the duct 216. At the opposite end to the plugs 283 and 284, the shaft 282 carries an element 287 which is made to slide axially, against the action of a spring 290, by the pressure exerted by a cam surface 288 operated by shifting a lever 220. By compression of a spring 289, the movement of the element 287 is transmitted elastically to the shaft 282. In use, the mixer 213 can be operated by shifting the lever 214, similarly to the mixer 13 of the first embodiment. When the lever 220 is shifted from the position shown in figure 6 to the position shown in figure 7, it initially shifts, by means of the spring 289, the shaft 282 so that the plugs 283, 284 cut off the flow of water to the mixer 213. By continuing the rotatory movement of the lever 220 the spring is compressed until the element 287 comes into contact with the hollow shaft 280 and forces it to open the duct 278, thus obtaining delivery of the water flowing from the duct (269, 270 or 271) which is selected by rotating the ring nut 273. This ensures that, whenever the lever 220 is operated while water is being delivered through the mixer 213, the delivery from the mixer is automatically interrupted before the delivery controlled by the tap 261 begins. At the same time, whenever the tap 261 is open and the mixer 213 is turned on, no water will be delivered from the latter. This makes it impossible for the water coming from the two sets of ducts 215, 216 and 269, 271 to be mixed, even in the case of incorrect manipulation by the user. Figure 9 shows a further example of a tap according to the invention. In this further embodiment, generically indicated by reference 310, the two sets of water to be kept separate from each other each comprise two sources consisting respectively of ducts 315, 316 and 393, 394. For example, the first can be connected to sources of hot water and cold water from the mains and the second can be connected to sources of purified water and refrigerated purified water. The sources of the first set can be mixed by means of the mixer 313, by shifting the lever 314, while the sources of the second set can be mixed by means of the mixer 391, by a similar movement of slanting and rotating the lever 392. The outlets of the two mixers are connected to separate delivery ducts, indicated by references 318 and 324, respectively, which lead into a delivery outlet which is similar to the outlet 25 of figure 1 and therefore not shown. When the lever 392 is slanted, to open the mixer 391, it pushes the edge of the casing element 327 against a C-shaped element 395, substantially identical to the element 33 of figure 3. In this way, a pin 331 connected to it is made to slide, against the action of a spring 332, so as to in turn push a C-shaped element 333 against the edge of the casing element 350. As a result, if the mixer 314 was open it is closed by the thrust of the element 333. Similarly, if the mixer 313 is opened when the mixer 391 is open, the latter is closed by the thrust of the element 395 against the edge of the casing 327, thus preventing the simultaneous operation of both mixers, which would result in the mixing of their respective flows of water. In figure 12 is shown a further tap made according to the invention, and generically indicated by 410, comprising a body 411 secured from below to a surface 412, for example the edge of a wash-basin. The body 411 in turn comprises a housing designed to receive a single-control mixer cartridge 413, of known technique (for example of the type with ceramic disks, well-known by any technician expert in the field). The cartridge has a control pin 421 connected, by means of a casing element 450, to an operating lever 414. By rotating and slanting the lever 414 with respect to the axis of the cartridge it is thus possible to control the delivery and adjust the mixing of the water flowing from two inlets 415, 416, typically for hot water and cold water, respectively. In the opposite position with respect to the cartridge 413, the body 411 has a housing for a known screw-type tap 419, which is made to rotate by means of a lever 420 protruding radially from a casing element 427 keyed onto the pin 428 controlling the screw. The screw tap 419 has an inlet duct 422 connected to any known source of treated water, for example purified, and an outlet connected, by means of a duct 423, to a chamber 400 which leads off into a first delivery pipe 418. An annular diaphragm 402 surrounds the pipe 418 and hermetically separates the chamber 400 from a second chamber 401 which leads off into a tubular element 403 connected to a second pipe 424. A duct 417 connected to the mixed outlet of the cartridge 413 also leads into the chamber 401. The pipes 424 and 418 are advantageously integrally and concentrically disposed so that their other ends open out into a delivery head 405 and are preferably connected to the body 411 in an axially rotating fashion, so as to enable the head to be oriented in a horizontal plane. The delivery head 405, which is advantageously axially rotatable with respect to the ducts 418 and 424 thanks to an airtight rotary coupling 404, comprises a delivery outlet 425 with a first passage 406 directly connected to the pipe 424. A second passage 407, coaxial to the first, is connected to the pipe 418 by means of a valve unit 408 comprising a piston 409 biased by a spring 454 to tightly close the mouth of the duct 418. The delivery head is advantageously fitted with a liquid crystal thermometer 456 in contact with the water dispensed by the mixer, so as to give an indication of its temperature. To use, let us assume that the lever 420 is operated so as to open the screw tap 419. The treated water arriving from the duct 422 will begin to flow into the duct 418 until it reaches the valve unit 408. The ratio between the flexibility of the diaphragm and the thrust of the spring is such that the pressure of the water flowing from the screw tap will first flex the diaphragm 402 and then the piston 409 will move against the action of the spring 454. Thus, before the water begins to flow from the outlet 425, the diaphragm flexes and comes to rest tightly against the edge 455 of the element 403 thereby closing the passage between chamber 401 and pipe 424. If at this point we were to open the mixer tap 413, the delivery of mains water from the ducts 415 and 416 would be prevented because the diaphragm 402 prevents it from flowing between duct 417 and pipe 424. It should be noted that the area of the diaphragm affected by the pressure of the treated water in the chamber 400 is double compared to the area of diaphragm affected by the pressure of the mains water in the chamber 401. Consequently, although the pressure of the different flows of water is the same, the water arriving from the duct 423 will always take precedence in the delivery. Therefore, whenever only the mixer tap 413 is opened the mains water is immediately delivered from the outlet 425, but if then the tap 419 is opened the diaphragm closes the passage between chamber 401 and pipe 424, impeding the flow of mains water, and the treated water is then delivered. This arrangement, together with the fact that the paths of the different flows of water are completely separate, prevents any possibility whatsoever of them becoming mixed together. In this way, the properties of the treated water (for example its purity) can in no way be altered by the water coming from the other ducts. The impossibility of even small quantities of liquid contained in the ducts of the delivery outlet becoming mixed is useful whenever the sources consist of liquids other than simply water, such as for example, soft drinks. The operating features described above are obviously identical also when the pressure of the incoming water in the two circuits differs, within certain limits In fact, in the worst of hypotheses, that is when the inlet pressure of the treated water is lower than the inlet pressure of the mains water, it should be borne in mind that whereas the water flowing through the duct 403 to the outlet encounters practically no resistance, the water flowing through the duct 418 encounters the resistance of opening the valve 408, and to this is added the different area of the diaphragm affected by the thrust of the two sources of water. Should it be desired to be able to choose from a wider range of sources, figures 10 and 11 show a selector which can be connected to an inlet duct of the previous embodiments and, in particular, to duct 22 or 122 of the embodiments shown in figures 1-3 and 4-5, respectively. This selector, which is generically indicated by reference 34, can be fitted into a surface 35, for example the edge of a wash-basin, and internally comprises a first fixed disk 36 with peripheral holes 37, 38, 39 connected respectively to inlet ducts 40, 41, 42 supplying water from different sources. The fixed disk 36 is also provided with an axial hole 43 connected to an outlet duct 44. Disposed matching with the disk 36 is a second disk 45 which can be rotated on its axis by means of an external control lever 46 which turns a shaft 47 coupled to the disk. The movable disk 45 has a hole 48 coaxial to the central hole 43 of the first disk and a peripheral hole 49 selectively matching with one of the peripheral holes in the fixed disk 36. Thus, by rotating the control lever 46 it is possible to connect one of the sources 40, 41, 42 to the outlet duct 44 which, when connected to the inlet duct of one of the previously described embodiments, supplies it alternatively with water. It is thus possible, for example with the embodiments of figures 1, 4, 12, for the control 20, 120, 420 to enable delivery from several sources by selection control by means of the device 34. It will be obvious at this point that the intended scopes are achieved by providing a tap-operated dispensing device for delivering water from different sources, while avoiding any possibility of undesirable mixing. The foregoing description of an embodiment applying the innovatory principles of this invention is obviously given by way of example in order to illustrate such innovatory principles and should not therefore be understood as a limitation to the sphere of the invention claimed herein. For example, the taps shown may also differ in shape in order to adapt to particular aesthetical or structural requirements. Moreover, even though the two delivery pipes are shown concentric, it will be obvious to any technician that it is also possible to obtain an embodiment with pipes disposed side by side or a single pipe divided by a longitudinal internal diaphragm. If complete separation of the paths for the water flowing from the two sets of sources connected to the two controls on the tap is not required, a single pipe can obviously be used. It will also be obvious to any technician that it is possible, in the embodiment shown in figures 1-3, to position the pin 31 biased elastically to the right, so that the movement of opening the lever 14 shifts the pin 31 towards the left to engage it in a housing in the element 27 thereby preventing it from rotating. Thus, contrarily, the movement of the lever 20 prevents the pin 31 from engaging in said housing and consequently the lever 14 cannot be slanted, thereby providing a locking device with reciprocal exclusion. Finally, the types of taps delivering water into the chambers 400 and 401 may differ from those shown. In fact, use may be made, for example, of two simple screw-type taps whenever there are only two sources to be kept separate, or of two mixing taps whenever there are two sets of water to be kept separate, each made up of two freely mixable sources.	A device (10, 110, 210, 310, 410) for dispensing water from at least one delivery outlet, comprising first means (19, 119, 391, 419, 281) for controlling the delivery from said outlet of water flowing from first sources, second means (13, 113, 213, 313, 413) for controlling the delivery from said outlet of water flowing from second sources, that at least said first means are operatively connected to disenabling means (31, 151, 280, 282, 331, 402) inhibiting delivery from the second means (13, 113, 213, 313, 413) when the first means are made to deliver water from their respective sources, characterized by the fact that at least the second means comprise a mixer tap (13, 113, 213, 313, 413) with two inlets connected to said second sources of water. Device as claimed in claim 1, characterized by the fact that said second means are operatively connected to further disenabling means (331) inhibiting delivery from the first means when the second means are made to deliver water from their respective sources. Device as claimed in claim 1, characterized by the fact that the first means comprise a cutoff tap with one inlet connected to said first sources of water. Device as claimed in claim 1, characterized by the fact that the disenabling means comprise a pin (31, 280, 282, 331) sliding axially against the action of a spring (32, 290, 332) when the first means are actuated in order to shift to a position in which it interferes with the movement for actuating the second means, to prevent it from opening to deliver water. Device as claimed in claim 4, characterized by the fact that the first means (19, 281) operated by rotating a control lever (20, 220) having a cam surface (29, 288) over which one end (30, 287) of the pin (31, 280, 282) slides during its axial sliding movement. Device as claimed in claim 4, characterized by the fact that when the pin (31, 331) is in the interfering position, it has one end (33, 333) which prevents a lever (14, 314) controlling the second means from shifting to a delivery position. Device as claimed in claim 6, characterized by the fact that the end (33, 333) of the pin which prevents the lever (14, 314) from shifting comprises an element constituting a wide surface which interferes with the shifting of said lever. Device as claimed in claim 7, characterized by the fact that the wide interference surface comprises a portion (30) shaped in the form of a semicircle so as to at least partially follow a rim covering the coupling of said lever and exert controlled interference thereon. Device as claimed in claim 1, characterized by the fact that the disenabling means comprise a piston (151) which is made to slide under the action of the flow of water from the first means into a first extreme position in which it obstructs the passage (117) between the second means and the delivery outlet, and made to slide under the action of the flow of water from the second means into a second opposite extreme position in which it obstructs the passage (123) between the first means and the delivery outlet. Device as claimed in claim 9, characterized by the fact that the piston (151) is biased by a spring (152) towards one of said extreme positions. Device as claimed in claim 1, characterized by the fact that the disenabling means comprise a shaft (280, 282) which slides axially to the movement of operation of the first means (281) to bring cutoff elements (283) in correspondence with flow passages in the second means (213). Device, as claimed in claim 1, characterized by the fact of comprising at least one selector device (34, 260) for selectively feeding a plurality of sources of water to an inlet of the delivery control means. Device as claimed in claim 11, characterized by the fact that the selector device (34, 260) comprises circumferentially disposed apertures each of which is connected to a source, over said apertures being axially rotatably disposed a disk (45, 272) tightly closing the apertures and having a passage which can be selectively positioned, on rotation of the disk, over one of said apertures to put it in communication with an inlet duct of the control means. Device as claimed in claim 11, characterized by the fact that the first means comprise a plug (281) for closing the passage between the source and the delivery outlet operatively connected to the sliding shaft (282) with the interposition of yielding elements, said sliding shaft being cam-operated by rotation of a control lever (220) in order to shift the cutoff elements (283) to the closed position before shifting the plug (281) to the open position. Device as claimed in claim 1, characterized by the fact that said disenabling means comprise a first chamber (400) for passage of the water between the first means (419) and the delivery outlet and a second chamber (401) for passage of the water between the second means (413) and the delivery outlet, said first and second chambers being divided by a flexible diaphragm (402), on aperture of the first means said diaphragm being flexed by the pressure of the water in the first chamber from a position of non-interference with the passage of the water between the second means and the delivery outlet to a position in which it closes the passage of the water between the second means and the delivery outlet. Device as claimed in claim 15, characterized by the fact that the delivery outlet is connected to the first and second chamber by means of respective first (418) and second ducts (424) disposed substantially co-axial, the first duct (418) being disposed inside the second duct (424) and having one end entering the first chamber (400) by passing through the second chamber (401) and the diaphragm (402). Device as claimed in claim 16, characterized by the fact that in its closing position the diaphragm rests on the mouth of the second duct in the second chamber. Device as claimed in claim 15, characterized by the fact that disposed between the first chamber (400) and delivery outlet (405) is a valve (408) which opens at a pre-established pressure, said opening pressure being greater than the pressure necessary in the first chamber to shift the diaphragm (402) to its closing position. Device as claimed in claim 18, characterized by the fact that the valve (408) comprises a piston (409 biased by a spring (454) against the flow of water to close an aperture through which it flows. Device as claimed in claim 1, characterized by the fact that the paths between the first means and the delivery outlet and between the second means and the delivery outlet are kept completely separate in order to prevent any mixing between the water flowing from the first sources and the water flowing from the second sources. Device as claimed in claim 20, characterized by the fact that said paths comprise two different ducts coaxially placed to form a single pipe. Device as claimed in claim 1, characterized by the fact that the delivery outlet leads off from a delivery head disposed at the end of a horizontally orientable pipe. Device as claimed in claim 22, characterized by the fact that the delivery head is rotatingly connected to the pipe according to a substantially horizontal axis.	TELMA GUZZINI S R L; TELMA GUZZINI S.R.L.	MORETTI GIOVANNI; MORETTI, GIOVANNI
EP-0489457-B1	489,457	EP	B1	EN	19,960,501	1,992	20,100,220	new	H04N9	H01J31	H04N9, G09G1, H01J29, H01J31	H04N 9/12, G09G 1/20	Flat-panel picture display device	Picture display device having a vacuum envelope with a face plate whose inner side is provided with a luminescent screen having a repetitive pattern of triplets of red, green and blue-luminescing phosphor elements, a rear plate at a short distance therefrom and in the space therebetween a plurality of electron emitters and juxtaposed, electron ducts cooperating therewith and having walls of substantially electrically insulating material having a secondary emission coefficient suitable for electron transport for transporting, through vacuum, produced electrons in the form of electron currents. Means are provided for withdrawing each electron current at predetermined locations from its duct and for directing this current towards a desired location on the luminescent screen for producing a picture composed of pixels.	The invention relates to a colour picture display device having a vacuum envelope with a front wall and a luminescent screen and with a rear wall, and particularly relates to a flat-panel picture display device (i.e. a picture display device having a small front-to-back dimension ) which is clearly distinguished from state-of-the-art display devices. Many research efforts in the field of picture display devices of the flat-panel type relate to devices having a transparent face plate and a rear plate which are interconnected by means of side walls and in which the inner side of the face plate is provided with a phosphor pattern, one side of which is provided with an electrically conducting coating (the combination generally being referred to as luminescent screen). A large number of electron-beam producing means is generally arranged on the rear plate and a large number of deflection means is provided to cause each produced electron beam to scan a part of the luminescent screen. If (video information-controlled) electron beams impinge upon the luminescent screen, a visual image is formed which is visible via the front side of the face plate. (The expression electron beam is understood to mean that the paths of the electrons in the beam are substantially parallel, or extend only at a small angle to one another, and that there is a main direction in which the electrons move.) The electron-beam controlled devices hitherto known require, inter alia, complicated electron-beam producing, focusing and/or amplifying means and complicated deflection means. In the case of a thin CRT display device having a flat face plate and rear plate the atmospheric pressure exerts a great force on the face plate and on the rear plate. The larger the dimensions of the display screen, the thicker the face plate and the rear plate must be, if internally no measures are taken. In view of the foregoing it is an object of the invention to provide a flat-panel picture display device which substantially does not have the drawbacks of the above-mentioned devices. According to the invention, a colour picture display device having a vacuum envelope with a front wall and a luminescent screen and with a rear wall therefore comprises a plurality of juxtaposed sources for emitting electrons, electron ducts adjacent to the rear wall and cooperating with the sources and having walls of substantially electrically insulating material having a secondary emission coefficient suitable for electron transport for transporting, through vacuum, electrons in the form of electron currents, means for withdrawing each electron current at predetermined (particularly successive) locations from its duct and means for directing said current towards a desired location on the luminescent screen, said luminescent screen having a repetitive pattern of triplets of dot-shaped phosphor elements luminescing in different colours (for example, red, green and blue), a flu-spacer structure of electrically insulating material being arranged adjacent to the luminescent screen. A flu-spacer structure is herein understood to mean a spacer which is adjacent to the luminescent screen. The inventive approach of providing a flat-panel picture display device is based on the discovery that electron transport is possible when electrons impinge on a wall of an elongate evacuated cavity (referred to as compartment) defined by walls of high-ohmic, electrically substantially insulating material (for example, glass) if an electric field of sufficient power is realised in the longitudinal direction of the compartment (by applying an electric potential difference across the ends of the compartment). The impinging electrons then generate secondary electrons by wall interaction which are attracted to a further wall section and in their turn generate secondary electrons by wall interaction. As will be further described, the circumstances (field strength, electrical resistance of the walls, secondary emission coefficient δ of the walls) may be chosen to be such that a constant vacuum current will flow in the compartment. By withdrawing electrons at desired locations (via apertures) from the compartments and directing them towards a luminescent screen, for example, by means of an accelerating field, a picture can then be formed on the luminescent screen. The maximal landing reserve is obtained by forming the colour pattern of dot-shaped phosphor elements on the luminescent screen as a delta configuration (triplets arranged in a triangular form). This landing reserve may be, for example, larger than in the case of a screen with colour lines. In EP-A-400 750, which is a prior art document according to article 54 (3), EPC, a flat screen colour display device is disclosed which has a such luminescent screen with triplets of red, green and blue phosphor lines. Moreover, in the case of matrix-oriented displays with a screen of colour lines, artefacts may occur in the picture (for example, a striped structure), which artefacts are now avoided. A first embodiment is characterized in that the means for directing each electron current to a desired location on the luminescent screen comprise an apertured selection plate of electrically insulating material separated from the luminescent screen by the flu-spacer structure, each aperture of the selection plate being associated with one of the dot-shaped phosphor elements via an aperture in the (in particular plate-shaped or honeycomb-shaped) flu-spacer structure. If the following components are present, the desired vacuum support is obtained by the combination: side walls of the electron ducts-selection plate-flu-spacer structure. The flu-spacer structure may be, for example, a system of mutually parallel walls extending at an angle (of approximately 60°) to the side walls of the electron ducts. This is possible because of the delta configuration of the phosphor elements and leads to a stabler construction than in the case where said side walls and the spacer walls would be parallel. A preferred embodiment is, however, characterized in that the flu-spacer structure comprises a plate-shaped or honeycomb-shaped structure having apertures which associate each dot-shaped phosphor element with one aperture in the adjacent selection plate. In addition to a greater stability, the use of these structures has the extra advantage that electrons backscattered from the luminescent screen cannot land on other dot-shaped phosphor elements, which leads to a better contrast and a better colour purity. A selection means is provided by providing the apertures in the selection plate row by row with electrodes which are energizable by means of a first (positive) electric voltage (pulse) so as to withdraw electron currents from the ducts via the apertures of a row, or they are energizable by means of a second (lower) electric voltage if no electrons should be locally withdrawn from the ducts. The electrons extracted by this selection means can be directed towards the screen by applying an acceleration voltage. All electron currents generated by the electron sources should be guided in the electron ducts across at least a part of the height towards the upper edge or the lower edge of the luminescent screen. For this purpose one row of electron sources or a plurality of parallel rows of electron sources may be provided. Each of these electron sources may be placed within the electron duct with which it cooperates, or they are alternatively located at the outer side, opposite an entrance portion, of the electron duct with which they cooperate. By applying a sufficiently large positive voltage difference between an electron source and the entrance portion of an electron duct cooperating-therewith, the emitted electrons are accelerated towards the electron duct, whereafter they generate secondary electrons in the electron duct by means of wall interaction. Electrons which are line-sequentially withdrawn from the electron ducts can be accelerated (as beams) towards the luminescent screen by a applying a sufficiently large voltage difference between the electron ducts and the screen, for example, a difference of 3 kV. One picture line at a time can thus be written. The video information (grey scales) can be presented, for example, in the form of pulse width modulation. The distance to the screen may be very small so that the spot remains small. These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter. Identical reference numerals are used for corresponding components. Fig. 1 is a diagrammatic perspective elevational view, partly broken away, of a part of a construction of a picture display device according to the invention, with electron ducts, a selection plate and a flu-spacer structure, whose components are not drawn to scale; Fig. 1A is a side elevation, broken away, of the construction of Fig. 1 to illustrate the general operation of the device according to the invention; Fig. 1B is a front elevation of a part of the - apertured - selection plate used in the construction of Fig. 1, Fig. 1C is an elevational view of a part of a selection plate provided with selection electrodes, viewed through the apertures in an adjacent flu-spacer structure, Fig. 2 shows a similar selection plate as Fig. 1B for an alternative construction, Fig. 3 shows a graph in which the secondary emission coefficient δ as a function of the primary electron energy Ep is plotted for a wall material which is characteristic of the invention, Fig. 4 is a vertical cross-section through a part of a construction with selection plates for preselection and fine selection, which is an alternative to the construction of Fig. 1A, Fig. 5 shows an alternative construction for the preselection, Fig. 6 shows a detail of Fig. 5, and Fig. 7 shows a honeycomb-shaped spacer structure for an alternative construction. Figs. 1 and 1A show a flat-panel picture display device 1 according to the invention having a display panel (window) 3 and a rear wall 4 located opposite said panel. A luminescent screen 7 having a repetitive pattern of triplets of red (R), green (G) and blue (B) luminescing phosphor elements, as shown in the inset, is arranged on the inner surface of window 3. In the relevant case the dot-shaped phosphor elements of a triplet are located at the apexes of an equilateral triangle with side a. An electron source arrangement 5,for example, a line cathode which by means of electrodes provides a large number of electron emitters, for example 600, or a similar number of separate emitters, is present proximate to a wall 2 which connects panel 3 and the rear wall. Each of these emitters is to provide a relatively small current so that many types of cathodes (cold or thermal cathodes) are suitable as emitters. The emitters may be arranged jointly or separately. They may have a constant or controllable emission. The electron source arrangement 5 is arranged opposite entrance apertures of a row of electron ducts extending substantially parallel to the screen, which ducts are constituted by compartments 6, 6', 6'', ..... etc., in this case one compartment for each electron source. These compartments have cavities 11, 11', 11'', .... defined by walls. At least one wall (preferably the rear wall) of each compartment is made of a material which has a suitable high electrical resistance for the purpose of the invention (for example, ceramic material, glass, synthetic material - coated or uncoated) and which have a secondary emission coefficient δ > 1 over a given range of primary electron energies (see Fig. 3). The electrical resistance of the wall material has such a value that a minimum possible total amount of current (preferably less than, for example, 10 mA) will flow in the walls in the case of a field strength in the axial direction in the compartments of the order of one hundred to several hundred volts per cm required for the electron transport. By applying a voltage of the order of several dozen to several hundred volts (value of the voltage is dependent on circumstances) between the row 5 of electron sources and the compartments 6, 6', 6'', electrons are accelerated from the electron sources towards the compartments, whereafter they impinge upon the walls in the compartments and generate secondary electrons. The invention is based on the recognition that vacuum electron transport within compartments having walls of electrically insulating material is possible if an electric field (Ey) of sufficient power is applied in the longitudinal direction of the compartment. Such a field realises a given energy distribution and spatial distribution of electrons injected into the compartment so that the effective secondary emission coefficient δeff of the walls of the compartment will on average be equal to 1 in operation. Under these circumstances one electron will leave for each electron which enters (on average), in other words, the electron current is constant throughout the compartment and is approximately equal to the current which enters. If the wall material is high-ohmic enough (which is the case for all appropriate untreated glass types as well as for kapton, pertinax and ceramic materials), the walls of the compartment cannot produce or take up any nett current so that this current, even in a close approximation, is equal to the entering current. If the electric field is made larger than the minimum value which is required to obtain emission coefficient δeff = 1, the following will happen. As soon as δeff is slightly larger than 1, the wall is charged inhomogeneously positively (due to the very small conductance this charge cannot be depleted). As a result, the electrons will reach the wall earlier on average than in the absence of this positive charge, in other words, the average energy taken up from the electric field in the longitudinal direction will be smaller so that a state with δeff = 1 adjusts itself. This is a favourable aspect because the exact value of the field is not important, provided that it is larger than the previously mentioned minimum value. Another advantage is that in the state δeff = 1 the electron current in the compartment is constant and can be made to be very satisfactorily equal via measuring and feedback or via current control for each compartment 50 that a uniform picture can be realised on the luminescent screen. The compartment walls facing the luminescent screen 7, which is arranged on the inner wall of the panel 3, are constituted by a selection plate 10 (see Fig. 1A) in the embodiment of Fig. 1. The selection plate 10 has extraction apertures 8, 8', 8'', .... etc. Individually driven emitters are preferably used in combination with a pattern of parallel, apertured strip-shaped selection electrodes 9, 9', 9'', .... to be energized by a selection voltage. These electrodes are present on one of the main surfaces of the plate 10, or on both main surfaces. In both cases the walls of the apertures 8, 8', 8'', .... may be metallized. A flu-spacer structure 12, in this case a plate having apertures 14, ... which form a connection between the apertures 8, 8', 8'', ..... and the phosphor elements R, G, B ..... keeps the plate 10 spaced apart from face plate 3 and ensures a lateral localization of extracted electron beams in that the apertures 14, ... closely surround the electron beam paths. If selection electrodes are arranged on the surface of the plate 10 facing the screen 7, it is advantageous if they entirely cover at least those surface areas which are located between the walls of the apertures 14 of the structure 12 (see, for example Fig. 1C). The selection electrodes 9, 9', 9'', .... are formed for each picture line, for example, in the manner shown in Fig. 1B (pierced electrodes widening at the areas of the apertures 8, 8', 8'', ....). The material of the electrodes may cover the walls of the apertures 8, 8', 8'', ... . Desired locations on the screen 7 can be addressed by means of (matrix) drive of the individual cathodes and the selection electrodes 9, 9', 9'', .... Voltages which increase substantially linearly (as viewed from the cathode side) are applied to the selection electrodes 9, 9', 9'', ....., for example, by means of voltage-dividing resistors. When a picture line must be activated, i.e. when electrons must be withdrawn via apertures in an aperture row from the electron currents flowing behind them in parallel columns, a pulsatory voltage ΔU can be added to the local voltage. In view of the fact that the electrons in the compartments have a relatively low velocity due to the collisions with the walls, ΔU may be comparatively low (of the order of, for example, 100 V to 200 V). A voltage difference Va is applied across the total compartment height so as to supply the transport field. The materials to be used for the walls of the electron ducts must have a high electrical resistance and a secondary emission coefficient δ > 1, see Fig. 3, at least over a certain range EI-EII of primary electron energies Ep. EI is preferably as low as possible, for example, one to several times 10 eV. Inter alia, specific types of glass (EI is approximately 30 eV), ceramic material, pertinax and kapton meet this requirement. Materials which do not meet this requirement may be provided, for example, with a suitable coating (of, for example, MgO). The electrical resistance depends on whether not only electron guidance but also amplification (over a part or over the total length) of the electron ducts is desired and how much total current may flow in the walls in connection with the power to be dissipated. The mode using electron guidance only is preferred. The electrical resistance may then be in the range between 10⁶ and 10¹⁵ Ω. As an alternative the cathode-sided portion of the electron ducts may have a relatively low resistance, for example, in the range between 10 kΩ and 100 kΩ so as to ensure amplification. At the above-mentioned values the required power can remain below 100 W. In a given case electron transport was realised in a compartment of lead glass with a length of 17 cm and a bore of 1 mm diameter (electrical resistance measured over the length > 10¹⁵ Ω) by applying an electric voltage of 3.5 kV across the ends. It is further to be noted that the walls of the ducts may consist of an electrically insulating material which has a constructive function as well as a secondary emission function. Alternatively, they may consist of an electrically insulating material having a constructive function (for example, a synthetic material), on which material a layer having a secondary emission function is provided (for example, quartz or glass or ceramic material such as MgO). The electric voltage across the electron ducts required for electron guidance increases with the length of the ducts. However, this voltage can be reduced by arranging the (line) arrangement of electron sources in, for example, the centre instead of near one end of the display device (as in Fig. 1). A voltage difference of, for example, 3 kV can then be applied between the centres of the ducts and their one ends so as to draw the electron current in one direction and subsequently the same voltage difference can be applied between the centres and their other ends so as to draw the electron current in the opposite direction, instead of applying a voltage difference of 6 kV throughout the height when the electron sources are arranged near one end of the display device. The use of a plurality of parallel rows of electron sources is even more advantageous in this respect. Electrons which are drawn from an aperture in an electron duct by a selection electrode are further directed towards the luminescent screen 7 where one picture line at a time can thus be written. The video information may be applied, for example, in the form of pulse width modulation. For example, a cathode cooperating with an electron duct can be energized for a shorter or longer time. For producing a white pixel, the cathode may be energized, for example, during the entire line period in this case. An alternative is for the cathode to be constantly energized during the entire line period and to control the emission level. Fig. 2 is an elevational view of a part of a selection plate 20 having apertures and selection strips. The phosphor elements R, G, B etc. of the luminescent screen are visible through the apertures. These elements are arranged in the manner as shown in the inset of Fig. 1. In this case the selection plate 20 does not cooperate with a plate-shaped spacer structure (having a hexagonal pattern of apertures), but with a spacer structure having mutually parallel walls 21, 22, 23, 24, .... arranged at a pitch a and extending at an angle of approximately 60° to electron duct side walls 25, 26, 27, ..... arranged at a pitch of a√3. As already noted in the opening paragraph, the use of an apertured, plate-shaped structure or a honeycomb spacer structure has advantages over the use of a spacer structure having walls arranged at an angle of 60°, as far as contrast and colour purity are concerned. A part of a honeycomb structure 28 is shown in Fig. 7. Fig. 4 shows in a diagrammatical cross-section an embodiment of a part of a display device according to the invention having a selection plate structure 32 which comprises a preselection plate 29A with apertures 31, 31', .... and a fine-selection plate 29B with apertures R, G, B. In this case three fine-selection apertures R, G, B are associated with each preselection aperture 31, 31', etc. (see inset). Other numbers are also possible. An intermediate spacer structure 29C is arranged between the preselection plate 29A and the fine-selection plate 29B. Electron transport ducts 30 are formed between the structure 32 and a rear wall. To be able to draw electrons from the transport ducts 30 via the apertures 31, 31', ...., pierced metal preselection electrodes 34, 34', etc. are arranged on the plate 29A. The walls of the apertures 31, 31',... are plated through, but there is little or no metal on the surface of plate 29A at the side where the electrons arrive. This is to ensure that no electrons remain on a selection electrode during addressing (i.e. the electrode should not draw current). Another solution to the problem of drawing current is to ensure that if there is electrode metal on the selection plate surface on which the electrons land, this metal has such a large secondary emission coefficient that the preselection electrodes do not draw any nett current. Similarly as the plate 10 of the Fig. 1 construction, the fine-selection plate 29B has (fine-) selection electrodes so as to realise colour selection. In this respect it is important that it should be possible to give the colour selection electrodes an electric through-connection for each colour (for example, via coupling capacitors). In fact, a preselection has already taken place and electrons can no longer reach the wrong location. This means that only one group, or a small number of groups, of three separately energizable colour selection electrodes is required for this form of colour selection. Although other modes are alternatively possible, the drive is effected, for example, as follows. Both the coarse-selection and the fine-selection electrodes are given a substantially linearly increasing potential (for example, by means of suitable voltage-dividing resistors), the fine-selection electrodes being at a slightly lower potential than the coarse-selection electrodes. One (or more) picture lines are selected by applying a positive voltage pulse of, for example 200 V to the desired coarse-selection electrode. The colour pixels are subsequently addressed by applying shorter pulses with an amplitude of, for example, 300 V to the fine-selection electrodes. The fine-selection plate 29B may be separated from the luminescent screen by one of the afore-mentioned flu-spacer structures (12'' in Fig. 1; 21 , 22 , 23 , 24 in Fig. 2; 28 in Fig. 7). The material of the flu-spacer preferably has either a low secondary emission, or a coating having this property should be provided on it. In addition, another condition for a satisfactory operation is important: each (fine-) selection electrode should be dimensioned in such a way that there is no isolator material of the selection plate to be seen when one looks through the spacer apertures, cf. Fig. 1C. Fig. 5 shows diagrammatically a part of a selection plate 40 constituting the front wall of transport ducts 41, 41', 41'', ..... with a pitch P. The horizontal picture resolution is determined by the pitch of the transport ducts. A better resolution can thus be obtained by reducing this pitch. However, this has the drawback that the voltage difference across the length of the ducts required for transporting the electron currents will increase, which is not always desirable. This problem can be solved by means of an adapted pattern of selection apertures and electrodes, in which the pitch of the transport ducts is unmodified, as will be illustrated with reference to Fig. 5. Fig. 5 shows the case where two preselection apertures are provided for each preselection location in each row, with a pitch (p/2). Each selection electrode 42 is divided in the manner shown into two apertured sub-electrodes 43a and 43b, which simplifies contacting. In this way the horizontal resolution can be doubled with respect to the construction shown in Fig. 4, while the transport ducts 11, 11', 11'', ...... cooperating with one electron emitter each can be operated in the same way and with the same voltages. Three fine-selection apertures in a fine-selection plate for selecting the colours red (R), green (G) and blue (B) are associated with each preselection aperture 44, 44', ...., for example, as shown in Fig. 6. The system described herein can be operated in the multiplex mode. This means that, for example, two parallel electron currents and six luminescent elements can be driven (multiplexed) in one line period by means of one electron emitter. Other multiplex modes are alternatively possible.	A colour picture display device having a vacuum envelope with a front wall and a luminescent screen and with a rear wall, comprising a plurality of juxtaposed sources for emitting electrons, electron ducts adjacent to the rear wall and cooperating with the sources and having walls of substantially electrically insulating material having a secondary emission coefficient suitable for electron transport for transporting, through vacuum, electrons in the form of electron currents, means for withdrawing each electron current at predetermined locations from its duct and means for directing said current towards a desired location on the luminescent screen, said luminescent screen having a repetitive pattern of triplets of dot-shaped phosphor elements Luminescing in different colours, a flu-spacer structure of electrically insulating material being arranged adjacent to the luminescent screen. A device as claimed in Claim 1, characterized in that the means for directing each electron current to a desired location on the luminescent screen comprise an apertured selection plate of electrically insulating material separated from the luminescent screen by the flu-spacer structure, each aperture of the selection plate being associated with one of the dot-shaped phosphor elements via an aperture in the flu-spacer structure. A device as claimed in Claim 2, characterized in that the flu-spacer structure comprises a plate-shaped or honeycomb-shaped structure having apertures which associate each dot-shaped phosphor element with one aperture in the selection plate. A device as claimed in Claim 2, characterized in that the selection plate cooperates with an apertured preselection plate, the apertures in the preselection plate communicating with the transport ducts, an intermediate spacer structure being arranged between the preselection plate and the selection plate and each aperture in the preselection plate being associated with at least two apertures in the selection plate. A device as claimed in Claim 4, characterized in that each aperture in the preselection plate is associated with three apertures in the selection plate and in that of said three apertures one is associated with a red-luminescing phosphor element, one is associated with a blue-luminescing phosphor element and one is associated with a green-luminescing phosphor element of one triplet. A device as claimed in Claim 2 or 4, characterized in that the apertures in the (pre)selection plate are provided row by row with strip-shaped (pre)selection electrodes which are pierced at the locations of the apertures. A device as claimed in Claim 6, characterized in that the (pre)selection electrodes are connected together via voltage-dividing resistors. A device as claimed in Claim 6, characterized in that the selection electrodes are electrically through-connected per colour. A device as claimed in Claim 4, characterized in that each transport duct communicates with two parallel rows of apertures in the preselection plate. A device as claimed in Claim 9, characterized in that the electron ducts have a pitch which is twice as large as that of the triplets of luminescing phosphor elements. A device as claimed in Claim 6, characterized in that the strip-shaped (pre)selection electrodes are arranged on the screen-sided surface of the (pre)selection plate. A device as claimed in Claim 11, characterized in that, viewed through the apertures of the flu-spacer structure, around the apertures in the selection plate only material of the selection electrodes is visible.	PHILIPS ELECTRONICS NV; PHILIPS ELECTRONICS N.V.	DE ZWART SIEBE TJERK; LAMBERT NICOLAAS; TROMPENAARS PETRUS HUBERTUS FR; VAN GORKOM GERARDUS GEGORIUS P; DE ZWART, SIEBE TJERK; LAMBERT, NICOLAAS; TROMPENAARS, PETRUS HUBERTUS FRANCISCUS; VAN GORKOM, GERARDUS GEGORIUS PETRUS
EP-0489458-B1	489,458	EP	B1	EN	19,950,607	1,992	20,100,220	new	C07D401	A61K31	A61K31, C07D401, A61P25	M07D401:04, M07D401:04+21+207, C07D 401/04, M07D401:04+233+215, M07D401:04+249B+215, M07D401:04+231+215, M07D401:04+215+209C, M07D401:04+215+207, M07D401:04+215+213	Hydroxyquinolone derivatives	A class of 4-hydroxy-2(1H)-quinolone derivatives, substituted at the 3-position by an N-linked heteroaromatic ring system, are selective non-competitive antagonists of NMDA receptors and/or are antagonists of AMPA receptors, and are therefore of utility in the treatment of conditions, such as neurodegenerative disorders, convulsions or schizophrenia, which require the administration of an NMDA and or AMPA receptor antagonist.	This invention relates to a class of 4-hydroxy-2(1H)-quinolones which are substituted in the 3-position by an optionally substituted heteroaromatic ring system. These compounds are selective non-competitive antagonists of N-methyl-D-aspartate (NMDA) receptors. More particularly, the class of compounds provided by the present invention are ligands for the strychnine-insensitive glycine modulatory site of the NMDA receptor and are therefore useful in the treatment and/or prevention of neurodegenerative disorders arising as a consequence of such pathological conditions as stroke, hypoglycaemia, cerebral palsy, transient cerebral ischaemic attack, cerebral ischaemia during cardiac pulmonary surgery or cardiac arrest, perinatal asphyxia, epilepsy, Huntington's chorea, Alzheimer's disease, Amyotrophic Lateral Sclerosis, Parkinson's disease, Olivo-ponto-cerebellar atrophy, anoxia such as from drowning, spinal cord and head injury, and poisoning by exogenous and endogenous NMDA receptor agonists and neurotoxins, including environmental neurotoxins. By virtue of their NMDA receptor antagonist properties, the compounds according to the present invention are also useful as anticonvulsant and antiemetic agents, as well as being of value in the prevention or reduction of dependence on dependenceinducing agents such as narcotics. NMDA receptor antagonists have recently been shown to possess analgesic (see, for example, Dickenson and Aydar, Neuroscience Lett., 1991, 121, 263; Murray etal., Pain, 1991, 44, 179; and Woolf and Thompson, Pain, 1991, 44, 293), antidepressant (see, for example, Trullas and Skolnick, Eur. J. Pharmacol., 1990, 185, 1) and anxiolytic (see, for example, Kehne etal., Eur. J. Pharmacol., 1991, 193, 283) effects, and the compounds of the present invention may accordingly be useful in the management of pain, depression and anxiety. The association of NMDA receptor antagonists with regulation of the nigrostriatal dopaminergic system has recently been reported (see, for example, Werling etal., J. Pharmacol. Exp. Ther., 1990, 255, 40; Graham etal., Life Sciences, 1990, 47, PL-41; and Turski etal., Nature (London), 1991, 349, 414). This suggests that the compounds of the present invention may thus be of assistance in the prevention and/or treatment of disorders of the dopaminergic system such as schizophrenia and Parkinson's disease. It has also been reported recently see Lauritzen etal., Journal of Cerebral Blood Flow and Metabolism, 1991, vol. 11, suppl. 2, Abstract XV-4) that NMDA receptor antagonists block cortical spreading depression (CSD), which may thus be of clinical importance since CSD is a possible mechanism of migraine. The class of substituted 2-amino-4-phosphonomethylalk-3-ene carboxylic acids and esters described in EP-A-0420806, which are stated to be selective NMDA antagonists, are alleged thereby to be of potential utility in the treatment of interalia migraine. Excitatory amino acid receptor antagonists, including interalia antagonists of NMDA receptors, are alleged in EP-A-0432994 to be of use in suppressing emesis. Recent reports in the literature have also suggested a link between the neurotoxicity of certain viruses and the deleterious effects of these viruses on an organism caused by the potentiation of neurotransmission via excitatory amino acid receptors. By virtue of their activity as antagonists of NMDA receptors, therefore, the compounds of the present invention may be effective in controlling the manifestations of neuroviral diseases such as measles, rabies, tetanus (cf. Bagetta etal., Br. J. Pharmacol., 1990, 101, 776) and AIDS (cf. Lipton etal., Society for Neuroscience Abstracts, 1990, 16, 128.11). NMDA antagonists have, moreover, been shown to have an effect on the neuroendocrine system. (see, for example, van den Pol etal., Science, 1990, 250, 1276; and Urbanski, Endocrinology, 1990, 127, 2223) and the compounds of this invention may therefore also be effective in the control of seasonal breeding in mammals. In addition, certain compounds of the invention are antagonists of 2-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptors, also known as quisqualate receptors. An excitatory amino acid projection from the prefrontal cortex to the nucleus accumbens (a particular region of the forebrain possessing dopamine-sensitive neurones) is well known to exist (see, for example, J. Neurochem., 1985, 45, 477). It is also well known that dopaminergic transmission in the striatum is modulated by glutamate (see, for example, Neurochem. Int., 1983, 5, 479), as also is the hyperactivity associated with presynaptic stimulation of the dopamine system by AMPA in the nucleus accumbens (cf. Life Sci., 1981, 28, 1597). Compounds which are antagonists of AMPA receptors are therefore of value as neuroleptic agents. A class of 4-hydroxy-2(1H)-quinolone derivatives, substituted at the 3-position by an optionally substituted benzotriazole ring system, is described in JP-A-50-159483. These compounds are stated to have u.v.-absorbing properties and thus to be useful as u.v. light stabilisers in the production of such things as cosmetics, fibres, foods and drugs. No therapeutic utility is disclosed for the compounds described in this publication. In particular, there is no suggestion that the compounds described therein would be of assistance in solving the problem of providing an effective agent for the treatment and/or prevention of conditions requiring the administration of an antagonist of NMDA and/or AMPA receptors. EP-A-0303387 describes a class of 4-oxo-1,4-dihydroquinoline derivatives which are stated to be specific antagonists of NMDA receptors as well as being, in some cases, potent kainate/quisqualate antagonists. These compounds are stated therein to be useful in the treatment of a variety of neurodegenerative disorders. The present invention accordingly provides a pharmaceutical composition comprising a compound of formula I or a pharmaceutically acceptable salt thereof or a prodrug thereof: wherein R¹ represents a group of formula (i), (ii) or (iii): in which E represents the residue of a five-membered heteroaromatic ring containing zero, 1, 2 or 3 further nitrogen atoms; R² and R³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃ -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom, or, where appropriate, a non-bonded electron pair; or R² and R³, when situated on adjacent atoms, together represent the residue of a saturated or unsaturated 4- to 9-membered carbocyclic or heterocyclic ring; and R⁴ represents hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; R⁵, R⁶, R⁷ and R⁸ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; and Ra and Rb independently represent hydrogen, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; in association with one or more pharmaceutically acceptable carriers and/or excipients. The invention also provides a compound of formula I as defined above or a pharmaceutically acceptable salt thereof or a prodrug thereof for use in therapy. In a further aspect, the present invention provides the use of a compound of formula I as defined above or a pharmaceutically acceptable salt thereof or a prodrug thereof for the manufacture of a medicament for the treatment and/or prevention of conditions, in particular neurodegenerative disorders, which require the administration of a selective non-competitive antagonist of NMDA receptors. The present invention further provides the use of a compound of formula I as defined above or a pharmaceutically acceptable salt thereof or a prodrug thereof for the manufacture of a medicament for the treatment and/or prevention of conditions, such as schizophrenia, which require the administration of an antagonist of AMPA receptors. The compound of formula I will in general exist in equilibrium with its other tautomeric forms, including those structures of formulae A to D: wherein R¹ and R⁵ to R⁸ are as defined with reference to formula I above. Indeed, in the prior art reference cited above, the compounds disclosed therein are designated by reference to tautomeric form (D) above. It is to be understood that all tautomeric forms of the compounds of formula I, as well as all possible mixtures thereof, are included within the scope of the present invention. The term hydrocarbon as used herein refers to straight-chained, branched and cyclic groups containing up to 18 carbon atoms, suitably up to 15 carbon atoms, and conveniently up to 12 carbon atoms. Suitable hydrocarbon groups include C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, C₃₋₇ cycloalkyl, C₃₋₇ cycloalkyl(C₁₋₆)alkyl, aryl and aryl(c₁₋₆)alkyl. The expression a heterocyclic group as used herein refers to groups containing up to 18 carbon atoms and at least one heteroatom preferably selected from oxygen, nitrogen and sulphur. The heterocyclic group suitably contains up to 15 carbon atoms and conveniently up to 12 carbon atoms, and is preferably linked through carbon. Examples of suitable heterocyclic groups include c₃₋₇ heterocycloalkyl, C₃₋₇ heterocycloalkyl(C₁₋₆)alkyl, heteroaryl and heteroaryl(C₁₋₆)alkyl. Suitable alkyl groups include straight-chained and branched alkyl groups containing from 1 to 6 carbon atoms. Typical examples include methyl and ethyl groups, and straight-chained or branched propyl and butyl groups. Particular alkyl groups are methyl, ethyl and t-butyl. Suitable alkenyl groups include straight-chained and branched alkenyl groups containing from 2 to 6 carbon atoms. Typical examples include vinyl and allyl groups. Suitable alkynyl groups include straight-chained and branched alkynyl groups containing from 2 to 6 carbon atoms. Typical examples include ethynyl and propargyl groups. Suitable cycloalkyl groups include groups containing from 3 to 7 carbon atoms. Particular cycloalkyl groups are cyclopropyl and cyclohexyl. Suitable aryl groups include phenyl and naphthyl groups. A particular aryl(C₁₋₆)alkyl group is benzyl. Suitable heterocycloalkyl groups include piperidyl, piperazinyl and morpholinyl groups. Suitable heteroaryl groups include pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, indolyl, pyranyl, furyl benzofuryl, thienyl, benzthienyl, imidazolyl, oxadiazoly and thiadiazolyl groups. Particular heteroaryl groups are pyridyl and oxadiazolyl. The five-membered heteroaromatic ring of which E is the residue may be, for example, a pyrrole, pyrazole, imidazole, triazole or tetrazole ring, preferably a pyrrole ring. Where R² and R³ together represent the residue of a saturated or unsaturated 4- to 9-membered carbocyclic or heterocyclic ring, the ring will preferably be a 5- or 6-membered ring. Where R² and R³ together represent the residue of a heterocyclic ring, this ring may contain up to four heteroatoms selected from oxygen, nitrogen and sulphur. Where the heteroatom is nitrogen it may, where appropriate, be shared with the heteroaromatic ring of which E is the residue Suitable carbocyclic rings completed by R² and R³ include cyclohexane, cyclohexene, cyclohexadiene and benzene rings. Suitable heterocyclic rings completed by R² and R³ include pyridine, pyrrole, furan, thiophene, thiazole and thiadiazole rings. Alternatively, R² and R³ may suitably together represent a methylenedioxy or ethylenedioxy group. The hydrocarbon and heterocyclic groups, as well as the carbocyclic or heterocyclic ring completed by R² and R³, may in turn be optionally substituted by one or more groups selected from C₁₋₆ alkyl, adamantyl, phenyl, halogen, C₁₋₆ haloalkyl, trifluoromethyl, hydroxy, C₁₋₆ alkoxy, aryloxy, keto, C₁₋₃ alkylenedioxy, nitro, cyano, carboxy, c₂₋₆ alkoxycarbonyl, c₂₋₆ alkoxycarbonyl(C₁₋₆)alkyl, C₂₋₆ alkylcarbonyloxy, arylcarbonyloxy, C₂₋₆ alkylcarbonyl, arylcarbonyl, C₁₋₆ alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ alkylsulphonyl, amino, mono- or di(C₁₋₆)alkylamino, C₂₋₆ alkylcarbonylamino and C₂₋₆ alkoxycarbonylamino. The term halogen as used herein includes fluorine, chlorine, bromine and iodine, especially chlorine. Particular values for the substituents R² and R³ include hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, di(C₁₋₆)alkylamino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, aryl, aryl(C₁₋₆)alkyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, aryloxy, aryl(C₁₋₆)alkoxy, C₁₋₆ alkylthio and C₂₋₇ alkoxycarbonyl. Suitably, one of R² and R³ represents hydrogen and the other represents hydrogen, halogen, trifluoromethyl, nitro, dimethylamino, C₁₋₆ alkyl, phenyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, phenoxy or phenyl(C₁₋₆)alkoxy. Alternatively, when the five-membered ring of which E is the residue is a triazole or tetrazole ring, one or both of R² and R³ is a non-bonded electron pair. Preferably, at least one of R² and R³ is other than hydrogen. Where R² and R³ together represent the residue of a carbocyclic or heterocyclic ring, this may be, in particular, an optionally substituted benzene ring. The substituent R⁴ may be, for example, hydrogen, C₁₋₆ alkyl or aryl. Preferably, R⁴ is hydrogen, methyl or phenyl. The benzo moiety of the hydroxyquinolone ring system shown in formula I above may be substituted or unsubstituted. Particular substituents include halogen, cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphonyl, nitro, hydroxy, amino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₁₋₆ alkoxy, C₁₋₆ alkylthio and C₂₋₇ alkoxycarbonyl. Suitably R⁸ is hydrogen and R⁵, R⁶ and R⁷ independently represent hydrogen, halogen, cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, trifluoromethylsulphonyl, nitro, C₁₋₆ alkyl or C₂₋₆ alkenyl, at least one of R⁵, R⁶ and R⁷ desirably being other than hydrogen. Preferably, R⁶ and R⁸ each represents hydrogen and R⁵ and R⁷ independently represent hydrogen, cyano, trifluoromethyl, nitro, methyl, ethyl, vinyl or halogen, especially chlorine or iodine. In a particular embodiment, R⁷ represents cyano, trifluoromethyl, nitro or halogen, especially chlorine; and R⁵ is hydrogen or ethyl. Certain compounds falling within the definition of formula I above are novel. Accordingly, in a further aspect, the invention provides a compound of formula IA or a salt or prodrug thereof: wherein R¹¹ represents a group of formula (iv), (v) or (vi): in which E¹ represents the residue of a five-membered heteroaromatic ring containing zero, 1, 2 or 3 further nitrogen atoms; R¹² and R¹³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom, or, where appropriate, a non-bonded electron pair; or R¹² and R¹³, when situated on adjacent atoms, together represent the residue of a saturated or unsaturated 4- to 9-membered carbocyclic or heterocyclic ring; and R¹⁴ represents hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; R¹⁵, R¹⁶, R¹⁷ and R¹⁸ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; and Ra and Rb independently represent hydrogen, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; provided that, when R¹¹ is a group of formula (iv), then this group is not a 1,2,3-benzotriazol-2-yl ring system optionally substituted by lower alkyl, lower alkoxy or halogen. Subject to the above proviso, the substituents R¹¹ to R¹⁸ and E¹ in the compounds of formula IA correspond to the substituents R¹ to R⁸ and E respectively as defined with reference to the compounds of formula I. For use in medicine, the salts of the compounds of formula IA will be non-toxic pharmaceutically acceptable salts. Other salts may, however, be useful in the preparation of the compounds according to the invention or of their non-toxic pharmaceutically acceptable salts. Suitable pharmaceutically acceptable salts of the compounds of formulae I and IA above include alkali metal salts, e.g. lithium, sodium or potassium salts; alkaline earth metal salts, e.g. calcium or magnesium salts; and salts formed with suitable organic ligands, e.g. quaternary ammonium salts. Where appropriate, acid addition salts may, for example, be formed by mixing a solution of the compound according to the invention with a solution of a pharmaceutically acceptable non-toxic acid such as hydrochloric acid, fumaric acid, maleic acid, succinic acid, acetic acid, citric acid, tartaric acid, carbonic acid or phosphoric acid. The present invention includes within its scope prodrugs of the compounds of formulae I and IA above. In general, such prodrugs will be functional derivatives of the compounds of formulae I and IA which are readily convertible in vivo into the required compound. Conventional procedures for the selection and preparation of suitable prodrug derivatives are described, for example, in Design of Prodrugs , ed. H. Bundgaard, Elsevier, 1985. Where the compounds according to the invention have at least one asymmetric centre, they may accordingly exist as enantiomers. Where the compounds according to the invention possess two or more asymmetric centres, they may additionally exist as diastereoisomers. It is to be understood that all such isomers and mixtures thereof are encompassed within the scope of the present invention. One sub-class of compounds according to the invention is represented by the compounds of formula IIA and salts and prodrugs thereof: wherein X and Y independently represent carbon or nitrogen; R²² and R²³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, di(C₁₋₆)alkylamino, carboxy, C₁₋₆ alkyl, C₂-₆ alkenyl, C₂₋₆ alkynyl, aryl, aryl(C₁₋₆)alkyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, aryloxy, aryl(C₁₋₆)alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl; and R²⁵, R²⁶ and R²⁷ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₁₋₆ alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl. Suitably, R²² and R²³ independently represent hydrogen, C₁₋₆ alkyl or aryl. Particular values of R²² and R²³ include hydrogen, methyl and phenyl. Preferably, one of R²² and R²³ represents hydrogen, and the other represents hydrogen, methyl or phenyl. Suitably, R²⁵ represents hydrogen, nitro, methyl, ethyl, vinyl or halogen, especially chlorine or iodine. Preferably, R²⁵ is hydrogen, ethyl or iodine. Suitably, R²⁶ represents hydrogen or chlorine, preferably hydrogen. Suitably, R²⁷ represents hydrogen, cyano, trifluoromethyl, nitro or halogen, preferably chlorine. Another sub-class of compounds according to the invention is represented by the compounds of formula IIB and salts and prodrugs thereof: wherein Z represents carbon or nitrogen; R³⁴ and R³⁹ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, di(C₁₋₆)alkylamino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, aryl, aryl(C₁₋₆)alkyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, aryloxy, aryl(C₁₋₆)alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl; and R³⁵, R³⁶ and R³⁷ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl. Preferably, Z represents carbon. Suitably, R³⁴ and R³⁹ independently represent hydrogen, C₁₋₆ alkyl, aryl or C₁₋₆ alkoxy. Particular values of R³⁴ and R³⁹ include hydrogen, methyl, phenyl and methoxy. Preferably, one of R³⁴ and R³⁹ represents hydrogen and the other represents hydrogen, methyl or phenyl. Suitably, R³⁵ and R³⁶ independently represent hydrogen, nitro, methyl, ethyl, vinyl or halogen, especially chlorine or iodine. Preferably, R³⁵ is hydrogen, ethyl or iodine. Preferably, R³⁶ is hydrogen. Suitably, R³⁷ represents hydrogen, cyano, trifluoromethyl, nitro or halogen, preferably chlorine. Specific compounds within the scope of the present invention include: 7-chloro-4-hydroxy-3-(pyrrol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(pyrazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-phenylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-phenylpyrrol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(indol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(4-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(5-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(5-methoxyindol-1-yl)-2(1H)-quinolone; 7-chloro-3-(3,5-dimethylpyrazol-1-yl)-4-hydroxy-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(imidazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(1,2,4-triazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(indazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(4-oxopyridin-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(2-oxopyridin-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(6-methylindol-1-yl)-2(1H)-quinolone; and salts and prodrugs thereof. The pharmaceutical compositions of this invention are preferably in unit dosage forms such as tablets, pills, capsules, powders, granules, sterile solutions or suspensions, or suppositories, for oral, intravenous, parenteral or rectal administration. For preparing solid compositions such as tablets, the principal active ingredient is mixed with a pharmaceutical carrier, e.g. conventional tableting ingredients such as corn starch, lactose, sucrose, sorbitol, talc, stearic acid, magnesium stearate, dicalcium phosphate or gums, and other pharmaceutical diluents, e.g. water, to form a solid preformulation composition containing a homogeneous mixture of a compound of the present invention, or a non-toxic pharmaceutically acceptable salt thereof. When referring to these preformulation compositions as homogeneous, it is meant that the active ingredient is dispersed evenly throughout the composition so that the composition may be readily subdivided into equally effective unit dosage forms such as tablets, pills and capsules. This solid preformulation composition is then subdivided into unit dosage forms of the type described above containing from 0.1 to about 500 mg of the active ingredient of the present invention. The tablets or pills of the novel composition can be coated or otherwise compounded to provide a dosage form affording the advantage of prolonged action. For example, the tablet of pill can comprise an inner dosage and an outer dosage component, the latter being in the form of an envelope over the former. The two components can be separated by an enteric layer which serves to resist disintegration in the stomach and permits the inner component to pass intact into the duodenum or to be delayed in release. A variety of materials can be used for such enteric layers or coatings, such materials including a number of polymeric acids and mixtures of polymeric acids with such materials as shellac, cetyl alcohol and cellulose acetate. The liquid forms in which the novel compositions of the present invention may be incorporated for administration orally or by injection include aqueous solutions, suitably flavoured syrups, aqueous or oil suspensions, and flavoured emulsions with edible oils such as cottonseed oil, sesame oil, coconut oil or peanut oil, as well as elixirs and similar pharmaceutical vehicles. Suitable dispersing or suspending agents for aqueous suspensions include synthetic and natural gums such as tragacanth, acacia, alginate, dextran, sodium carboxymethylcellulose, methylcellulose, polyvinylpyrrolidone or gelatin. In the treatment of neurodegeneration, a suitable dosage level is about 0.01 to 250 mg/kg per day, preferably about 0.05 to 100 mg/kg per day, and especially about 0.05 to 5 mg/kg per day. The compounds may be administered on a regimen of 1 to 4 times per day. In a particular embodiment, the compounds may be conveniently administered by intravenous infusion. The compounds of formula I above, including the novel compounds according to the invention, may be prepared by a process which comprises cyclising a compound of formula III: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are as defined above; and Q¹ represents a reactive carboxylate moiety. The reaction is conveniently carried out in the presence of a base, followed by a mild acidic work-up, as described, for example, in J. Heterocycl. Chem., 1975, 12, 351. Suitable bases of use in the reaction include sodium hydride and potassium hexamethyldisilazide. Suitable values for the reactive carboxylate moiety Q¹ include esters, for example C₁₋₄ alkyl esters; acid anhydrides, for example mixed anhydrides with C₁₋₄ alkanoic acids; acid halides, for example acid chlorides; orthoesters; and primary, secondary and tertiary amides. Preferably, the group Q¹ represents methoxycarbonyl or ethoxycarbonyl. The intermediates of formula III above may conveniently be prepared by reacting a compound of formula Q².CH₂.R¹ with a compound of formula IV: wherein R¹, R⁵, R⁶, R⁷, R⁸ and Q¹ are as define above; and Q² represents a reactive carboxylate moiety. The reaction is conveniently effected by mixing the reagents in an inert solvent, such as dichloromethane or 1,2-dichloroethane, and heating the reaction mixture at an elevated temperature, for example the reflux temperature of the solvent employed. Suitable values for the reactive carboxylate moiety Q² correspond to those defined above for Q¹. Preferably, the group Q² is an acid halide group, in particular an acid chloride group. A compound of formula Q².CH₂.R¹ wherein Q² represents an acid chloride group may be prepared from the corresponding compound of formula Q².CH₂.R¹ wherein Q² represents a carboxy group -CO₂H by treatment with oxalyl chloride or bis(2-oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl) under standard conditions well known from the art. Alternatively, where the heteroaromatic moiety R¹ is basic, for example where R¹ represents a 1,2,4-triazolyl ring system, the intermediate of formula III may be prepared by reacting a compound of formula R¹-H with a compound of formula V: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are defined above; and Hal represents a halogen atom, e.g. iodine. The reaction is conveniently effected, for example, by treating the halide of formula V with the sodium salt of the heterocycle R¹-H in a polar solvent such as N,N-dimethylformamide at room temperature. In an alternative process, the compounds of formula I above, including the novel compounds according to the invention, may be prepared in a single step from the intermediates of formulae IV and Q².CH₂.R¹ as defined above by treating a mixture of these reagents with approximately two equivalents of a strong base such as potassium hexamethyldisilazide. In a further process, the compounds of formula I above, including the novel compounds according to the invention, may be prepared by cyclisation of a compound of formula VI: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are as defined above; and Q³ represents a reactive carboxylate moiety. The reaction is conveniently effected in the presence of a base such as potassium hexamethyldisilazide. Suitable values for the reactive carboxylate moiety Q³ correspond to those defined above for Q¹. Preferably, the group Q³ represents a C₁₋₄ alkyl ester group such as methoxycarbonyl or ethoxycarbonyl. Where Q³ represents a C₁₋₄ alkyl ester group, the intermediates of formula VI may conveniently be prepared by Claisen ester condensation of a compound of formula IV with a compound of formula Q³.CH₂.R¹, wherein Q¹ and Q³ both represent C₁₋₄ alkyl ester groups. This involves treating a mixture of the reactants with a strong base such as potassium hexamethyldisilazide. Under these conditions, the reactants will usually be converted in situ directly into the desired cyclised product of formula I without the necessity for isolation of the intermediate of formula VI. The intermediates of formulae Q².CH₂.R¹, Q³.CH₂.R¹, IV and V above, including the precursors of formula Q².CH₂.R¹ wherein Q² represents -CO₂H, where they are not commercially available, may be prepared by the methods described in the accompanying Examples, or by methods analogous thereto which will be readily apparent to those skilled in the art. It will be appreciated that any compound of formula I or IA initially obtained from any of the above processes may, where appropriate, subsequently be elaborated into a further desired compound of formula I or IA respectively using techniques known from the art. Where the above-described processes for the preparation of the compounds according to the invention give rise to mixtures of stereoisomers, these isomers may be separated by conventional techniques such as preparative chromatography. The compounds may be prepared in racemic form, or individual enantiomers may be prepared either by enantiospecific synthesis or by resolution. The compounds may, for example, be resolved into their component enantiomers by standard techniques, such as the formation of diastereomeric pairs by salt formation with an optically active acid, such as (-)-di-p-toluoyl-d-tartaric acid and/or (+)-di-p-toluoyl-l-tartaric acid followed by fractional crystallisation and regeneration of the free base. The compounds may also be resolved by formation of diastereomeric esters or amides, followed by chromatographic separation and removal of the chiral auxiliary. During any of the above synthetic sequences it may be necessary and/or desirable to protect sensitive or reactive groups on any of the molecules concerned. This may be achieved by means of conventional protecting groups, such as those described in Protective Groups in Organic Chemistry, ed. J.F.W. McOmie, Plenum Press, 1973; and T.W. Greene, Protective Groups in Organic Synthesis, John Wiley & Sons, 1981. The protecting groups may be removed at a convenient subsequent stage using methods known from the art. The following Examples illustrate the preparation of compounds according to the invention. The compounds useful in this invention potently and selectively block responses to NMDA and/or AMPA in a brain slice from rat cortex, and inhibit the binding of agonists and antagonists to the strychnine-insensitive site present on the NMDA receptor and/or AMPA binding to rat forebrain membranes. Cortical Slice StudiesThe effects of compounds of the invention on responses to NMDA and AMPA were assessed using the rat cortical slice as described by Wong et al., Proc. Natl. Acad. Sci. USA, 1986, 83, 7104. The apparent equilibrium constant (Kb) was calculated from the righthand shift in the NMDA or AMPA concentration-response curves produced by the compound under test. of those compounds of the accompanying Examples which were tested, all were found to possess a Kb value in response to NMDA of below 150 µM. Binding StudiesThe ability of test compounds to displace ³H-L-689,560 (trans-2-carboxy-5,7-dichloro-4-phenyl-aminocarbonylamino-1,2,3,4-tetrahydroquinoline) binding to the strychnine-insensitive site present on the NMDA receptor of rat forebrain membranes was determined by the method of Grimwood etal., Proceedings of The British Pharmacological Society, July 1991, Abstract C78. The concentration of the compounds of the accompanying Examples required to displace 50% of the specific binding (IC₅₀) is below 50 µM in each case. EXAMPLE 17-Chloro-4-hydroxy-3-(pyrrol-1-yl)-2(1H)-quinolonePyrrole-1-acetic acid methyl ester (0.7g, 0.005M) and 7-chloro anthranilic acid methyl ester (0.94g, 1meq) were dissolved in dry tetrahydrofuran (40ml) and potassium hexamethyl disilazide (KHMDS) (24.15ml of a 0.5 molar solution in toluene, 2.4 molar equivalents) added in one portion. The reaction mixture was stirred at room temperature for 3h then quenched with methanol (10ml) and concentrated in vacuo. The residue was partitioned between sodium hydroxide solution and diethyl ether then the separated aqueous extracts were acidified to pH1 with concentrated hydrochloric acid and the solid produced was collected by filtration then recrystallised from dimethylformamide/water to give the title compound as an off-white solid (0.048g) m.p.> 280°C dec; δ (360MHz, DMSO) 6.15(2H, t, J = 2.1Hz, 2' pyrrole protons); 6.76 (2H, t, J = 2.1Hz, 1' pyrrole protons); 7.26(1H, dd, J = 8.6 and 2.0Hz, 6-H ; 7.34 (1H, d, J = 2.0Hz, 8-H), 7.96 (1H, d, J = 8.6Hz, 5-H); m/e 260 (M⁺); Found C, 58.75; H, 3.42; N, 10.30. C₁₃H₉ClN₂O₂.0.25 H₂O requires C, 58.88; H, 3.61; N, 10.58%. EXAMPLE 27-Chloro-4-hydroxy-3-(pyrazol-1-yl)-2(1H)-quinoloneThis compound was prepared in the same way as that described in Example 1 except using pyrazole-1-acetic acid methyl ester instead of pyrrole-1-acetic acid methyl ester to give the title compound as an off-white solid (m.p. 310°C) δ (360MHz, DMSO) 6.59 (1H, s, 4' pyrazole proton); 7.29(1H, dd, J = 8.5 and 2.0Hz, 6-H); 7.37 (1H, d, J = 2.0Hz, 8-H); 7.90 (1H, d, J = 1.4Hz, 3' or 5' pyrazole proton); 7.96 (1H, d, J = 8.Hz, 5-H); 8.89 (1H, d, J = 1.4Hz, 3' or 5' pyrazole proton); 12.00 (1H, br, s, NH); m/e 261 (M⁺); Found C, 54.90; H, 2.99; N, 15.86. C₁₂H₈ClN₃O₂ requires C, 55.08; H, 3.08; N, 16.06%. EXAMPLE 37-Chloro-4-hydroxy-3-(3-phenylindol-1-yl)-2(1H)-quinolone3-Phenyl indole (2g, 0.0094M) in dry tetrahydrofuran (100ml) was cooled to -78°C and potassium hexamethyldisilazide (18.78ml of a 0.5 molar solution in toluene, 1 molar equivalent) was added. The reaction mixture was removed from cooling and stirred for 15 minutes then cooled again to -78°C and methyl bromoacetate (0.98ml, 1.1 molar equivalents) was added. The reaction solution was allowed to warm to room temperature and stirred for 14h, concentrated in vacuo and partitioned between ethyl acetate and water. The organic layer was dried (Na₂SO₄), filtered and concentrated under vacuum to leave a residue which was dissolved in dry tetrahydrofuran (100ml) with 7-chloro anthranilic acid methyl ester (1.725g, 0.0094M) and potassium hexamethyldisilazide (52.64ml of a 0.5 molar solution in toluene) which was added in one portion. After stirring at room temperature for 3h, the reaction mixture was quenched with methanol (15ml) and the solvents evaporated under vacuum. The residue was partitioned between diethyl ether and sodium hydroxide solution, the aqueous layer was acidified to pH1 with concentrated hydrochloric acid and the solid produced was collected by filtration and recrystallised from dimethylformamide/water (850mg, m.p. 224-226°C) δ (360MHz, DMSO) 7.10-7.32 (5H, m, 6-H and 4 other aromatic protons); 7.39 (1H, d, J = 1.8Hz, 8-H); 7.48 (2H, m, aromatic protons ; 7.64 (1H, s, 2' indole proton); 7.73 (2H, aromatic protons); 7.95 (1H, m, aromatic proton); 7.99 (1H, d, J = 8.7Hz, 5-H); 11.48 (1H, br, s, OH); 11.83 (1H, br, s, NH); m/e 386 (M⁺); Found C, 69.01; H, 4.09; N, 6.91. C₂₃H₁₅ClN₂O₂.0.75H₂O requires C, 69.00; H, 4.15; N, 7.00%. EXAMPLE 47-Chloro-4-hydroxy-3-(3-phenylpyrrol-1-yl)-1(1H)-quinoloneThis compound was prepared in the same way as that described in Example 3 except using 3-phenyl pyrrole in place of 3-phenyl indole to give the title compound as a white solid (m.p. > 320°C dec) δ (360MHz, DMSO) 6.59 (1H, s, pyrrole proton); 6.81 (1H, s, pyrrole proton), 7.10-7.58 (8H, m, 1 pyrrole proton. 6-H, 8-H and 5 aromatic protons); 7.96 (1H, d, J = 8.7Hz, 5-H); 11.29 (1H, br, s, OH); 11.78 (1H, s, NH); m/e 336 (M⁺); Found C, 65.67; H, 3.76; N, 7.99. C₁₉H₁₃ClN₂O₂.0.6H₂O requires C, 65.66; H, 4.12; N, 8.06%. EXAMPLE 57-Chloro-4-hydroxy-3-(indol-1-yl)-2(1H)quinoloneThis compound was prepared in the same way as that described for Example 3 except using indole in place of 3-phenyl indole to give the title compound as a white solid (m.p. 288°C decomp). δ (360MHz, DMSO) 6.60 (1H, d, J = 3.2Hz, indole proton); 7.01 (1H, m, indole proton); 7.07 (2H, m, indole protons); 7.27 (2H, m, 6-H and 8-H); 7.38 (1H, d, J = 1.9Hz, indole proton); 7.60 (1H, m, indole proton); 7.98 (1H, d, J = 8.6Hz, 5-H); 11.31 (1H, br, s, OH); 11.78 (1H, s, NH); m/e 310 (M⁺); Found: C, 62.98; H, 3.79; N, 8.90. C₁₇H₁₁ClN₂O₂.1.5H₂O requires C, 62.99; H, 8.64; N, 3.89%. EXAMPLE 67-chloro-4-hydroxy-3-(3-methylindol-1-yl)-2(1H)-quinoloneThis compound was prepared in the same way as that described for Example 3 except 3-methyl indole was used in place of 3-phenyl indole to give the title compound as a white solid (m.p. > 290°C decomp). δ (360MHz, DMSO) 2.31 (3H, d, J = 0.6Hz, indole methyl); 6.93 (1H, m, indole proton); 7.03 (1H d, J = 0.9Hz, indole proton); 7.06 (2H, m, indole protons); 7.28 (1H, dd, J = 8.6 and 1.8Hz, 6-H); 7.36 (1H, d, J = 1.8Hz, 8-H); 7.53 (1H, m, indole proton); 7.95 (1H, d, J = 8.6Hz, 5-H); 11.16 (1H, br, s, OH); 11.75 (1H, s, NH); m/e 324 (M⁺); Found: C, 66.03; H, 4.07; N, 8.32. C₁₈H₁₃ClN₂O₂.0.1H₂O requires C, ,66.20; H, 4.07; N, 8.58%. EXAMPLE 77-Chloro-4-hydroxy-3-(4-methylindol-1-yl)-2(1H)quinoloneThis compound was prepared in the same way as that described for Example 3 except using 4-methyl indole in place of 3-phenyl indole to give the title compound as a white solid (m.p. > 350°C decomp); δ (360MHz, DMSO) 2.52 (3H, s, indole methyl); 6.62 (1H, d, J = 2.9Hz, 3' indole proton); 6.80 (1H, d, J = 8.1Hz, 5' indole proton); 6.86 (1H, d, J = 7.1Hz, 7' indole proton); 6.97 (1H, m, 6' indole proton); 7.23 (1H, d, J = 3.2Hz, 2' indole proton); 7.28 (1H, dd, J = 8.6Hz and 1.9Hz, 6-H); 7.37 (1H, d, J = 1.8Hz, 8-H); 7.96 (1H, d, J = 8.6Hz, 5-H); 11.25 (1H, br, s, OH); 11.75 (1H, s, NH); m/e 324 (M⁺). EXAMPLE 87-Chloro-4-hydroxy-3-(5-methylindol-1-yl)-2(1H)-quinoloneThis compound was prepared in the same way as that described for Example 3 except using 5-methyl indole in place of 3-phenyl indole to give the title compound as a white solid (m.p. > 350°C dec); δ (360MHz, DMSO) 2.39 (3H, s, indole methyl); 6.50 (1H, d, J = 3.1Hz, indole proton); 6.89 (2H, m, indole protons); 7.20 (1H, d, J = 3.1Hz, indole proton); 7.28 (1H, dd, J = 8.6Hz and 2.0Hz, 6-H); 7.37 (1H, d, J = 2.0Hz, 8-H); 7.97 (1H, d, J = 8.6Hz, 5-H); 11.24 (1H, br, s, OH); 11.76 (1H, s, NH); m/e 324 (M⁺); Found: C, 66.53; H, 4.15; N, 8.41; C₁₈H₁₃ClN₂O₂ requires C, 66.57; H, 4.03; N, 8.63%. EXAMPLE 97-Chloro-4-hydroxy-3-(5-methoxyindol-1-yl)-2(1H)-quinoloneThis compound was prepared in the same way as that described in example 1 using 5-methoxyindole-1-acetic acid methyl ester instead of pyrrole-1-acetic acid methyl ester to give the title compound as an off-white solid (m.p. 298°C decomp.) δ (360MHz, DMSO) 3.77 (3H, s, OCH₃) 6.51 (1H, d, J = 3.0Hz, indole-H), 6.73 (1H, dd, J = 8.8 and 1.8Hz, indole-6H), 6.68 (1H, d, J = 8.8Hz, indole 7-H), 7.11 (1H d, J = 1.8Hz, indole-4H ), 7.22 (1H, d, J = 3.0Hz, indole-H), 7.28 (1H, d, J = 2.0Hz, 6-H), 7.27 (1H, dd, J = 8.5 and 2.0Hz, 8-H), 7.96 (1H, d, J = 8.5Hz, 5-H), 11.25 (1H, br, s, OH), 11.76 (1H, s, NH); m/e 341 (M+I); Found C, 62.45; H, 3.59; N, 7.88; C₁₈H₁₃ClN₂O₃.0.2H₂O requires C, 62.78; H, 3.92; N, 8.13%. EXAMPLE 107-Chloro-3-(3,5-dimethylpyrazol-1-yl)-4-hydroxy-2(1H)-quinolone3,5-Dimethyl pyrazole (5g, 0.052M) was dissolved in dry THF (300ml) under an atmosphere of nitrogen and cooled to -78°C. Potassium hexamethyldisilazide (11.4ml of a 0.5 molar solution in toluene, 1.1 molar equivalent) was added then the reaction mixture was removed from cooling and stirred for 30 minutes, then cooled again to -30°C and methyl bromoacetate (4.92ml, 0.052M 1 molar equivalent) was added. The reaction solution was allowed to warm to room temperature and stirred for 17 hours, then concentrated in vacuo. 6N HCl (200ml) was added and the reaction mixture was extracted with dimethyl ether. The aqueous extracts were neutralised with solid sodium carbonate, extracted with dichloromethane and the combined organic layers were washed successively with water, saturated sodium hydrogen carbonate and saturated sodium chloride then dried (MgSO₄) filtered and concentrated under vacuum to give a residue which was dissolved in methanol (60ml), acetone (60ml) and water (120ml) with solid sodium hydroxide (1g). After stirring at room temperature for 15 hours, the organic solvents were removed under vacuum and the aqueous layer was washed with diethyl ether and acidified to pH4 with concentrated hydrochloric acid. After extraction with ethyl acetate the organic layer was dried (MgSO₄), filtered and concentrated in vacuo. The residue was dissolved in dry dichloromethane (15ml) under an atmosphere of nitrogen, cooled to 0°C and oxalyl chloride (0.425ml, 4.5mmol 1.5 molar equivalents) and a few drops of dry N,N-dimethylformamide was added. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours. then concentrated in vacuo to leave a residue which was azeotroped with toluene and evaporated under reduced pressure. The residue was dissolved in dry dichloromethane (20ml) under a nitrogen atmosphere with 7-chloro anthranilic acid methyl ester (0.56g, 0.003mol 1 molar equivalent) The solution was heated to reflux for 15 hours, cooled to room temperature and concentrated in vacuo. The residue was chromatographed on SiO₂ eluting with 10% ethyl acetate/dichloromethane. The residue was dissolved in dry tetrahydrofuran (15ml) under a nitrogen atmosphere, cooled to 0°C and potassium hexamethyldisilazide (6.3ml of 0.5M solution in toluene 2.4 molar equivalents) added. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours, then methanol (5ml) was added and the solvents were evaporated under vacuum. The residue was partitioned between diethyl ether and 1N sodium hydroxide solution, the aqueous layer was acidified to pH1 with concentrated hydrochloric acid and the solid produced was collected by filtration and recrystallised from dimethyl formamide/water (134mg, m.p. 305°C) δ (360MHz, DMSO) 2.01 (3H, s, pyrazole methyl); 2.16 (3H, s, pyrazole methyl); 5.99 (1H, s, pyrazole proton); 7.24 (1H, dd, J = 8.6Hz and 2.0Hz, 6-H); 7.32 (1H, d, J = 2.0Hz, 8-H); 7.91 (1H, d, J = 8.6Hz, 5-H); 11.62 (1H, s, NH); m/e 289 (M⁺); Found: C, 57.69; H, 4.04; N, 14.14. C₁₄H₁₂ClN₃O₂ requires C, 58.04; H, 4.18; N, 14.50%. EXAMPLE 117-Chloro-4-hydroxy-3-(imidazol-1-yl)-2-(1H) quinoloneThis compound was prepared in the same way as that described in example 1 except using imidazole-1-acetic methyl ester to give the title compound as an off-white solid (m.p. 360°C decomp.) δ (360MHz, DMSO) 7.00 (1H, dd, J = 8.4 and 1.8 Hz, 6-H), 7.17 (1H, d, J = 1.75Hz, 8-H), 7.58 (1H, s, imidazole-H), 7.75 (1H, s, imidazole-H), 7.90 (1H, d, J = 8.4Hz, 5-H), 9.12 (1H, s, imidazole-H), 10.48 (1H, s, NH), m/e 262 (M+1), Found C, 55.00; H, 3.31; N, 16.16; C₁₂H₈ClN₃O₂ requires C, 55.08; H, 3.08; N, 16.06. EXAMPLE 127-Chloro-4-hydroxy-3-(1,2,4 triazol-1-yl)-2-(1H)-quinoloneTo a solution of 7-chloro-anthranilic acid methyl ester (1g) in dry dichloroethane (30ml) was added chloroacetylchloride (0.42ml). The mixture was heated to reflux for 2hrs then cooled to room temperature and concentrated in vacuo to give a crude product (1.1g). To a portion of this crude product (0.65) in dry acetone was added sodium iodide (4g) and the solution was heated under reflux for 1 hour, cooled to room temperature, filtered and concentrated in vacuo to yield a crude product. To this product was added dry dimethylformamide (15ml) and 1,2,4-triazole sodium salt (226mg). The mixture was stirred at room temperature for 2h then a solution of potassium hexamethyldisidazide (9.92ml of a 0.5 molar solution in toluene) was added. The reaction mixture was stirred at room temperature for 2hrs then quenched with methanol (5ml) and concentrated in vacuo. The residue was partitioned between sodium hydroxide solution (1M) and diethylether, the separated aqueous extract was acidified to pH1 with concentrated hydrochloric acid and the solid produced was collected by filtration then recrystallised from dimethylformamide/water to give the title compound as an off-white solid (0.90g, m.p. 228-230°C decomp.) δ (360Mhz, DMSO) 7.26 (1H, dd, J = 8.6 and 2.6Hz, 6-H), 7.37 (1H, d, J = 2.6Hz, 5-H), 7.95 (1H, d, J = 8.6Hz, 8-H), 8.12 (1H, s, triazole-H), 8.70 1H, s, triazole-H), 11.97 (1H, s, NH); m/e 263 (M+1); Found C, 50.26; H, 2.55; N, 20.48; C₁₁H₇ClN₄O₂. 0.2 CH₃OH requires C, 50.00; H, 2.92; N, 20.82%. EXAMPLE 137-Chloro-4-hydroxy-3-(indazol-1-yl)-2-(1H)-quinoloneThis compound was prepared in the same way as that described in example 1 except using benzimidazole-1-acetic acid to give the title compound as a white solid (m.p. > 410°C), (360MHz, NaOD, D₂O) δ 7.11 (1H, dd, J = 8.7 and 2.0Hz, 6-H), 7.26-7.40 (4H, m, 8-H and 3 x benzimidazole protons), 7.80 (1H, dd, J = 8.5 and 2.0Hz, benzamidazole protons), 7.91 (1H, d, J = 8.7Hz, 5-H), 8.12 (1H, s, benzamidazole-2H). EXAMPLE 147-Chloro-4-hydroxy-3-(2-oxo pyrid-1-yl)-2(1H)quinoloneThis compound was prepared in same way as that described in example 1 except using 2-pyridone-1-acetic acid methyl ester to give the title compound as a white solid (m.p. 355°C slow decomp.) δ (360MHz, DMSO) 6.23 (1H, m, pyridone-H), 6.43 (1H, d, J = 9.2Hz, pyridone-H), 7.25-7.47 (4H, m, pyridone-H x 3, 6-H, 8-H), 7.92 (1H, d, J = 8.6Hz, 5-H), 11.54 (1H, br, s, OH), 11.77 (1H, s, NH), m/e 289 (M+1); Found C, 58.15; H, 3.24; N, 9.37; C₁₄H₉ClN₂O₃ requires C, 58.25; H, 3.14; N, 9.70. EXAMPLE 157-Chloro-4-hydroxy-3-(4-oxo pyrid-1-yl)-2(1H)quinoloneThis compound was prepared in the same way as that described in Example 1 except using 4-pyridone-1-acetic acid methyl ester to give the title compound as a white solid (m.p. 340°C slow decomp.) δ (360MHz, NaOD-D₂O) 6.70 (2H, d, J = 7.5Hz, 3 and 5 pyridone protons), 7.06 (1H, dd, J = 8.7 and 2.0Hz, 6-H), 7.35 (1H, d, J = 2.0Hz, 8-H), 7.71 (2H, d, J = 7.5Hz, 2 and 6 pyridone protons), 7.89 (1H, d, J = 8.7Hz, 5-H), m/e 289 (M+1). EXAMPLE 167-Chloro-4-hydroxy-3-(6-methylindol-1-yl-2(1H)-quinolineThis compound was prepared in the same way as that described for example 3 except using 5-methyl indole in place of 3-phenyl indole to give the title compound as a white solid (m.p. > 350°C decomp.); δ (360MHz, DMSO) 2.34 (3H, s, indole methyl); 6.53 (1H, d, J = 3.2Hz, indole proton); 6.79 (1H, s, indole proton); 6.89 (1H, d, J = 8.0Hz, indole proton), 7.16 (1H, d, J = 3.2Hz, indole proton), 7.28 (1H, dd, J = 8.6 and 2.0Hz, 6H), 7.38 (1H, d, J = 1.8Hz, 8H); 7.47 (1H, d, J = 8.0Hz, indole proton), 7.98 (1H, d, J = 8.6Hz, 5H), 11.26 (1H, br, s, OH), 11.75 (1H, s, NH); m/e 324 (M⁺). EXAMPLE 17Tablet PreparationTablets containing 1.0, 2.0, 25.0, 26.0, 50.0 and 100.0mg, respectively of the following compounds are prepared as illustrated below: 7-Chloro-4-hydroxy-3-(pyrrol-1-yl)-2(1H)-quinolone 7-Chloro-4-hydroxy-3-(3-phenylindol-1-yl)-2(1H)-quinolone 7-Chloro-4-hydroxy-3-(3-phenylpyrrol-1-yl)-1(1H)-quinolone TABLE FOR DOSES CONTAINING FROM 1-25MG OF THE ACTIVE COMPOUND Amount-mg Active Compound1.02.025.0 Microcrystalline cellulose49.2548.7537.25 Modified food corn starch49.2548.7537.25 Magnesium stearate0.500.500.50 TABLE FOR DOSES CONTAINING FROM 26-100MG OF THE ACTIVE COMPOUND Amount-mg Active Compound26.050.0100.0 Microcrystalline cellulose52.0100.0200.0 Modified food corn starch2.214.258.5 Magnesium stearate0.390.751.5 All of the active compound, cellulose, and a portion of the corn starch are mixed and granulated to 10% corn starch paste. The resulting granulation is sieved, dried and blended with the remainder of the corn starch and the magnesium stearate. The resulting granulation is then compressed into tablets containing 1.0mg, 2.0mg, 25.0mg, 26.0mg, 50.0mg and 100mg of the active ingredient per tablet.	A pharmaceutical composition Comprising a compound of formula I or a pharmaceutically acceptable salt thereof or a prodrug thereof: wherein R¹ represents a group of formula (i), (ii) or (iii): in which E represents the residue of a five-membered heteroaromatic ring containing zero, 1, 2 or 3 further nitrogen atoms; R² and R³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa,-CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom, or, where appropriate, a non-bonded electron pair; or R² and R³, when situated on adjacent atoms, together represent the residue of a saturated or unsaturated 4- to 9-membered carbocyclic or heterocyclic ring; and R⁴ represents hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; R⁵, R⁶, R⁷ and R⁸ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃ -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; and Ra and Rb independently represent hydrogen, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; in association with one or more pharmaceutically acceptable carriers and/or excipients. A compound of formula I as defined in claim 1 or a pharmaceutically acceptable salt thereof or a prodrug thereof for use in therapy. The use of a compound of formula I as defined in claim 1 or a pharmaceutically acceptable salt thereof or a prodrug thereof for the manufacture of a medicament for the treatment and/or prevention of conditions which require the administration of a selective non-competitive antagonist of NMDA receptors. The use of a compound of formula I as defined in claim 1 or a pharmaceutically acceptable salt thereof or a prodrug thereof for the manufacture of a medicament for the treatment of conditions which require the administration of an antagonist of AMPA receptors. A compound of formula IA or a salt or prodrug thereof: wherein R¹¹ represents a group of formula (iv), (v) or (vi): in which E¹ represents the residue of a five-membered heteroaromatic ring containing zero, 1, 2 or 3 further nitrogen atoms; R¹² and R¹³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa,-CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom, or, where appropriate, a non-bonded electron pair; or R¹² and R¹³, when situated on adjacent atoms, together represent the residue of a saturated or unsaturated 4- to 9-membered carbocyclic or heterocyclic ring; and R¹⁴ represents hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; R¹⁵, R¹⁶, R¹⁷ and R¹⁸ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, -ORa, -OCF₃, -SRa, -SCF₃, -SORa, -SOCF₃, -SO₂Ra, -SO₂CF₃, -SO₂NRaRb, -NRaRb, -NRaCORb, -NRaCO₂Rb, -CORa, -CO₂Ra, -CONRaRb, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; and Ra and Rb independently represent hydrogen, a hydrocarbon group comprising a straight-chained, branched or cyclic group containing up to 18 carbon atoms, or a heterocyclic group containing up to 18 carbon atoms and at least one heteroatom; provided that, when R¹¹ is a group of formula (iv), then this group is not a 1,2,3-benzotriazol-2-yl ring system optionally substituted by lower alkyl, lower alkoxy or halogen. A compound as claimed in claim 5 represented by formula IIA and salts and prodrugs thereof: wherein X and Y independently represent carbon or nitrogen; R²² and R²³ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, di(C₁₋₆)alkylamino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, aryl, aryl(C₁₋₆)alkyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, aryloxy, aryl(C₁₋₆)alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl; and R²⁵, R²⁶ and R²⁷ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₁₋₆ alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl. A compound as claimed in claim 5 represented by formula IIB and salts and prodrugs thereof: wherein Z represents carbon or nitrogen; R³⁴ and R³⁹ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, di(C₁₋₆)alkylamino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₂₋₆ alkynyl, aryl, aryl(C₁₋₆)alkyl, phenyl(C₂₋₆)alkynyl, C₁₋₆ alkoxy, aryloxy, aryl(C₁₋₆)alkoxy, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl; and R³⁵, R³⁶ and R³⁷ independently represent hydrogen, halogen, cyano, trifluoromethyl, nitro, hydroxy, amino, carboxy, C₁₋₆ alkyl, C₂₋₆ alkenyl, C₁₋₆ alkylthio or C₂₋₇ alkoxycarbonyl. A compound as claimed in claim 5 selected from: 7-chloro-4-hydroxy-3-(pyrrol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(pyrazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-phenylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-phenylpyrrol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(indol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(3-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(4-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(5-methylindol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(5-methoxyindol-1-yl)-2(1H)-quinolone; 7-chloro-3-(3,5-dimethylpyrazol-1-yl)-4-hydroxy-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(imidazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(1,2,4-triazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(indazol-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(4-oxopyridin-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(2-oxopyridin-1-yl)-2(1H)-quinolone; 7-chloro-4-hydroxy-3-(6-methylindol-1-yl)-2(1H)-quinolone; and salts and prodrugs thereof. A process for the preparation of a compound of formula IA as defined in claim 5, which process comprises: (A) cyclising a compound of formula III: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are as defined in claim 1; and Q¹ represents a reactive carboxylate moiety; or (B) reacting a compound of formula Q².CH₂.R¹ with a compound of formula IV: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are as defined in claim 1, Q¹ is as defined above, and Q² represents a reactive carboxylate moiety; in the presence of approximately two equivalents of a strong base; or (C) cyclisation of a compound of formula VI: wherein R¹, R⁵, R⁶, R⁷ and R⁸ are as defined in claim 1; and Q³ represents a reactive carboxylate moiety; and (D) where appropriate, converting a compound of formula I initially obtained into a further compound of formula I using methods known perse.	MERCK SHARP & DOHME; MERCK SHARP & DOHME LTD.	CARLING WILLIAM R; LEESON PAUL D; MOORE KEVIN W; CARLING, WILLIAM R.; LEESON, PAUL D.; MOORE, KEVIN W.
EP-0489459-B1	489,459	EP	B1	EN	19,950,809	1,992	20,100,220	new	G09G3	null	G02F1, G09G3	S09G3:36C2, S09G213:22, G09G 3/36C10	Method of driving a matrix display device and a matrix display device operable by such a method	In operation of an active matrix display device comprising an array of display elements (12), for example liquid crystal elements, each connected in series with an associated two terminal non-linear switching device (30), e.g. a MIM, between row and column address conductors (22,24), and row and column driver circuits (40,43) for applying selection signals to each row conductor in turn and data signals to the column conductors, the data signals are applied for part only of the row address period and a row selection signal commences prior to the data signal and while a reference potential is applied to the column conductors whereby during a row address period a display element is initially charged to a level approaching the lower end of the display element's operational range of voltages and thereafter charged to the required level according to the data signal. Vertical cross-talk is reduced and peak current density through the non-linear devices is kept low, thereby avoiding the risk of damage.	The present invention relates to a method of driving a matrix display device comprising an electro-optical display medium between two supporting plates, an array of display elements arranged in rows and columns with each display element being constituted by electrodes provided on the facing surfaces of the supporting plates, and sets of row and column conductors, each display element being connected in series with a two-terminal non-linear switching device between associated row and column conductors, in which each row of display elements is selected during a row address period by a selection signal of a row signal waveform applied to the row conductors and data signals are applied via the column conductors for a part of the address period by means of which selection and data signals a range of operational voltages can be produced at the display elements for display purposes, a reference potential being applied to the column conductors during the remainder of the address period. The invention also relates to a matrix display device which can be operated using such a method. An active matrix display device of the above type is suitable for displaying video, for example, TV, pictures using passive electro-optical display media such as liquid crystal material, electrophoretic suspensions and electrochromic materials, although it can be used to display alphanumerical information instead. A conventional drive scheme for liquid crystal display devices using two terminal non-linear switching devices involves applying a selection voltage to a row conductor during a selection period, corresponding in the case of TV display to a maximum of a TV line period, causing the switching devices associated with that row conductor to operate in the charging region of their characteristic so that the capacitances of the display elements concerned rapidly charge to a display voltage according to a data signal voltage present on the column conductor at that time. The display voltage produced lies in a predetermined operational voltage range used for picture display which in the case of a liquid crystal display device has lower and upper limits in the range of transition in the transmission/voltage characteristic of the liquid crystal material, commonly referred to as the threshold and saturation voltages respectively, at which the display element exhibits substantially maximum and minimum transmission, or vice versa depending on the relative orientation of associated polarising layers on the two supporting plates. At the end of the selection period the row conductor voltage falls to a lower, hold, value selected so that the mean voltage across the switching device during the period until it is next addressed, is minimised. Assuming an ideal situation, this hold voltage is equal to the mean of the rms saturation and threshold voltages of the display element. In a known drive scheme, described in US-A-4892389, the display element addressing period is shortened in order to reduce vertical cross-talk caused by the capacitance of the switching devices which can result in display element voltages varying over a field period due to data signal voltages intended for other display elements. This can be achieved by reducing the length of time for which data voltage is present on the column conductors to a fraction of the available line period, determined by the video signal. During the remainder of the line period, the column voltage is returned to a constant reference voltage level. At the same time the row selection period is reduced so that it is no greater than the duration of the data signal. However, a problem can arise with such a drive scheme particularly, but not exclusively, where the switching devices comprise MIMs. The reduction in the row selection period means that the same display element capacitance must be charged in a shorter time which, in turn, means that a larger selection voltage must be used. This results in an increase in the peak current density in the switching device which can, if large enough, lead to damage or even destruction of the switching device. It is an object of the present invention to provide an improved method of driving a matrix display device, and a matrix display device capable of operating by this method, in which the effects of cross-talk are lessened while avoiding, at least to some extent, the risk of the switching devices being damaged. According to one aspect of the present invention, a method of driving a matrix display device as described in the opening paragraph is characterised in that for a row of display elements the row selection signal commences prior to the application of the data signals and during the application of the reference potential whereby the display elements are initially charged to a level approaching the lower end of the operational range of voltages and thereafter are charged to the required level according to the applied data signals. When addressed, therefore, the display elements of a row are charged to a preliminary level, preferably close to, but below, the lower end of the operational range, during a first portion of the row address, selection, period and then the charge on the display elements is modified in a subsequent portion of the address period by in effect adding the data (video) signal so as to produce the required display effect, e.g. grey scale, in accordance with the level of the data signal. This method offers significant benefits. As in the known drive scheme for improving cross-talk performance the data signals are applied for only a part of the address period available for row selection and are of shorter duration than conventionally-used data signals so that a reduction in vertical cross-talk can be achieved. In addition, however, the pre-charging of the display elements prior to the application of the data signal means that the peak current density through a non-linear switching device is maintained at a comparatively low level. Consequently the risk of damage being caused to the non-linear devices through large peak current densities is removed and a greater freedom on the choice of the dimensions of the display elements is permitted since the constraints on the physical characteristics of the non-linear devices are relaxed. The latter benefit is especially important for display devices using MIMs as the non-linear switching devices. However, the method is applicable to display devices employing other types of two terminal non-linear switching devices known in the art, for example diode rings, back-to-back diodes, or pip or nin diode structures. Preferably, the level to which a display element is initially charged approaches the lower end of the range of transition in the transmission/voltage characteristic of the electro-optical display medium, which for example, corresponds to the threshold voltage in the case of a liquid crystal display element. It is customary for display devices using liquid crystal material to reverse periodically the voltage applied to the display elements so as to prevent a net DC voltage appearing across the material which can lead to degradation of the material. To this end the polarity of the voltage applied across the display element is inverted at given intervals, usually after each line (line inversion), after every two lines (double line inversion, or every field (field inversion). The row signal waveform may be of a known kind comprising a succession of said selection signals separated by hold signal portions whose polarity is periodically inverted, making a four level waveform. The row signal waveform may be of a known kind comprising a succession of said selection signals separated by hold signal portions whose polarity is periodically inverted, making a four level waveform. In an embodiment of the invention the reference potential is then preferably periodically switched between two predetermined levels in accordance with the periodic inversion of the selection and data signals. For line inversion, double line inversion and field inversion drive schemes the reference level changes every line, every two lines and every field respectively. The two predetermined reference levels correspond to the absolute value of the data signal which produces the smallest operating voltage across the display element, that is, a voltage across a display element substantially corresponding to the level required for the lower end of the operating or transition range. For a display device using twisted nematic liquid crystal material with polarisers and operating in transmissive mode, this value of the data signal produces peak white, i.e. maximum transmission, in the case of the polarisers being crossed and black, i.e. maximum absorption, in the case of parallel polarisers. The switching of the reference potential level in this manner overcomes problems which might possibly be experienced when a single reference potential level is utilised due to the display elements pre-charging towards the level of this single reference potential. Preferably also, the rising edge of selection signal is at least substantially complete before the voltage on the column conductor changes from the reference potential to the data signal. The rise of the selection signal thus starts a certain, short, time before the transition on the column conductor. During this precharging period the display element is charged towards the lowest end of its operating voltage range. Most usefully, the precharging period is chosen to lie in the range whose minimum is approximately equal to the rise time of the row selection signal and whose maximum is substantially equal to the the duration of the data signal on the column conductor. The invention is applicable also to a drive scheme of the kind described in EP-A-0362939 in which the row signal waveform comprises five levels and includes a reset signal for the purpose of correcting non-uniformities in the behaviour of the two terminal switching elements across the array. Therefore, another embodiment of the invention using such a drive scheme is characterised in that the row signal waveform applied to each row conductor further includes a second selection signal comprising a reset signal portion by means of which the display elements of the row are charged at least to the upper end of the range of operational voltages followed by a setting signal portion by means of which the display elements are set at a level in the range of operational voltages according to the applied data signals, and in that for a row of display elements the setting signal portion commences prior to the application of the data signals and during the application of a reference potential whereby the display elements are charged from the level obtained by the reset signal portion back to a level close to the upper end of the range of operational voltages. This leads to a reduction in the current flowing in the switching devices during two of the three comparatively large transitions involved in such a five level row signal waveform which might otherwise result in damage. The reference potentials for use with the first mentioned selection signal and the setting signal portion may conveniently be applied to each column conductor in respective intervals between successive data signals applied to the column conductor. In order to reduce the possibility of damage occuring in all three transitions, then preferably the reset signal portion commences prior to the application of the data signals to the column conductors intended for a preceding row of display elements and during the application of a further reference potential to the column conductors whereby the display elements of the row are charged to a level approaching the lower end of the range of operational voltage and thereafter are charged to at least the upper end of the said range. In this case the reference potentials for use with the first-mentioned selection signal and the reset signal portion may conveniently be applied to each column conductor consecutively in an interval between successive data signals applied to the column conductor. According to another aspect of the present invention, there is provided a matrix display device having a row and column array of display elements comprising electrodes carried on facing surfaces of two supporting plates with an electro-optical display medium therebetween, sets of row and column conductors, each display element being connected in series with a non-linear switching device between associated row and column conductors, and row driver and column driver circuits for providing during respective row address periods a selection signal to each row conductor and data signals to the column conductors for a part of the address period by means of which signals a range of operational voltages can be produced at display elements for display purposes, the column driver circuit being arranged to provide a reference potential during the remainder of the address period, which is characterised in that the row driver circuit is arranged to start a row selection signal in a row address period a predetermined time before the beginning of the data signal provided by the column driver circuit and during the application of the reference potential to the column conductors, the reference potential provided by the column driver circuit being operable to charge the display elements of the row are charged towards the lower end of their operational voltage range prior to the application of the data signal. Methods of driving a matrix display device, and a matrix display device, particularly a liquid crystal display device, operable by such a method, in accordance with the invention will now be described, by way of example, with reference to the accompanying drawings in which:- Figure 1 is a schematic cross-section through a part of the liquid crystal display device showing a few display elements; Figure 2 is a simplified block diagram of the display device; Figure 3 illustrates graphically the transmission/voltage characteristic of a typical display element of the display device; Figures 4a and 4b show examples of waveforms applied to column and row conductors respectively in a known drive scheme; Figures 5a and 5b shows examples of waveforms applied to column and row conductors respectively in another known drive scheme and a modified drive scheme according to one embodiment of the present invention; Figure 6 illustrates graphically a relationship between a display element voltage and data signal level for the modified device scheme of Figures 5a and 5b; Figures 7a, 7b and 7c illustrate column conductor waveforms used in a second embodiment of the present invention for alternative modes of operation; Figures 8a and 8b are waveforms showing the relative timing of row and column conductor signals used in the second embodiment of the present invention; Figure 9 shows the display element voltage for the case illustrated in Figures 8a and 8b; Figures 10 and 10b illustrate for comparison the voltages appearing across a typical non-linear switching device of the display device during operation using respectively a known drive scheme and the method according to the second embodiment of the present invention; and Figures 11 and 12 illustrate typical row and column conductor signal waveforms in a further embodiment according to the present invention using an alternative drive scheme. It should be understood that the Figures are merely schematic and are not drawn to scale. It should also be understood that the same reference numerals are used throughout the Figures to indicate the same or similar parts. Referring to Figures 1 and 2, the display device, which is intended to display video, for example TV, pictures, includes an active matrix liquid crystal display panel 10 consisting of r rows (1 to r) with s display elements 12 (1 to s) in each row. Only a few display elements are depicted in Figure 2 and in practice the total number of display elements (rxs) may be several hundreds of thousands. The panel 10, which operates in transmissive mode, comprises two spaced, transparent and insulating supporting plates 14 and 15, for example of glass, with twisted nematic liquid crystal material 16 disposed therebetween. The facing surfaces of the two plates 14 and 15 are covered with electrically and chemically insulating layers 17 and 18. In accordance with standard practice, the outer surfaces of the plates are provided with polarising layers (not shown). The plate 14 carries a row and column array of generally rectangular display element electrodes 20 of transparent conductive material and a set of row conductors 22 which, apart from the first, extend between adjacent pairs of display element rows. Each display element electrode 20 in a row is connected to an associated one of the row conductors through a bidirectional, non-linear resistance device 30 (not visible in Figure 1) exhibiting a substantially symmetric threshold characteristic and functioning in operation as a switch, which in this example comprises a MIM. The plate 15 carries a set of strip-shape column conductors 24 of transparent conductive material, each of which extends over a respective column of display element electrodes 20. At least where they overlie the electrodes 20 the conductors 24 are of similar width to the electrodes and these portions constitute opposing display element electrodes. Each display element 12 thus consists of two spaced electrodes between which liquid crystal material is disposed and is connected electrically in series with a MIM between associated row and column conductors. In an alternative configuration, the MIMs may be connected between the display elements and the column conductors. The exposed surfaces of the layers on the two plates 14 and 15 are covered by LC orientation layers 25 and 26 in known manner. In common with known display devices, the row conductors 22 serve as scanning electrodes and are controlled by a row driver circuit 40 which applies a selection signal to each row conductor 22 sequentially in turn during a respective row address period. In synchronism with the selection signals, achieved by means of the timing and control circuit 42, data signals are applied to the column conductors 24 from a column driver circuit 43 connected to the output of a video processing circuit 50 to produce a display effect from the rows of display elements 12 associated with the row conductors 22 as they are scanned. These data signals comprise video information and are obtained by sampling a TV line with serial to parallel conversion. As a result of the application of the selection and data signal voltages, the optical transmissivity of the display elements 12 of a row are controlled to produce the required visible display effect. The individual display effects of the display elements 12, addressed one row at a time, combine to build up a complete picture in one field, the display elements being addressed again in a subsequent field. The transmission (T)/voltage (VLC) characteristic of a typical display element is depicted graphically in Figure 3. In this case it is assumed that crossed polarisers are used. Below a certain threshold voltage, Vth, the maximum transmission occurs giving a peak white output, whereas beyond a saturation voltage, Vsat, transmission is substantially at a minimum, corresponding to a black output. The intermediate range (Vth to Vsat) constitutes the operational voltage range of the display element and forms the transition range allowing grey scale levels to be achieved. If parallel polarisers are used, the output effect is opposite with Vth and Vsat corresponding to minimum (black) and maximum (peak white) transmission respectively. The voltage/conduction characteristic of the two-terminal non-linear devices 30 is bidirectional and substantially symmetrical with respect to zero voltage so that by reversing the polarity of the scanning and data signal voltages periodically a net dc bias across the display elements is avoided. Following known practice this inversion may be carried out after every line, every two lines or every field, commonly referred to as, respectively, line inversion, double line inversion and field inversion. Each time a display element is addressed, in successive fields, the polarity of the applied voltage is reversed. Although the particular embodiment described employs MIMs, it will be appreciated that other forms of bidirectional non-linear switching devices exhibiting a threshold characteristic such as back-to-back diodes, diode rings, n-i-n or p-i-p diode structures etc., may be used instead. Active matrix liquid crystal display devices employing two terminal non-linear devices as switching elements in series with the display elements are generally well known and for further information reference is invited to earlier publications describing such types of display devices, such as, for example, US Patent Specifications 4,223,308 and 4,642,620 using diode structures and US Patent Specifications 4413883 and 4683183, using MIMs. Row scanning in known display devices is conventionally accomplished using a waveform as depicted in Figure 4b where the voltage VR of the (n+1)th row comprises a row selection signal portion of a duration corresponding to a TV line period Tl, e.g. 64 microseconds for a PAL system, and magnitude Vs followed immediately by a hold signal portion of lower, but similar polarity, voltage, Vh, for the remainder of the field period. In this example, the device is driven with field inversion so that the hold and select signal portions alternate between Vh+ and Vh- and Vs+ and Vs- respectively. The voltage waveform applied to a column conductor, Vc, is depicted in Figure 4a and comprises data signals for a display element in each row, (Vn, Vn+1, etc.), each data signal having a duration substantially corresponding to the selection signal, i.e. a TV line period. In order to reduce vertical cross talk problems, an alternative scheme has been proposed in US-A-4892389. An example of this alternative scheme is depicted by the waveforms in solid lines in Figures 5a and 5b which respectively show typical column and row conductor waveforms, and their relative timing, present using the line inversion drive approach. In this scheme, the length of time for which a data signal representing video information is present on the column conductors is reduced from the whole line period, Tl, (Tl=A+B in Figure 5a) to a fraction F of the line time, i.e. F.Tl (=B). For the remainder of the line time, indicated at A and of duration (1-F).Tl, the column conductor voltage is returned to a constant reference voltage level Vo so that the waveform comprises a succession of data signals separated by periods of the constant reference potential. The reference level Vo remains constant for successive fields. A single row address period is constituted by the duration of the reference potential part indicated at A together with the duration of the subsequent data signal indicated at B so that in one row address period, Tl, the parts A and B are applied to the column conductor. At the same time, the row selection signal, shown in solid lines Figure 5b, is shortened such that it is no greater than F.Tl. This has the effect of reducing the vertical cross-talk by a factor F so that the acceptable ratio of switching device to display element capacitance is increased by the same factor. However, the reduction of the row selection signal time means that the display element capacitance must be charged in a shorter time and to achieve this a larger selection signal voltage (Vs) is required. This results in an increase in the peak current density in the switching device and can have serious consequences as damage or destruction of the switching devices may then occur. With the method of the present invention the drive waveforms are modified so as to achieve display element charging in the shorter time required for cross-talk reduction whilst at the same time maintaining a comparatively low peak current density in the non-linear switching devices during operation. A part of the available row address period, corresponding to a TV line time, is used to charge the display elements in the row to an initial level and in a further, small, period the video information is in effect added to provide the required display effect output, e.g. the appropriate grey scale. Using shortened data signals provides improved cross-talk performance in similar manner as in the above scheme. In addition a reduction in peak current density in the switching devices is obtained. To this end, the row driver circuit 40 is operable to provide signal waveforms to the row conductors 22 in which the leading edge of a row selection signal pulse occurs before the beginning of the associated data signal applied to the column conductor 24 and while a reference potential is being applied during the row address period. In a simple scheme, and referring to Figure 5a, the selection signal applied to the row in which a display element is to provide a display according to the data signal level Vn+1 is thus initiated during the period indicated at A in which the column conductor is at the reference potential Vo. The leading edge of the selection signal depicted in Figure 5b is therefore shifted to the left in the Figure as shown by the dotted lines so that it precedes the leading edge of the data signal (Vn+1), the falling edge of this pulse staying as before, substantially coincident with termination of the data signal. As a consequence of this shifting of the leading edge, the display element concerned during the row address period Tl is initially partially charged according to the level Vo in the period A and subsequently finally charged to the required value according to the level of the data signal, Vn+1, when this signal is applied to the column conductor during the period B. In this simple modified drive scheme illustrated in Figure 5a and 5b the pre-charging of the display elements is towards the constant level, Vo, of the reference potential. The level Vo is determined in the known scheme having regard to the cross-talk reduction requirement and corresponds to a mid-grey video level which is equivalent to a data signal level lying at the mid-point of the signal range applied to the column conductor. As a result then of the initial charging of the display element during period A the display element is charged towards, and assuming the pre-charging period is adequately long, substantially reaches the level of the lower end (white) of the display element's operational voltage range. In this embodiment, and referring to Figure 3, this level corresponds with the threshold level, Vth, and thus the lower end of the display element transition range in the transmission/voltage characteristic of the liquid crystal material. If the level of the data signal following this precharging corresponds to a larger display element voltage then there is no difficulty and the charge on the display element is increased to the required value. However, if the level of the following data signal corresponds to a lower display element voltage, the display element is not discharged back to this level because the change in the signal on the column conductor (to a lower value) turns the non-linear device 30 off. The result of this is a transfer characteristic for video drive to display element voltage of the form illustrated graphically in Figure 6, in which column voltage, Vc, is plotted against display element voltage, VLC. With a conventional drive scheme (Figure 4), the relationship is as shown by the solid line and extends over the full range of operating voltage of the display element from Vth (peak white) to Vsat (black). With the above, modified, scheme the relationship changes to that shown by the dotted line from which it will be seen almost half the required display element voltage range is inaccessible. The simple modified drive scheme can be used to advantage to provide improved performance and reliability in some display applications. However, for many display applications, such as TV displays for example where a full range of grey scale is needed, this limitation is not acceptable. For this reason, in a preferred embodiment certain further changes are incorporated to enhance performance. More particularly the drive waveforms applied to the column conductors are also modified, by suitable adaptation of the column driver circuit 43. Examples of the modified column waveforms are shown in Figures 7a, b and c which illustrate forms present when utilising respectively line inversion, double line inversion, and field inversion drive schemes. Instead of returning the column voltage to a single, constant, level, (Vo), for the period (I-F).Tl when a data signal is not present, the reference potential is changed periodically between two levels, Vo+ and Vo-. For a line inversion drive scheme, Figure 7a, in which the row conductor waveforms and data signals reverse sign every TV line, the reference level changes every TV line. For a double line inversion scheme, Figure 7b, in which the row conductor waveforms and data signals reverse sign every two lines, the reference level similarly changes every two lines. For a field inversion drive scheme, Figure 7c, in which the row conductor waveforms and data signals reverse sign every field, f, the reference level changes every field, f(N) and f(N+1) being successive field periods. The two levels of the column reference voltage, Vo+ and Vo-, correspond to the levels of data signals which, in combination with selection signals, would produce the smallest voltage in the range of operating voltages across the display element, i.e. Vth. In a display device using crossed polarisers, this level corresponds to peak white display while for parallel polarisers it corresponds to a black display. In addition, and as in the previous embodiment, the timing of the row selection signal pulse is determined relative to the data signal so that its rising edge is at least substantially complete before the column voltage changes from the reference level to the data signal level. Referring to Figures 8a and 8b, which illustrate the timing relationship between an example of a column waveform, (Figure 8a), and a row conductor waveform, (Figure 8b), in a line inversion scheme, the rise of the row selection pulse signal therefore commences a time Δt before the transition on the column conductor. During this period Δt the display element is charged towards the lowest end of its operating voltage range, Vth, as determined by the level Vo+, and the peak voltage across the non-linear switching device, and hence its peak current density, is minimised. The remainder of the display element charging towards the required display element voltage continues after the period Δt when the column voltage is switched to the video (data) level. Vertical cross-talk reduction is achieved as in the known scheme because the varying data (video) voltage is only present on the column conductors for the fraction, F, of the line time, Tl. Moreover, because the display element pre-charging is towards the lowest of the display element's operating voltage range the non-linearity in the relationship between column voltage and display element voltage illustrated in Figure 6 is removed, or at least significantly reduced. Some residual non-linearity may remain if Δt is too large. Conversely, if Δt is made too small the current density in the non-linear device rises. The preferred useful range of Δt is, therefore, from a minimum approximately equal to the rise time of the row selection pulse signal to a maximum substantially equal to the width i.e. duration, of the data pulse signal, F.Tl. As can be seen from Figures 8a and 8b, the row selection pulse signal is of such a duration that its trailing edge reaches the reference hold level, Vh+, slightly before, or substantially coincident with but not later than, the change in the column voltage from the data signal to the reference potential Vo-. To this end, termination of the selection signal is commenced a short time before the change in column voltage to allow for the finite fall time of the signal, as shown by the sloping trailing edge. The voltage appearing at the display element during the row address period as a result of the application of the waveforms shown in Figures 8a and 8b is illustrated in Figure 9. The display element voltage increases during the period Δt and reaches an initial level according to the level Vo+. Thereafter, during the period F.Tl it is further increased to a level determined by the level of the data signal, Vn+1, and then drops back at the termination of the data signal and selection signal, due to capacitive coupling via the capacitance of the non-linear device 30, to the required display level. The hold level, Vh+, of the row conductor waveform is applied for the remainder of a field period, until the row concerned is next addressed. The hold level is approximately equal to the mean of the rms saturation and threshold voltages of the display elements, that is, Vh = (Vsat + Vth)/2. This level is chosen to minimise the voltage appearing across the non-linear device during this time and maintain the device in the off condition so that the display element voltage is retained until it is driven again in the subsequent field period. However, due to the fact that the liquid crystal material has a finite resistance, some charge leakage will occur and consequently the display element voltage decays slightly. To counter the possible effects of this decay, the hold voltage level may be varied over the field period, rather than held constant, as is described in EP-A-0320054. Figure 10a shows the voltage appearing across the non-linear device 30, Vnld, during a row address period for a display element which is charged to its highest level. For comparison, Figure 10b shows the voltage of a non-linear device in similar circumstances in the case of a display device operating with the known cross-talk reduction drive scheme. As can be seen, the peak voltage, Vp, of the non-linear device is significantly lower when using the drive scheme according to the present invention. Accordingly the probability of non-linear device failure is considerably reduced. In the above described embodiment, the drive scheme involves a row signal waveform having four levels, consisting of selection signal and hold signal portions whose polarity is periodically inverted. The invention is applicable also to drive schemes of a kind in which the row signal waveforms in addition to selection signals similar to those in the four level drive scheme also include an additional selection signal in the form of a reset signal which is applied to a row address conductor followed immediately a setting signal, serving as another selection signal, for the row of display elements which in conjunction with display data signals, which are presented for a part only of the row address period, establishes the desired display element voltages to produce the required display effect from the display elements. Such a drive scheme is described in EP-A-0362939 to which reference is invited for further information and whose disclosure is incorporated herein by reference. Briefly, the purpose of the reset selection signals, which are applied to a row of display elements during the row address period associated with the preceding row of display elements, is to correct for non-uniformities in the behaviour of MIMs across the display device. Prior to presenting a setting signal which together with data signals provides the display elements of a row with a display element voltages of a certain voltage sign, the display elements are charged or discharged by means of the reset selection signal to an auxiliary voltage of the same voltage sign, this auxiliary voltage lying beyond or on the limit of the range used for picture display. The row signal waveform in this type of drive scheme consists then of five levels. Figure 11 illustrates portions of typical row and column signals waveforms VR and VC in an alternative embodiment of the invention using this kind of drive scheme and operating in a line inversion mode. Referring to Figure 11, Vs₁ and Vs₂ are respectively selection and setting signals for the nth row conductor which together with data signals, Vn, applied to the column conductors determine the display state of the associated display elements, and Vs₃ is the reset selection signal applied immediately prior to the setting signal Vs₂ during an address period for the preceding row of display elements in which a selection signal VS₁ is applied to that preceding row. The signal VS₃ is effective to charge the display elements of the row to the black level or beyond whereas the signals VS₁ and VS₂ set the display elements to the required display condition according to the data signal levels. The row signal waveform comprises three transitions, indicated at Tr1, Tr2 and Tr3 which could result in a high peak MIM current. The row and column signal waveforms are controlled in relation to one another in a manner similar to that of the previous embodiment such that the row selection signal commences before the data signal and while a reference potential, constituting a pre-charge voltage level for the display elements, is applied to the column conductors. The data signal Vn, whose level is in a range of possible values, as denoted by the horizontal lines, determining the display element's output, begins after the transition Tr1 of the selection signal Vs1. With regard to the selection signal VS₁ the manner in which this drive scheme operates corresponds to that for the selection signals (Vs) in the previous embodiment and effectively the same results are achieved. During the transition Tr1 a pre-charge reference level, P1, equivalent to the white level for this inversion polarity, is present on the column conductor in an interval between successive data signals. Similarly, in the succeeding field the data signal begins after the transition Tr3 with a pre-charge reference level, P2, equivalent to the black level for this inversion polarity being applied during this transition Tr3 in an interval between successive data signals. The reference levels P1 and P2 thus serve to reduce the peak current through the MIMs for two of the three transitions, Tr1 and Tr3, in the row signal waveform. In the illustrated example, the levels P1 and P2 are equal and correspond to a white signal level for a display element being addressed by a negative selection signal, Vs1, and a black signal level for a display element being addressed by a combination of a reset selection signal Vs3 and positive selection signal Vs2. Although in this particular embodiment the levels of P1 and P2 will often be the same, this need not necessarily always be the case and in certain situations the levels P1 and P2 can be different to one another. A reduction in peak current through the MIMs for all three transitions, Tr1, Tr2 and Tr3, can be obtained using the modified drive scheme illustrated in Figure 12. Figure 12 shows portions of the row signals, VR for the n and n+1 row conductors and portions of a typical column conduction signal Vc containing data signals, Vn and Vn+1, for display elements in these rows. As can be seen, the selection signals VS1 and VS2 are of slightly shorter duration than the reset signal VS3 and the selection signal VS1 for row n in the type of drive scheme using a five level row signal waveform is applied during the interval the reset selection signal VS3 is applied to the succeeding n+1 row conductor and such that the selection signal VS1 occurs after the transition Tr2 and before the transition Tr3 of the reset selection signal. In order then to reduce peak current through the MIMs during the transitions Tr2, the period between successive data signals, e.g. Vn and Vn+1, applied to a column conductor is divided into two parts during which respective and successive pre-charge reference levels are applied. The reference levels P1 and P2 correspond to those described previously and would usually be equal in value. The reference level, P3, applied immediately prior to those levels P1 and P2 coincides with the transitions Tr2 and corresponds to a signal level which is at or near the opposite end of the data signal range to the level P1. The level P3 remains the same, although as before the levels P1 and P2 need not necessarily be equal to one another but could instead be different. With regard to the drive schemes depicted in both Figure 11 and Figure 12 it should be noted that all polarities of the row and column signal waveforms can be inverted while retaining precisely the same basic operating principles. The combination of pre-charging the display elements together with short selection times in accordance with the drive schemes described is highly effective in reducing cross-talk without increasing the probability of non-linear device failure. The drive schemes can allow a wider range of display element dimensions to be used as the technological limits on the size of the non-linear devices are relaxed. Various modifications are possible to the above described embodiments as will be apparent to persons skilled in the art. For example, a sub-pixellation technique can be used in which rather than using a single electrode 20, a display element comprises a plurality of sub-elements, each defined by a respective electrode carried on the plate 14 which are individually connected to a row conductor 22 via a respective non-linear device. While the invention has been described with reference particularly to a twisted nematic liquid crystal display device, it is envisaged that other electro-optical materials can be used. Moreover, while the invention is particularly beneficial in the case of MIMs being used in view of their tendency to become damaged as a result of relatively high current densities, the invention can be applied advantageously to display devices employing other forms of two terminal non-linear switching devices known in the art, such as diode rings, back-to-back diodes, n-i-n, p-i-p or p-i-n-i-p elements, assuming that their switching characteristics meet the requirements.	A method of driving a matrix display device comprising an electro-optical display medium between two supporting plates, an array of display elements arranged in rows and columns with each display element being constituted by electrodes provided on the facing surfaces of the supporting plates, and sets of row and column conductors, each display element being connected in series with a two-terminal non-linear switching device between associated row and column conductors, in which each row of display elements is selected during a row address period by a selection signal of a row signal waveform applied to the row conductors and data signals are applied via the column conductors by means of which selection and data signals a range of operational voltages can be produced at the display elements for display purposes, and in which the data signals are applied for a part of the address period, a reference potential being applied to the column conductors during the remainder of the address period, characterised in that for a row of display elements the row selection signal (Vs) commences prior to the application of the data signals (Vn) and during the application of the reference potential (Vo) whereby the display elements are initially charged to a level approaching the lower end of the operational range of voltages and thereafter are charged to the required level according to the applied data signals. A method according to Claim 1, characterised in that in response to the selection signal the display elements are initially charged to a level approaching the lower end of the range of transition in the transmission/voltage characteristic of the electro-optical display medium. A method according to Claim 1 or Claim 2, characterised in that the reference potential is periodically switched between two levels in accordance with a periodic inversion of the selection and data signals. A method according to any one of Claims 1 to 3, characterised in that the leading edge of the selection signal is at least substantially complete before the voltage on a column conductor changes from the reference potential to the data signal. A method according to any one of the preceding claims, characterised in that the interval between the beginning of the selection signal and the beginning of the data signal is at least substantially equal to the rise time of the selection signal and at most substantially equal to the duration of the data signal. A method according to any one of the preceding claims, characterised in that the selection signal terminates before or coincident with the termination of the data signal. A method according to Claim 1 or Claim 2, characterised in that the row signal waveform applied to each row conductor further includes a second selection signal comprising a reset signal portion by means of which the display elements of the row are charged at least to the upper end of the range of operational voltages followed by a setting signal portion by means of which the display elements are set at a level in the range of operational voltages according to the applied data signals, and in that for a row of display elements the setting signal portion commences prior to the application of the data signals and during the application of a reference potential whereby the display elements are charged from the level obtained by the reset signal portion back to a level close to the upper end of the range of operational voltages. A method according to Claim 7, characterised in that the reference potentials for use with the first-mentioned selection signal and the setting signal portion are applied to each column conductor in respective intervals between successive data signals applied to the column conductor. A method according to Claim 7, or Claim 8, characterised in that for a row of display elements the reset signal portion commences prior to the application of the data signals to the column conductors intended for a preceding row of display elements and during the application of a further reference potential to the column conductors whereby the display elements of the row are charged to a level approaching the lower end of the range of operational voltage and thereafter are charged to at least the upper end of the said range. A method according to Claim 9, characterised in that the reference potentials for use with the first-mentioned selection signal and the reset signal portion are applied to each column conductor consecutively in an interval between successive data signals applied to the column conductor. A method according to any one of Claims 7 to 10, characterised in that the first-mentioned selection signals and the second selection signals are applied to a row conductor alternately in successive field periods. A method according to any one of Claims 7 to 11, characterised in that the setting signal portion terminates before or coincident with the termination of a data signal. A method according to any one of the preceding claims, characterised in that the electro-optical display medium comprises liquid crystal material. A method according to any one of the preceding claims, characterised in that the switching devices comprise MIMs. A matrix display device having a row and column array of display elements comprising electrodes carried on facing surfaces of two supporting plates with an electro-optical display medium therebetween, sets of row and column conductors, each display element being connected in series with a non-linear switching device between associated row and column conductors, and row driver and column driver circuits for providing during respective row address periods a selection signal to each row conductor, and data signals to the column conductors for a part of the address period by means of which signals a range of operational voltages can be produced at display elements for display purposes, the column driver circuit being arranged to provide a reference potential during the remainder of the address period, characterised in that the row driver circuit is arranged to start a row selection signal (Vs) in a row address period a predetermined time before the beginning of the data signal (Vn) provided by the column driver circuit and during the application of the reference potential (Vo) to the column conductors, the reference potential provided by the column driver circuit being operable to charge the display elements of the row towards the lower end of their operational voltage range prior to the application of the data signal.	PHILIPS ELECTRONICS NV; PHILIPS ELECTRONICS UK LTD; PHILIPS ELECTRONICS N.V.; PHILIPS ELECTRONICS UK LIMITED	ANNIS ALEXANDER DAVID C O PHIL; KNAPP ALAN GEORGE; SANDOE JEREMY NOEL; WOLFS PETER BAS ANTON; ANNIS, ALEXANDER DAVID, C/O PHILIPS ELECTRONICS; KNAPP, ALAN GEORGE; SANDOE, JEREMY NOEL; WOLFS, PETER BAS ANTON
EP-0489460-B1	489,460	EP	B1	EN	19,960,214	1,992	20,100,220	new	H04N5	H04N5	H04N7, H04N5	H04N 5/956	Pick-up and/or display device, and an imaging system comprising such a device	A pick-up and/or display device comprises a memory in which a video signal is written at a write frequency under the control of a clock and is read therefrom at a read frequency. Image expansion or image compression can thus be realised. The clock, a clock input of which is connected to a synchronizing pulse generator, comprises an oscillator having an adjustable frequency, an oscillator output constituting a clock output and being connected to a frequency divider whose output signal is applied to an integrating comparator circuit, an output signal variation of which is proportional to a difference between a mean input signal and a predetermined reference voltage, the comparator circuit being connected to a frequency set input of the oscillator, the oscillator comprising a trigger input which serves to switch the oscillator on and off and which constitutes the clock input. A clock of this kind exhibits an accurate phase relationship with the synchronizing signal which is not subject to temperature drift and noise. The frequency of the clock can be accurately adjusted by adjustment of the reference voltage.	The invention relates to a pick-up and/or display device, comprising a memory for the storage of a video signal, a clock for the supply of write or read clock pulses to the memory, and a synchronizing pulse generator for applying synchronizing pulses to a clock input of the clock. A pick-up and display device of this kind is known from European Patent Application EP-0 213 912-A2. The cited Patent Application describes a pick-up and display device in which a video signal of a television image having a 5:3 aspect ratio is compressed in a line direction in the television pick-up device so as to form a video signal associated with an image having a 4:3 aspect ratio. To this end, in the television pick-up device the video signal is digitized and written into a line memory at a first clock frequency which is generated by a first clock. This clock comprises, for example a phase-locked loop and generates 1100 clock pulses within a line period, so that an image line is composed of 1100 pixels. During reading the video signal is sampled so that one or two pixels are lacking between two neighbouring pixels in each image line in the line memory. The line memories are read by a second clock which generates clock pulses having a second clock frequency, for example amounting to 910 times the line frequency. Both clocks are controlled by the line synchronizing signal. Because an image line read from the line memory contains fewer pixels than an image line written into the line memory, image compression occurs. When the compressed video signal is displayed on an image display unit having a 4:3 aspect ratio, the video signal remains compressed. When the video signal is displayed on an image display unit having a 5:3 aspect ratio, the video signal is again written into a line memory in the television display device at a frequency equal to the read frequency prior to the image compression. When the line memory is subsequently read at the frequency equal to the write frequency prior to the image compression, the image compression is cancelled. It is an object of the invention to provide a television pick-up and/or display device of the kind set forth in which a clock frequency can be accurately adjusted and in which the clock signal has a fixed phase with respect to a reference signal, notably a line synchronizing signal. To achieve this, a pick-up and/or display device in accordance with the invention is characterized in that the clock comprises an oscillator having an adjustable frequency for supply of an output signal to the memory and to an integrating comparator circuit which is suitable to produce an output signal variation which is proportional to a difference between a mean input signal and a predetermined reference voltage for supply to a frequency set input of the oscillator, the oscillator comprising a trigger input which is coupled to the synchronizing pulse generator in order to switch the oscillator on and off. Because the oscillator is triggered by the synchronizing pulse generator, notably the line synchronizing pulse generator, the oscillator always has the correct phase with respect to the line synchronizing signal. This offers inter alia the advantage that the image information read from the memory for each image line appears in the same horizontal position on the display screen of the image display unit, thus preventing so-called phase jitter. The frequency of the clock can be simply adjusted to a multiple of the line frequency by adaptation of the reference voltage of the comparator circuit. Another advantage of such a clock consists in that, contrary to the known phase-locked loops, the phase of the oscillator with respect to the line synchronizing signal is not determined exclusively for one integer frequency ratio of the oscillator frequency to the line synchronizing frequency and that the clock is insensitive to thermal drift and noise. Furthermore, the frequency of the oscillator can be highly accurately adjusted to a freely adjustable multiple (which need not necessarily be an integer multiple) of the frequency of the synchronizing signal by adjustment of the reference voltage of the comparator circuit. A further embodiment of a pick-up and/or display device in accordance with the invention is characterized in that the oscillator is coupled to the integrating comparactor circuit via a frequency divider. The frequency of the oscillator is adjusted by means of the frequency divider and the integrating comparator circuit. When the integrated output signal of the frequency divider is equal to the predetermined reference voltage within a line period, the frequency of the oscillator becomes constant. The frequency divider is preferably formed by a counter which is connected to the synchronizing pulse generator by way of a trigger input for resetting to zero. The oscillator preferably comprises a voltage-controlled oscillator. A pick-up and/or display device in accordance with the invention can be used in an imaging system comprising an image pick-up device which includes an image pick-up face and an optical system for imaging a circular object plane as an ellipse on the image pick-up face, the image pick-up device being connected to a memory of a television pick-up and/or display device in accordance with the invention, which memory is connected to an image display unit for displaying a circular object plane as a circular image. In an imaging system comprising an X-ray examination apparatus, the optical system images a circular image of an exit screen of an X-ray image intensifier tube as an ellipse on a rectangular CCD sensor. In comparison with the case where a circular image were imaged as an inscribed circle on the rectangular CCD sensor, the horizontal resolution of the image picked up is thus enhanced. Such an X-ray examination apparatus is disclosed in European Patent Application EP-0 295 728-A1. The video signal from the CCD sensor is stored in an image memory having a predetermined write frequency. When the image memory is read, the read clock frequency is higher than the write clock frequency, thus giving rise to image compression so that the circular image of the exit screen of the X-ray image intensifier tube is again displayed as a circle on an image display unit. The use of a television pick-up and/or display device in accordance with the invention is also attractive for imaging systems such as endoscopes, microscopes and other imaging systems comprising a circular object plane and a rectangular image pick-up device, and in systems in which image transformation is used, for example interactive image display devices comprising an optical data carrier such as digital or analog optical video discs. The invention will be described in detail hereinafter with reference to the accompanying drawing. Therein: Fig. 1 shows a block diagram of a clock for use in a television pick-up and/or display device in accordance with the invention, and Fig. 2 shows diagrammatically the pulse sequences in a television pick-up and/or display device in accordance with the invention. Fig. 1 shows a clock 1, comprising a voltage-controlled oscillator (VCO) 2, a counter 3, a comparator circuit comprising an amplifier 5 and a capacitor 6, an oscillator 7, a synchronizing pulse generator 9, a memory 11, an image pick-ip device 13, and an image display unit 15. An image pick-up face in the image pick-up device 13, for example a CCD camera, is line-wise read under the control of the synchronizing pulse generator 9. The video signal generated by the image pick-up device 13 is stored in the memory 11 which is, for example a line memery. A first clock signal having a write frequency f1 is applied to the memory 11 by the oscillator 7. When the video signal stored in the memory 11 is displayed on the image display unit 15, the video signal is read from the memory 11 at a read frequency f2. The video signal modulates the intensity of an electron beam which frame-wise scans a display screen in the image display unit 15 under the control of the synchronizing pulses. The synchronizing pulse generator 9 applies line synchronizing pulses to a trigger input 17 of the voltage-controlled oscillator 2, which pulses have a sequence as designated by the reference H-sync in Fig. 2. One period of the line synchronizing pulses comprises 856 write clock pulses and the pulse width of the line synchronizing pulses amounts to (856 - 792) write clock pulses. The line synchronizing pulse H-sync triggers the counter 3 which is a 1024 counter in the present embodiment but which is in a most general sense an N-counter, where N may also have the value 1. The counter counts the number of positive going edges of the pulses appearing on its input 19. The input signal of the counter 3, having the write clock frequency f2, is designatedby the reference f2 in Fig. 2. The signal designated by the reference CNTR-Q10 in Fig. 2 appears on the output of the counter 3. The frequency of the voltage-controlled oscillator 2 becomes constant if the mean value of the output signal of the counter 3 is equal to the reference voltage αVcc, the supply voltage Vcc being applied to a terminal 4. The factor α equals R1/(R1+R2). When the frequency of the voltage-controlled oscillator 2 is constant: (tQ/tH)Vcc = αVcc. Therein, tH is the line period and tQ is the period of time during which the output of the counter 3 is high. For the line period tH it holds good that tH = 856/f1 and for tQ that tQ = 792/f1-1024/f2. The ratio of the write frequency f1 to the read frequency f2 is thus found: f1/f2 = 0.773-0.836α. The ratio of the write frequency to the read frequency is independent of the supply voltage Vcc and hence is free from noise and drift. The factor 0.773 in the expression for the ratio of the write frequency f1 to the read frequency f2 is determined exclusively by the dividends of the synchronizing frequency and the counter 3 and is free from tolerances. This factor is preferably chosen so that it approximates a desired frequency ratio as well as possible, thus enabling fine control by variation of the second term, i.e. 0.836α. To this end, one of the resistors R1 and R2 may be constructed as a variable resistor, or instead of two resistors use can be made of a controlled voltage source which produces, for example the deviation of the oscillation frequency from the mains frequency.	A pick-up and/or display device, comprising a memory (11) for the storage of a video signal, a clock (1) for the supply of write or read clock pulses to the memory, and a synchronizing pulse generator (9) for applying synchronizing pulses to a clock input of the clock, characterized in that the clock comprises an oscillator (2) having an adjustable frequency for the supply of an output signal to the memory (11) and to an integrating comparator circuit (5, 6) which is suitable to produce an output signal variation which is proportional to a difference between a mean input signal and a predetermined reference voltage for supply to a frequency set input (18) of the oscillator (2), the oscillator (2) comprising a trigger input (17) which is coupled to the synchronizing pulse generator (9) in order to switch the oscillator on and off. A pick-up and/or display device as claimed in Claim 1, characterized in that the oscillator (2) is coupled to the integrating comparator circuit (5, 6) via a frequency divider (3). A pick-up and/or display device as claimed in Claim 2, characterized in that the frequency divider (3) comprises a counter. A pick-up and/or display device as claimed in Claim 3, characterized in that the counter (3) comprises a trigger input (20) which is connected to the synchronizing pulse generator (9). A pick-up and/or display device as claimed in Claim 1, 2, 3 or 4, characterized in that the oscillator (2) comprises a voltage-controlled oscillator. A pick-up and/or display device as claimed in Claim 1, 2, 3, 4 or 5, characterized in that the synchronizing pulse generator (9) generates line synchronizing pulses. An imaging system, comprising an image pick-up device (13) which includes an image pick-up face and an optical system for imaging a circular object plane as an ellipse on the image pick-up face, the image pick-up device (13) being connected to a memory of a pick-up and/or display device as claimed in any one of the preceding Claims, said memory being connected to an image display unit (15) for displaying a circular object plane as a circular image. An imaging system as claimed in Claim 7, comprising an X-ray source, an X-ray image intensifier which is arranged so as to face the X-ray source and which comprises an exit window, the image pick-up device being arranged so as to face the exit window, the optical system being arranged between the exit window and the image pick-up device. A clock comprising an oscillator (2) having an adjustable frequency for the supply of an output signal to a memory (11) and to an integrating comparator circuit (5, 6) which is suitable to produce an output signal variation which is proportional to a difference between a mean input signal and a predetermined reference voltage for supply to a frequency set input (18) of the oscillator, the oscillator comprising a trigger input (17) which is coupled to a synchronizing pulse generator (9) in order to switch the oscillator on and off.	PHILIPS ELECTRONICS NV; PHILIPS ELECTRONICS N.V.	LOONEN ANTONIE ROCHUS MARIA; LOONEN, ANTONIE ROCHUS MARIA
EP-0489461-B1	489,461	EP	B1	EN	19,941,109	1,992	20,100,220	new	H05G1	H04N5	H05G1, A61B6, H04N5	H05G 1/64, H04N 5/32	X-ray imaging system	The invention relates to an X-ray imaging system, comprising an X-ray source (2) for emitting an X-ray beam, a power supply unit (14) which is connected to the X-ray source, an X-ray detector (8) for converting the X-ray beam into an optical image, a television pick-up device (10) for converting the optical image into a video signal, a detection device (12) which is connected to the television pick-up device and which serves to form a control signal from the video signal, an output of the detection device being connected to the power supply unit for adjustment thereof, and a display unit which is connected to the output of the television pick-up device via an amplifier (18). When the reciprocal of the signal generated by the detection device is used as the gain factor for the amplifier, a stable brightness is obtained on the television monitor without giving rise to a light flash when the X-ray source is switched on. As a result, the duration of exposure can be reduced during medical imaging so that the dose applied is less and motional unsharpness is reduced.	The invention relates to an X-ray imaging system, comprising an X-ray source for emitting an X-ray beam, a power supply unit which is connected to the X-ray source, an X-ray detector for converting the X-ray beam into an optical image, a television pick-up device for converting the optical image into a video signal, a detection device for applying to the power supply unit a first control signal that is a function of the light intensity of the optical image , a display unit for displaying the video signal from the television pick-up device after amplification by an amplifier and means for supplying a second control signal to a set terminal of the amplifier for adjustment of a gain factor of the amplifier. An X-ray imaging device of this kind is known from US-A-4 910 592. This document describes an X-ray imaging system comprising two control loops. The first control loop is an automatic dose control loop which adjusts the dose generated by the X-ray source so that the mean light intensity of the optical image produced by the X-ray detector is constant. A signal that is a function of this mean light intensity is detected by a detection device and applied as a first control signal to the power supply unit of the X-ray source. Thus, for objects which differ as regards X-ray absorption there are obtained video signals which have the same mean value or peak value. The video signal is applied to a television monitor via an amplifier which forms part of the second control loop, being an automatic gain control loop. A control component which is included in the second control loop provides an external control signal for adjusting the gain of the amplifier. As a result of the use of an automatic gain control loop, the brightness of the image on the television monitor remains constant also if, in the case of very thick objects or objects exhibiting a high radiation absorption, the automatic dose control loop cannot increase the dose to such an extent that the mean light intensity on the entrance screen of the television pick-up device is sufficient. It is desirable that, when the dose increases upon activation of the X-ray source, the automatic gain control loop also increases the gain factor for the video signal applied to the television monitor, so that an image having the desired mean brightness appears on the television monitor already during the adjustment period of the automatic dose control loop. Because the X-ray dose and the gain factor for the video signal then increase simultaneously, the video signal, however, exhibits a peak which is perceived as a disturbing flash in the X-ray image. It is an object of the invention to provide an X-ray imaging system in which an X-ray image of good quality is quickly obtained during dynamic imaging. To achieve this, an X-ray imaging system according to the preamble of Claim 1 is characterized in that the detection device is adapted to supply the second control signal, for which purpose the detection device determines a mean or peak value of the video signal in a measurement field within the video image, the second control signal supplied by the detection device adjusting the gain factor of the amplifier such that the gain factor is held at a predetermined maximum value until the mean or peak value exceeds a predetermined threshold value, after which the gain factor is adjusted in order to maintain the mean level of the signal applied to the display unit constant. As a result of these measures, the video signal applied to the television monitor quickly reaches its desired mean value or peak value, substantially without said values exhibiting overshoot. Because the video signal applied to the television monitor quickly reaches the correct value, in an X-ray system in accordance with the invention the first usable X-ray images become available already 0.17 s after activation of the X-ray source. This compares favourably with another known X-ray system disclosed in US-A-4 101 776 in which for the same circumstances the automatic gain control loop requires 0.45 s for correct adjustment of the video signal applied to the television monitor. As a result, the radiation dose applied to the object is more efficiently used; this is a major advantage in medical diagnostics considering the possible detrimental effects of X-rays on living organisms. An embodiment of the X-ray system in accordance with the invention is characterized in that an output of the detection device on which the first control signal is supplied is connected to a divider for forming the gain factor on a divider output, which gain factor is proportional to the reciprocal of the first control signal applied to the divider, the divider output being connected to the set terminal of the amplifier for supplying the second control signal thereto. In the divider the video signal supplied by the television pick-up device, referred to hereinafter as the camera signal, is divided by a peek value or mean value determined in the detection device during a sampling period, for example during a frame period (40 ms) or a field period (20 ms). In static situations, where the mean light intensity on the entrance face of the television pick-up device is constant, a normalized video signal appears at the amplifier output. In dynamic situations, the mean values or peak values of the video signals generated by the television pick-up device during successive frame of field periods deviate from one another, so that a small deviation from the normalized video signal arises, which deviation depends on the difference in mean brightness or peak brightness between two successive frames or fields. A further embodiment of an X-ray imaging system in accordance with the invention is characterized in that the detection device comprises at least two detection modules, an input of each module being connected to the television pick-up device, the output of a first detection module being connected to the power supply unit, the output of a second detection module being connected to the set terminal of the amplifier. Because the automatic dose control and the gain factor for the video signal applied to the television monitor can be independently adjusted, an optimum image quality can be combined with an as low as possible dose, for example by peak value detection within a measurement field in the first detection module and by detection of the mean value within a second measurement field in the second detection module. Furthermore, the control behaviour of the automatic dose control loop can be adjusted by adaptation of the size and the location of the measurement field of the second detection module within the video image. Some embodiments of an X-ray imaging system in accordance with the invention will be described in detail hereinafter with reference to the accompanying drawing. Therein: Fig. 1 diagrammatically shows a known X-ray imaging system, Figs. 2a and 2b show the peak value of the video signal generated by the television pick-up device and the video signal applied to the television monitor for an increasing radiation dose in a known X-ray imaging system, Fig. 3 diagrammatically shows an X-ray imaging system in accordance with the invention, Fig. 4 shows the measure response of an X-ray imaging system in accordance with the invention to a linearly increasing radiation dose, Fig. 5 shows the peek value of the video signal applied to the television monitor in an X-ray imaging system in accordance with the invention for a video signal from the television pick-up device which increases in accordance with Fig. 2a, and Fig. 6 shows a block diagram of a detection device in accordance with the invention. Fig. 1 shows an X-ray imaging system which comprises an X-ray source 2 emitting an X-ray beam 4 which irradiates an object 6. An X-ray detector 8, preferably an X-ray image intensifier, converts the X-ray beam, locally intensity-modulated by the object 6, into an optical image which appears on an exit screen of the X-ray image intensifier. This optical image is converted into a video signal Vc by a television pick-up device, for example a video camera comprising a pick-up tube or a CCD sensor. This video signal is applied to a first detection device 12 which determines a mean value or a peak value of the video signal in a measurement field within the video image generated by the video camera 10. The first control signal formed in the detection device 12 is applied to a power supply unit 14 of the X-ray source 2. When the current through the filament of the X-ray source 2 is increased, the intensity of the X-rays increases; when the high voltage of the X-ray source is increased, the electrons are accelerated faster to the anode, so that the energy and hence the penetrating power of the X-rays increases. The mean light intensity on the entrance screen of the video camera 10 is kept constant by varying the current and the high voltage of the X-ray source 2 in dependence on the thickness of the object 6 to be irradiated, which variation is between, for example 0.1 mA and 1200 mA and between 40 kV and 125 kV, respectively. Because the dose control loop I, formed by the X-ray source 2, the video camera 10, the detection device 12 and the power supply unit 14, cannot increase the X-ray dose sufficiently to keep the mean light intensity on the entrance screen of the video camera 10 constant in the case of very thick or highly radiation-absorbing objects 6, a gain control loop II is required to keep the mean brightness level of the image displayed on the television monitor 16 constant. The video signal generated by the video camera 10 is amplified by an amplifier 18. The output signal Vm of the amplifier 18 is applied to a second detection device 20 which determines a mean value or a peak value in a measurement field within the video image. Via a differential amplifier 22, the signal originating from the detection device 20 is compared with a reference voltage Vref which corresponds to a desired mean brightness level of the video image. The difference voltage originating from the differential amplifier 22 is applied, via an integrator 21, as a second control signal to a set terminal 24 of the amplifier 18 so that the gain factor is adapted. Fig. 2a shows the variation of the video signal Vc generated by the video camera 10 when the X-ray source 2 of a Philips X-ray apparatus type BV 25 is switched on. Fig. 2b shows the variation of the video signal Vm applied to the television monitor 16 when use is made of the known gain control loop II. Because the average value of the video signal Vc applied to the amplifier 18 is lower than the reference voltage Vref, the gain factor of the amplifier 18 is increased. However, because the video signal Vc from the video camera 10 increases during the period of time required by the gain control loop II to increase the gain factor, an overshoot of 190 mV occurs in the video signal Vm applied to the television monitor. This overshoot could be prevented by incorporating a greater delay in the gain control loop II. However, this has the drawback that radiation which is strongly attenuated by the object 6 cannot be used for medical imaging. Making the gain control loop II faster would cause more overshoot and would not lead to an improvement either. The response as shown in Fig. 2b occurs in the case of critical damping of the gain control loop II and is optimum for such a control loop. Fig. 3 shows an X-ray imaging system in which the automatic gain control loop is replaced by a divider 19. The divider 19 forms the second control signal for adjusting the gain factor of the amplifier 18 by dividing the reference voltage Vref by the signal applied to the divider 19 by the detection device 12 and applies the second control signal to the set terminal 24 of the amplifier 18. During a field period a mean value or peek value of the video signal Vc is determined in the detection device 12. The video signal formed by the video camera 10 is divided by this value during the next field period. When the video signal from the video camera 10 increases, as shown in Fig. 2a, the peek values and/or the mean values of the video signal are small during the initial field periods of the video signal, so that the gain factor of the amplifier 19 becomes very high. In order to prevent this, the detection device 12 forms a predetermined threshold value on its output, for example for mean values or peak values below this threshold value. As soon as the output signal of the detection device 12 exceeds the threshold value, the mean level of the video signal Vm applied to the television monitor 16 is controlled to Vref. This is illustrated in Fig. 4. In Fig. 4 it is assumed that the mean level of the video signal Vc from the video camera 10 linearly increases as a function of time: Vc = t. In Fig. 4 the voltage is plotted as a function of time in arbitrary units. In the divider 19 the gain factor k(t) is formed by the quotient of the reference voltage Vref and the mean value or peak value measured during a preceding frame period T. In the case of uniform illumination of the entrance screen of the video camera 10, the brightness in any point of the video image is equal to the mean value and the peek value. In this case the gain factor k(t) is given by: k(t) = Vref/Vc(t-T). For a reference voltage Vref amounting to 10 V and a frame period T amounting to 1 s, k(t) is shown as a curve a in Fig. 4. For small values of t the gain factor k(t) tends to become infinite. If the threshold value of the detection device 12 is 5 V, the maximum gain factor in this case equals 2. For the time interval 0 < t < 6 s: Vm = 2Vc = 2t. After 6 seconds the gain factor k(t) decreases if Vref/(t-T) = 10/(t-1) as denoted by the non-interrupted part of the curve a in the Figure. For the signal Vm(t) applied to the television monitor 16 it then holds good that: Vm(t) = Vc(t).k(t) = 10t/(t-1). As is shown in Fig. 4, after 6 seconds Vm(t) follows the non-interrupted part of the curve b. Fig. 4 shows that the video signal Vm(t) exhibits an overshoot with respect to the reference voltage Vref which is greater as the maximum gain factor of the amplifier 18 is greater (the threshold value of the detection device is then lower). For a smaller maximum gain factor (less slope of Vm(t)) less overshoot occurs, but more time is required before Vm(t) is stabilized at the level of Vref. It can also be deduced from Fig. 4 that the overshoot can be reduced by way of a shorter integration time of the detection device. Fig. 5 shows the response of the X-ray imaging system in accordance with the invention to a video signal Vc which increases according to the curve shown in Fig. 2a. After 0.17 s, the level of the video signal has been stabilized at the level Vref which amounts to 300 mV in the present case. The overshoot, amounting to 30 mV, is so small that the light flash occuring on the monitor 16 when the known gain control loop is used is now absent. It has been found that when the video signal Vm applied to the television monitor is appropriately adjusted, the exposure duration can be reduced by 36% in the so-called snapshot mode. As a result, less motional unsharphess occur in the image and the dose applied to a patient is reduced. Fig. 6 diagrammatically shows the detection device 12. The detection device comprises three detection modules 30, 32 and 34, the detection module 32 being formed by a video mean value detector, the detection modules 30 and 34 being formed by video peak value detectors. The video signal Vc from the television camera 10 is applied to the detection modules 30, 32 and 34 after amplification by way of an amplifier 36 having a variable gain factor. Depending on the position of the switch 38, the signal Vs applied to the power supply unit is formed by a mean value or by a peak value. These values are determined within a measurement field of the video image, which measurement field can be adjusted via adjusting terminals 42 and 44. Depending on the position of the switch 40, the divider 19 receives a mean value or a peak value of the video signal Vc. The divider 19 forms the quotient of the gain factor of the amplifier 36 and the amplified video signal Vc, so that the reciprocal of the peak value or the mean value of the video signal Vc appears at the output of the divider 19. This value is applied to the amplifier 18 which is in this case formed by a multiplier, an input of which constitutes the amplifier set terminal 24. In the multiplier 18 the video signal Vc is divided by the mean value or the peak value, so that the video signal Vm applied to the television monitor 16 has a constant mean brightness level. The advantage of separate detection modules 30-34 resides in the fact that the control behaviour of the automatic dose control loop and the adjustment behaviour of the gain of the video signal Vm can be separately adapted, by selection of peak value detection or mean value detection within an adjustable measurement field, to the imaging method used, for example fluoroscopy or snapshots.	An X-ray imaging system, comprising an X-ray source (2) for emitting an X-ray beam (4), a power supply unit (14) which is connected to the X-ray source, an X-ray detector (8) for converting the X-ray beam into an optical image, a television pickup device (10) for converting the optical image into a video signal, a detection device (12) for applying to the power supply unit (14) a first control signal that is a function of the light intensity of the optical image, a display unit (16) for displaying the video signal from the television pick-up device (10) after amplification by an amplifier (18) and means for supplying a second control signal to a set terminal (24) of the amplifier for adjustment of a gain factor of the amplifier, characterized in that the detection device (12) is adapted to supply the second control signal, for which purpose the detection device determines a mean or peak value of the video signal in a measurement field within the video image, the second control signal supplied by the detection device adjusting the gain factor of the amplifier (18) such that the gain factor is held at a predetermined maximum value until the mean or peak value exceeds a predetermined threshold value, after which the gain factor is adjusted in order to maintain the mean level of the signal applied to the display unit (16) constant. An X-ray imaging system as claimed in Claim 1, characterized in that an output of the detection device (12) on which the first control signal is supplied is connected to a divider (19) for forming the gain factor on a divider output, which gain factor is proportional to the reciprocal of the first control signal applied to the divider, the divider output being connected to the set terminal (24) of the amplifier (18) for supplying the second control signal thereto. An X-ray imaging system as claimed in Claim 2, characterized in that the amplifier (18) comprises a multiplier, a first input terminal of which constitutes the set terminal (24), a second input terminal thereof being connected to the television pick-up device (10). An X-ray imaging system as claimed in Claim 1, 2 or 3, characterized in that the detection device (12) comprises at least two detection modules (30, 32, 34), an input of each module being connected to the television pick-up device (10), the output of a first detection module being connected to the power supply unit (14), the output of a second detection module being connected to the set terminal (24) of the amplifier (18).	PHILIPS NV; N.V. PHILIPS' GLOEILAMPENFABRIEKEN	LOONEN ANTONIE ROCHUS MARIA; LOONEN, ANTONIE ROCHUS MARIA
EP-0489462-B1	489,462	EP	B1	EN	19,960,612	1,992	20,100,220	new	G05D23	G05F1	H02M1, H02M5, G05F1	G05F 1/45, H02M 5/257C	Improved system for triac trigger control in combination with a sensing element	The invention relates to a circuit of the kind wherein a load (L) is supplied via a triac (TC) with current from an AC voltage supply source (A, B) under the control of a triac control means (IC) in combination with a sensing element (RT). In previous circuits the sensing element is energised by a current from a DC source which is derived by rectification and smoothing of the alternating current of an alternating voltage supply source, which has limitations in integrated circuitry. In the present invention the sensing element (RT) is energised by an alternating current to produce a sensed alternating current. The triac control means (IC) includes an integration means (6) for producing a control signal which is representative of the integral of the difference between a value corresponding with the average peak to peak magnitude of the sensed alternating current and a reference value. The triggering or otherwise of the triac (TC) being determined by a latch (LCH) actuated in response to the magnitude of the control signal relative to one or more threshold levels. The present invention may be used in thermostats or other sensing devices.	The present invention relates to a circuit arrangement comprising a load supplied via a triac with current from an alternating voltage source under control of a triac trigger control means in combination with a sensing element. Such an arrangement is known from UK Patent Application GB-A-2 075 723. As a rule, the alternating voltage source is formed by an alternating mains voltage source. Usually the sensing element is sensitive to the effects produced by the load. For example, the sensing element may be a temperature dependent resistance located in proximity to a load in the form of a heating element, in which case variations of the sensing element may be utilised to control triggering of the triac to ensure that the heat produced by the load remains within certain temperature limits. In known circuit arrangement the sensing element is energised by a current from a direct current source so as to produce a voltage for influencing operation of said triac control means. Additionally, the triac trigger control means form part of an integrated circuit assembly incorporating a direct current supply source which, in operation, is able to be energised by the alternating voltage source. Accordingly, the sensing element is readily able to be energised from the direct current supply source forming part of the integrated circuit assembly. Employing direct current energisation of the said sensing element has the disadvantage that, unless battery supplies are available as a direct current source, it is necessary to provide a source of direct current by rectification and smoothing of alternating current derived from the alternating voltage supply source. The provision of battery supplies is expensive, likewise the provision of a rectification and smoothing circuit if a direct current source is energised from a mains supply. In instances where the triac trigger control means form part of an integrated circuit assembly incorporating a direct current supply source energised by the said alternating voltage source, utilisation of the incorporated direct current supply source has the limitation that typical incorporated direct current supply sources deliver voltages of less than 12 volts in order to suit the power supply needs of the triac control system. For the energisation of the sensing element from a source of direct current it is preferable for the source to have a terminal voltage significantly larger than 12 volts in order to utilise the available operating range of the sensing element. For example, the resistance of a thermistor employed as a sensing element for an electric cooking appliance may vary by three orders of magnitude over the anticipated cooking range. With circuit arrangements of the kind to which the invention relates, in practice it may be necessary for the load and the sensing element to be located remotely from the remainder of the circuit arrangement with the consequence that connection leads between the remotely located sensing element and the remainder of the circuit arrangement are susceptible to the pick-up of interference which may impair satisfactory operation of the circuit arrangement when the sensing element is energised from a source of direct current, unless the interference is filtered. Moreover, circuit arrangements of the kind to which the invention relates frequently employ a temperature setting element in addition to a temperature sensing element, which temperature setting element is energised from the same source of direct current so that in the event of the temperature setting element being remotely located, the connection leads thereto are also susceptible to the pick-up of interference unless provision is made for filtering such interference. A circuit arrangement in accordance with the present invention has a number of novel features and, in comparison with known circuit arrangements of the kind to which the invention relates, displays many advantages which will be apparent from the following general description thereof and from the following description of individual embodiments of the invention. For this purpose, the circuit arrangement in accordance with the invention is characterised in that said sensing element is energised by alternating current derive from the alternating voltage source to produce a sense alternating current and the said triac trigger control means includes an integration means for producing a control signal, triggering or otherwise of the said triac being determined by the state of a latch actuated in response to the magnitude of the control signal relative to one or more threshold levels, during at least one state of the latch the control signal produced by the integration means representing the integral of the difference between a value corresponding with the average peak to peak magnitude of the sensed alternating current and a reference value. The control signal can be produced by integration of the difference between the average peak to peak magnitude of the sensed alternating current and that of a reference alternating current but the invention is not limited to production of the said control signal in this way. One form of the invention is based upon the use of a single threshold and actuation of the said latch in response to the magnitude of the control signal which is able to be carried out only when the latch is in a given state, such actuation being in response to the magnitude of the control signal relative to the single chosen threshold level, with actuation of the latch when in it's opposite state being produced by means other than in response to the control signal. For instance, the latch may be designed to automatically return to the given state after a fixed time period in it's opposite state. In this way the latch may be arranged to function as a cyclic switch controlling the triggering of the triac in accordance with a duty cycle having a fixed time interval of continuous triac triggering and variable time interval of non-triggering or vice versa, the length of each variable time interval being determined by the time taken for the magnitude of the control signal to reach the chosen threshold level. Another form of the invention may be based upon the use of two thresholds. In this case, the latch has a reset state and a set state and changeover of the latch state from the set state to the reset state (or vice versa) is actuated by the magnitude of the control signal exceeding a first threshold level whereas changeover of the latch state from the reset state to the set state (or vice versa) is actuated by the magnitude of the control signal falling below a second threshold level. With a two threshold level form of the invention, the triac trigger control means may be arranged so that here also the latch functions as a cyclic switch controlling the triggering of the triac in accordance with a duty cycle having a fixed time interval of continuous triac triggering and a variable time interval of non-triggering or vice versa. However, with the triac control means so arranged, whilst the length of each variable time interval is determined during one latch state, as before, by the time taken for the magnitude of the control signal to reach one threshold level( for example, the first threshold level) there is a significant difference from the single threshold level form of the invention in that, during the other latch state, the control signal produced by the integration means does not represent the integration of the difference between the magnitude of the sensed alternating current and that of a reference alternating current. Instead, by utilization of a source of constant current the control signal produced by the integration means, during this other latch state, changes in magnitude at such a rate as to reach the other threshold level ( for example, the second threshold level) at the end of a fixed time interval. Alternatively with a Two Threshold Level form of the invention, the triac trigger control means may be arranged so that the latch functions as a cyclic switch controlling the triggering of the triac in accordance with a duty cycle having a variable time interval of continuous triac triggering and a variable time interval of non-triggering. In one system for achieving this, the integration means comprises a capacitance which is charged and discharged at a rate proportional to the difference in magnitude between the said sensed alternating current and the said reference alternating current, with the voltage corresponding to the charge on the capacitance serving as the control voltage. With this system, the respective durations of both variable time intervals, commencing from the instant of latch changeover, is determined by the time taken for the magnitude of the control signal to reach the threshold level for the next latch actuation. In another system for achieving this the triac trigger control means comprises comparator means for comparing the sensed alternating current with the reference alternating current and producing a first output signal when the sensed alternating current exceeds the reference alternating current and a second output signal when the sensed alternating current is below the reference alternating current, switching means for coupling a first constant current source and a second constant current source to the integration means in response to the first output signal and the second output signal respectively. The invention will now be described in greater detail with reference to the accompanying drawings in which :- Figure 1 is a schematic diagram, partly in block form, of an embodiment of the invention forming part of an electrical heating appliance. Figure 2 is a family of graphs related to the operation of the circuit arrangement of Figure 1. Figure 3 is a diagram showing a variation of the circuit arrangement of Figure 1. Figures 4 and 5 are diagrams of schematic circuit arrangements showing other variations of the circuit arrangement of Figure 1. Figure 6 is a diagram of a schematic circuit arrangement, partly in block form, of another embodiment of the invention. In the circuit arrangement of Figure 1, a triac device TC having main current path terminals TM1 and TM2 and a gate terminal G is connected with it's main current path in series with a load L across the terminals A and B of a conventional alternating mains voltage supply source ( not shown ) delivering a supply voltage of 240 volts at a frequency of 50 hertz to the terminals A and B, the terminal A being the active terminal and the terminal B being the neutral terminal of the mains supply source. The load L constitutes the heating element of the appliance and the remainder of the circuit arrangement of Figure 1 provides a system for controlling the supply of current to the load L so that the heat produced by the load L maintains the temperature of the mass being heated at or near a temperature selected by the user. The triac TC is triggered by gating pulses supplied to it's gating electrode G from an output terminal of an integrated circuit assembly IC generally signified by that portion of the Figure enclosed within dotted lines, the gating pulses being supplied from a trigger pulse generator TPG forming part of the integrated circuit assembly IC. The operating condition of the trigger pulse generator TPG is dictated by the on and the off state of a latch LCH in such a manner that the trigger pulse generator TPG is operative when the latch LCH is in the on state and is inoperative when the latch LCH is in the off state. When the trigger pulse generator TPG is operative, a continuous stream of gating pulses in synchronism with the alternating supply voltage is supplied to the electrode G of the triac TC. In a known manner, the application of gating pulses to the electrode G renders the triac TC conductive so that current flows from the alternating mains voltage source via the load L and the triac TC causing heat to be dissipated in the load L. The trigger pulse generator TPG may, for example, be in the form described in the applicant's co-pending Australian Patent Application No. 31615/89 in which a trigger pulse is produced at every so-called zero crossing point between alternate half cycles of the alternating voltage of the mains supply. A direct current supply source DC is incorporated within the integrated circuit assembly IC and is energised from the alternating mains voltage supply, for this purpose the source DC is connected via a voltage dropping resistance 5 to the terminal A and also to the terminal B via the terminal VCC. In known manner, direct current is produced by the source DC by means (not shown) of a zener diode and associated circuitry in combination with a capacitance connected between terminals VCC and VEE of the integrated circuit assembly IC so that a fixed potential of 7.5 volts is produced between the terminals VCC and VEE, the terminal VCC being positive relative to the terminal VEE. By means of connections ( not shown ) the voltage present between the terminal VCC and VEE is supplied inter alia to energise the trigger pulse generator TPG and the latch LCH. In addition to the trigger pulse generator TPG and the latch LCH, the triac trigger control means includes a pair of voltage comparators CP1 and CP2, a current difference detection means generally denoted as CDD, an integration means in the form of a capacitance 6 connected between the terminal CAP and the terminal VEE and a current sensing circuit denoted generally as CSC. The current sensing circuit CSC includes a pair of current dividing networks. One current dividing network comprises the series combination of a fixed resistance 1 and a temperature sensing resistance RT being a negative temperature co-efficient resistance whereas the other current dividing network comprises the series combination of a fixed resistance 2 and an adjustable resistance RS. Both current dividing networks are connected across the terminals A and B of the alternating mains voltage source and in this way the temperature sensing resistance RT and the adjustable resistance RS are respectively energised thereby so that the current which flows via the Resistance RT may be termed a Sensed Alternating Current and the current which flows via the resistance RS may be teamed a Reference Alternating Current . The resistance values of the Resistances 1 and 2 are so chosen relative to the respective resistance values of the resistances RT and RS that the voltages developed respectively across the resistance RT and RS are variable over a satisfactory voltage range in proportion to variation of the magnitude of the sensed alternating current and that of the reference alternating current, variation of the magnitude of the sensed alternating current being produced by temperature changes sensed by the resistance RT and variation of the reference alternating current being produced by manual adjustment of the resistance RS by a user operation to select a desired temperature. In practice, it may be intended for the temperature sensing resistance RT to be located in close proximity to the mass being heated by the load L and, as a consequence the conductors for providing electrical connection between the resistance RT and the remainder of the network are susceptible to the pick-up of interference. In practice, it is sometimes required for the adjustable resistance RS also to be remotely located from the remainder of the network of which it forms part so as to facilitate manual adjustment of the temperature desired by the user and, as a consequence in such circumstances, conductors for providing electrical connection to the remotely located resistance RS are also susceptible to the pick-up of interference. The junction of the resistance 1 with the temperature sensing resistance RT is connected via the current setting resistance 3 to the terminal SA of the integrated circuit assembly IC for supplying thereto a sensed alternating current whereas the junction of the resistance 2 with the adjustable resistance RS is connected via the current setting resistance 4 to the terminal SB of the integrated circuit assembly IC for supplying thereto a reference alternating current. The current difference detector means CDD is composed of the series combination of the emitter collector paths of three transistors T1,T2 and T3 between the terminal SA and the terminal VEE and the series combination of the emitter collector paths of three transistors T4,T5 and T6 between the terminal SB and the terminal VEE. The terminal SA is connected via the diodes D1 and D2 to the terminal VCC whereas the terminal SB is connected via the diodes D3 and D4 to the terminal VCC. The base electrodes of the transistors T1, T4 and T7 and the collector electrode of the transistor T7 are all connected to a common point which is connected via a constant current source to the terminal VEE with the emitter electrode of the transistor T7 being connected to the terminal VCC so that the base voltages of transistor T1 and transistor T4 are held one VBE below the voltage on terminal VCC; so that when the transistors are operating, the normal operating VBE of transistor T1 and transistor T4 ensures that the voltage on the emitters of these transistors is close to the voltage of terminal VCC. The transistors T2,T5,T3 and T6 are interconnected so as to function as a current mirror circuit in which the magnitude of the flow of the current via the series combination of the collector emitter paths of the transistors T2 and T3 tends to follow and be equivalent with the magnitude of the flow of current via the series combination of the collector emitter paths of the transistors T5 and T6. The collector electrode of the transistor T1 is connected via the terminal CAP and the capacitance 6 to the terminal VEE. It will be appreciated that the temperature sensing resistance RT is shunted by the resistance 3 in series with the parallel combination of the emitter of the transistor T1 and the diodes D1 and D2 whereas the adjustable resistance RS is shunted by the resistance 4 in series with the parallel combination of the emitter of the transistor T4 and the diodes D3 and D4. However, the resistance value of the resistance 3 is large relative to that of the temperature sensitive resistance RT and the resistance value of the resistance 4 is large relative to that of the adjustable resistance RS. In addition, the emitter-collector paths of the transistors T1, T2 and T3 are connected in series with the output circuit of the direct current source DC across the diodes D1 and D2 whereas the emitter-collector paths of the transistors T4, T5 and T6 are connected in series with the output circuit of the direct current source DC across the diodes D3 and D4. The difference between the current applied to terminal SA and to terminal SB dictate the operation of the circuit of Figure 1 and in this respect, owing to the action of the diodes D1 and D3, the respective voltages produced at the terminals SA and SB are clamped at a voltage equal to one VBE below the voltage of the terminal VCC during each negative half cycle of the alternating supply voltage across the terminals A and B. During these negative half cycles, the transistors T1 and T4 are both biased-off and non-conductive. During positive half-cycles of the alternating supply voltage both of the transistors T1 and T4 are conductive, the respective voltages present at the terminals SA and SB being both within a few millivolts of the voltage of the terminal VCC. During such positive half-cycles, the relative magnitudes of the respective emitter-collector currents of the transistors T1 and T4 are determined by the relative magnitudes of the current supplied to the terminal SA from the junction of resistance 1 and the temperature sensitive resistance RT and the current supplied to the terminal SB from the junction of the resistance 2 with the adjustable resistance RS. The diodes D2 and D4 do not conduct during positive half cycles of the supply voltage unless abnormal conditions exist. In operation, if the magnitude of the sensed alternating current fed via the terminal SA is larger than the reference alternating current fed via the terminal SB then the emitter collector current of the transistor T1 will be greater than the emitter collector current of the transistor T4 causing the capacitance 6 to be charged by the current difference in a direction for the terminal CAP to go positive relative to the terminal VEE. On the other hand, if the magnitude of the reference alternating current fed via the terminal SB is larger than the sensed alternating current fed via the terminal SA then the emitter collector current of the transistor T4 will be greater than that of the transistor T1. In these circumstances, owing to the current mirror action of the transistors T2,T3,T5 and T6, the magnitude of current drawn by the collector emitter path of transistor T2 will be greater than collector emitter current of the transistor T1 causing the capacitance 6 to be discharged towards the potential VEE. With alternating current flow of equal magnitude via the respective terminals SA and SB the charge on the capacitance 6 will remain constant. Assuming that the resistive value of the resistance 1 is equal to that of the resistance 2, the relative magnitudes of the alternating current flow via the terminals SA and SB is dictated by the relative resistive values of the temperature sensing resistance RT and the adjustable resistance RS. By means of the two voltage comparators CP1 and CP2, the voltage across the capacitance 6 ( i.e. the voltage present at the terminal CAP relative to the voltage of the terminal VEE ) is employed as a control signal for controlling the on/off state of the latch LCH and hence for controlling operation or otherwise of the trigger pulse generator TPG. To this end, the terminal CAP is connected to the positive input of the comparator CP1 and to the negative input of the comparator CP2. The negative input of the comparator CP1 is connected to a potential which is 0.6 volts negative relative to the terminal VCC whereas the positive input of the comparator CP2 is connected to a potential which is 1.2 volts positive relative to the terminal VEE. In this way the potentials applied respectively to the negative terminal of the comparator CP1 and to the positive terminal of the comparator CP2 serve as threshold levels whereby the output of the comparator CP1 is activated if the potential of the terminal CAP exceeds the potential of its negative input causing the latch LCH to be switched to its on state. Alternatively the output of the comparator CP2 is activated if the potential of the terminal CAP falls below the potential of its positive input causing the latch LCH to be switched to its off state. It will be realised that the circuit arrangement of Figure 1 is a two-threshold level form of the invention. The cyclic operation of the circuit arrangement of Figure 1 may be understood from the drawings of Figure 2 which shows graphs depicting conditions at different parts of the circuit arrangement of Figure 1 over a period of time, a common time relationship existing between all the graphs of Figure 2. In this respect, in Figure 2 (a) the temperature of the sensing resistance RT is denoted by the solid line 21. In Figure 2 (b) the average magnitude of the sensed alternating current relative to zero, fed to the terminal SA via the resistance 3 is denoted by the solid line 22 and the average magnitude of the reference alternating current relative to zero fed to the terminal SB via the resistance 4 is denoted by the solid line 23. In Figure 2 (c) the solid line 24 denotes the magnitude of the difference between the currents represented respectively as 22 and 23. It follows that the portion of the line 24 above the zero - reference line 0 represents the current flowing into the capacitance 6 and the portion of the line 24 below the zero - reference line 0 represents the current flowing out of the capacitance 6. In Figure 2(d), the solid line 25 represents the voltage present across the capacitance 6, the dotted line 26 representing the upper threshold level at a voltage equivalent to the voltage at the terminal VCC less 0.6 volts. and the dotted line 27 representing the lower threshold level at a voltage equivalent to the voltage of the terminal VEE plus 1.2 volts. In Figure 2 (e) the line 28 represents the on and the off state of the latch LCH and in Figure 2 (f), the line 29 represents the state of operation of the trigger-pulse generator TPG and hence indicates also whether or not the triac TC is being triggered. If now the circuit arrangement of Figure 1 is considered together with the family of graphs of Figure 2 and it is assumed the circuit arrangement of Figure 1 is switched on at the instant t1 with the adjustable resistance RS set to a desired temperature, which is a higher temperature at the instant t1 than that of the mass intended to be heated by the load L. Under such conditions, the resistance of the sensing resistance RT will be higher than the resistance of the adjustable resistance RS and consequently the voltage developed across the sensing resistance RT will be high relative to the voltage developed across the resistance RS so that the magnitude of the sensed alternating current supplied via the terminal SA will be greater than the magnitude of the reference alternating current supplied via the terminal SB as indicated in Figure 2 (b) by the currents denoted as 22 and 23. At the instant t1, the voltage across the capacitance 6 is assumed to be zero with the latch LCH in its off state so that the trigger pulse generator TPG is non-operative and the triac TC is non-conductive and no current is flowing via the load L. Since current supplied via the terminal SA is greater in magnitude than the current supplied via the terminal SB then, owing to the action of the current difference detector CDD, the capacitance 6 is charged via the emitter-collector path of the transistor T1 so that the voltage at the terminal CAP rises relative to the voltage at the terminal VEE as shown by the line 25 of Figure 2 (d). The voltage at the terminal CAP continues to rise towards the voltage at the terminal VCC until at the instant t2 the voltage at the terminal CAP reaches the upper threshold level denoted by the dotted line 26 whereupon the output of the comparator CP1 is activated and the latch LCH is switched to its on state causing the trigger generator TPG to operate and generate a continuous supply of trigger-pulses which are fed to the gate electrode G of the triac device TC so that the triac TC conducts and alternating current flows from the mains alternating current source via the load L and via the triac TC. The flow of alternating current via the load L heats the mass associated with the load L and the temperature of the sensing resistance RT commences to rise as indicated by the line 21 in Figure 2 (a) between the instant t2 and the t3. As the temperature of the mass sensed by the sensing resistance RT rises, in due course the resistance of the sensing resistance RT falls and the difference between the magnitude of the sensed alternating current fed to the terminal SA and that of the reference alternating current fed to the terminal SB diminishes as indicated by the line 22 in Figure 2 (c) and by convergence of the lines 22 and 23 in Figure 2 (b). As the temperature sensed by the resistance RT continues to rise, the difference between the magnitude of the sensed alternating current and that of the reference alternating current grows less and less until at the instant t3 the difference between the two is zero, the instant t3 being the instant at which the resistance of the sensing resistance RT is equal to the resistance of the adjustable resistance RS. At this instant, the magnitude of the sensed alternating current fed to the terminal SA is equal to that of the reference alternating current fed to the terminal SB and the emitter-collector current of the transistor T4 is equal in magnitude to that of the transistor T1. Owing to the previously described current mirror action, the collector-emitter current of the transistor T2 corresponds with the emitter-collector current of the transistor T4 so that, at the instant t3, current flow charging the capacitance 6 via the transistor T1 is in balance with the current flow discharging the capacitance 6 via the transistor T2. Following the instant t3, the magnitude of the sensed alternating current fed via the terminal SA is less than that of the reference alternating current fed via the terminal SB, accordingly current flow via the emitter-collector path of the transistor T4 and also current flow via the collector-emitter path of the transistor T2 is greater than the current flow via the emitter-collector path of the transistor T1 so that the capacitance 6 commences to be discharged via the transistor T2. Between the instant t3 and t4, since the sensed alternating current is less than the reference alternating current, the capacitance 6 discharges and as the voltage at the terminal CAP reaches the lower threshold, as denoted by the intersection of the line 25 with the dotted line 27 at the instant t4, the output of the comparator CP2 is activated causing switch over of the latch LCH to its off state, switching off the generator TPG and hence the supply of trigger pulses to the triac TC which ceases to conduct, cutting off the supply of alternating current to the load L. Between the instants t3 and t4, the generator TPG is operational and current is being supplied to the load L via the triac TC so that the mass sensed by the resistance RT continues to be heated and the resistance of the sensing resistance RT continues to fall so that the difference between the magnitude of the sensed alternating current and that of the reference alternating current increases in the opposite direction, i.e. with the reference alternating current greater than the sensed alternating current. However, following the instant t4, owing to the cut-off of the supply of current to the load L, the temperature of the sensing resistance RT reaches a maximum as indicated by the line 21 in Figure 2 (a), at the same time the sensed alternating current reaches a maximum as shown by the line 22 in Figure 2 (b) and the difference current (i.e. the current at the terminal CAP) as denoted by the line 24 in Figure 2 (c) reaches a maximum in the reverse direction. After reaching a maximum, the temperature of the resistance RT starts to fall, the magnitude of the difference current as denoted by the line 24 starts to diminish falling to zero at the instant t5 when the current fed via the emitter-collector path of the transistor T1 is once again equal in magnitude to the collector-emitter current of the transistor T2. Subsequent to the instant t5, as the temperature continues to fall and with the magnitude of the sensed alternating current becoming greater than the reference current, the capacitance 6 commences to be charged again and the voltage at the terminal CAP starts to rise once more towards the upper threshold level denoted by the dotted line 26 in Figure 2 (d). When the upper threshold level is reached, the output of the comparator CP1 is activated and the generator TPG again supplies triggering pulses to the triac TC so that current is again supplied to the load L whereupon the sequence of operations is repeated cyclically as depicted by the family of graphs of Figure 2. It can be seen from the graphs of Figure 2 that subsequent to the instant t3, the temperature sensed by the resistance RT remains within a particular temperature range about a mean temperature level denoted by the dotted line TM. Adjustment of the resistance RS permits the magnitude of the reference alternating current to be adjusted with corresponding adjustment of the resultant mean temperature level. For a given mass being heated by the load L, subsequent to the instant t3 the duty cycle performed by the latch LCH automatically stabilises at a ratio determined by the setting of the adjustable resistance RS and the ambient temperature thereby governing the mean temperature of the mass and the resultant sensed temperature which cyclically fluctuates at the same frequency as that of the switching frequency of the latch LCH over a certain temperature range approximately centred on the temperature TM which is, of course, also dependent upon the setting of the resistance RS. The circuit arrangement of Figure 1 permits a temperature sensitive resistance to be utilized as the resistance RT having a resistance which varies by several orders of magnitude over the temperature range to be sensed. The integration means constituted by the capacitance 6 and associated circuitry inter alia performs a filtering function preventing inadvertent switching of the latch LCH by transient voltages resulting from the pick-up of interference by connection leads to the sensing resistance RT and to the adjustable resistance RS. The graphs of Figure 2 indicate thermal mass delay effects. That is to say, the shape of the line 21 in Figure 2 (a), consequently the shape of the line 22 of Figure 2 (b) and the shape of the line 24 of Figure 2 (c) show that the load L of Figure 1 is employed, in this instance, to heat a mass having characteristics such that a significant period of time elapses for the temperature sensed by the resistance RT to be effected by switch on or switch off of the generator TPG and hence conductivity or otherwise of the triac TC. If the circuit arrangement of Figure 1 were to be employed so that the load L heated a mass having no thermal mass delay then at the instant t4, the temperature shown by the line 21 in Figure 2 (a) would immediately and rapidly fall owing to switch off of the generator TPG and also at the instant t6, the temperature shown by the line 21 would immediately start to rise owing to switch on of the generator TPG. In addition, in such circumstances, the time period between the instants t4 and t5 would be significantly reduced since the rapid temperature drop would cause the sensed current to rapidly increase in magnitude. However, in the circumstances illustrated by the graphs of Figure 2, not only does the sensed temperature denoted by the line 21 continue to rise following the instant t3 (when the sensed alternating current is equal to the reference alternating current) during the reaction time up until the instant t4 whilst the capacitance 6 is discharging to the lower threshold level as indicated by the line 25 but, as previously mentioned, the sensed temperature denoted by the line 21 continues to rise following the instant t4 owing to thermal mass delay. Corresponding effects in the reverse direction are evident between the instant t5 and the instant t6 and between the instants t6 and t7. In total, there is significant overshoot and undershoot by the line 21 of the mean temperature denoted by the dotted line TM in Figure 2 (a). In other words, subsequent to the instant t3, there is a variation of the temperature of the mass and also of the sensed temperature denoted by the line 21 over a considerable range about the mean temperature TM. The shape of the line 21 is typical of a situation in which the circuit arrangement of Figure 1 is employed for heating a water bed where a large mass is being heated by the load L, which mass is also subject to the effects of convection and there may be a significant temperature gradient between the load L and the sensing resistance RT. It will be realised that the overshoot and undershoot previously referred to results from a combination of the reaction time of the circuit arrangement of Figure 1 and of the thermal mass delay of the mass being heated by the load L. Thermal mass delay is determined, inter alia, by the rate of heat radiation by the mass being heated (which depends, of course, upon the size and the nature of the mass.) as well as the size and nature of the heating element together with the rate at which heat is able to flow between the heating element and the mass being heated. Reduction of the overshoot and undershoot may be desirable in some instances. Many variations of the circuit arrangement of Figure 1 are possible within the scope of the present invention. One such variation is depicted by the circuit arrangement of Figure 3 which shows systematically a portion of the circuit arrangement of Figure 1 which has been modified to provide a two-position switching unit SU between the terminal CAP and the junction of the collector electrodes of the transistors T1 and T2. The switching units SU has two positions. In position A, the terminal CAP is connected to the junction of the collector electrodes of the transistors T1 and T2 and the resultant circuit arrangement corresponds with the circuit arrangement of Figure 1. When the switching unit SU is in position B, the terminal CAP is connected to the terminal VEE via a constant current source SCE. The switching unit SU is controlled by the output of the latch LCH in such a manner that with the latch LCH in the off state the switch SU is in position A whereas with the latch LCH in the on state, the switch SU is in position B. The current supplied by the source SCE flows in the direction which will discharge the capacitance 6 when the latter is positively charged relative to the voltage of the terminal VEE. The variation provided by the circuit arrangement of Figure 3 causes the resultant modified circuit arrangement of Figure 1 to operate in a basically similar manner to the operation of Figure 1 described with reference to the graphs of Figure 2 except that each occurrence when the charge on the capacitance 6 reaches the upper threshold level thereby causing the latch LCH to be switched to its on state so that the triac TC is triggered and current flows via the load L heating the mass then the switch SU is changed to position B and causes the capacitance 6 to be discharged towards the low threshold level at a steady rate. With each such occurrence, since discharge of the capacitance 6 from the voltage of the upper to that of the lower threshold level is at a steady rate, each period of time taken to complete the discharge to the voltage of the lower threshold level is a fixed duration. Of course, when the charge on the capacitance 6 reaches the lower threshold level, the latch LCH is switched to its off state so that the triac TC commences to be triggered, cutting-off the supply of the current to the load L whilst the switch SU is returned once more to the position A permitting the capacitance 6 to be charged once more towards the upper threshold level whenever the magnitude of the sensed alternating current supplied via the terminal SA is greater than that of the reference alternating current supplied via the terminal SB. The variation provided by the circuit arrangement of Figure 3, in operation results in the latch LCH having on periods of fixed duration and off periods of variable duration. The duration of the off periods of the latch LCH is determined by the difference between the magnitude of the sensed alternating current supplied via the terminal SB and that of the reference alternating current supplied via the terminal SA. If the setting of the adjustable resistance RS corresponds with a temperature which is greater than the temperature sensed by the resistance RT, then the magnitude of the sensed current will be greater than that of the reference alternating current. The larger the magnitude of the sensed alternating current relative to that of the reference alternating current then the shorter is the duration of the off period of the latch LCH. The constant current source SCE should be proportioned so as to produce a current of magnitude which will result in the latch LCH having fixed on periods of a duration which is long relative to the duration of an off period of the latch LCH under conditions when the magnitude of the sensed alternating current is much larger than that of the reference alternating current so that, under such conditions, the resultant duty-cycle of the latch LCH is composed of a fixed on period and a relatively short off period whereby the flow of mains alternating current through the load L is interrupted only for relatively short intervals. When the mass being heated by the load L has reached a temperature such that the temperature sensed by the resistance RT is at or near the temperature setting of the resistance RS then the difference in magnitude between the sensed alternating current supplied via the terminal SA and that of the reference alternating current supplied via the terminal SB will be relatively small so that the duration of time for the capacitance 6 to be charged from the voltage of the lower threshold to that of the upper threshold will be relatively long and these conditions will result in the duration of the off periods of the latch LCH being comparable to the fixed duration of the on periods. Accordingly, the duty cycle performed by the latch LCH becomes stabilised so that the mean level of the mass being heated by the load L and consequently the sensed temperature corresponds with the temperature setting of the adjustable resistance RS. Another variation of the circuit arrangement of Figure 1 is depicted by the schematic circuit arrangement in Figure 4 of the accompanying drawings in which like parts to those of Figure 1 are denoted by like numerals or letters. A consideration of the graphs provided by Figure 2 (a) and Figure 2 (c) shows that the presence of thermal mass delay causes overshoot and undershoot and thus imposes a hysteresis effect upon the operation of the circuit arrangement of Figure 1. In the circuit arrangement of Figure 4, the fixed resistances 41 and 43 are connected in series across the terminals A and B with the sensing resistance RT connected between the junction of the resistances 41 and 43 and the terminal VCC. Likewise, the fixed resistances 42 and 44 are connected in series across the terminals A and B with the adjustable temperature-setting resistance RS connected from the junction of the resistances 42 and 44 to the terminal VCC. The resistances 42, 43 and 44 each have a resistance value of 470 kilohms whereas the resistance 41 has a resistance value of 420 kilohms. The terminal VCC is connected to the junction of the triac TC and the load L. In operation, when the triac TC is conducting the whole of the mains alternating voltage is developed across the load L but, when the triac TC is cut-off, the whole of the mains alternating voltage is developed across the triac TC. Since the resistances RT and RS are connected to the junction of the triac TC and the load L, the current drive for both the sensing resistance RT and for the adjustable resistance RS are taken from across the triac TC when the latch LCH is in the off state and from across the load L when the latch LCH is in the on state. Accordingly, the circuit arrangement of Figure 4 provides a feedback system since, owing to the imbalance of the bridge network formed by the resistances 41, 42, 43 and 44 as a consequence of the lower resistance value of the resistance 41, each time the latch LCH is switched from one state to the other and the current drive for the resistance RT and RS is changed then the sensed alternating current supplied via the terminal SA is driven further out of balance then would be the case if the resistance 41 was equal in value to the resistances 42, 43 and 44. The feedback system provided in the circuit arrangement of Figure 4 is such that the out of balance current drive to the resistance RT increases the magnitude of the current difference between the sensed alternating current supplied via the terminal SA and the reference alternating current supplied via the terminal SB causing more rapid charge or discharge of the capacitance 6 from one threshold level to the other than would otherwise be the case resulting in a reduction of the cycling period of the latch LCH and a reduction of overshoot and undershoot of the selected mean temperature determined by the setting of the resistance RS. It will be understood that, in the feed back system of the circuit arrangement of Figure 4, the percentage of feed back will depend upon the relative values of resistances 41 and 43. Moreover, feed back in the opposite direction is produced when the resistance value of the resistance 41 is greater than that of the resistance 43. Feed back is also able to be produced if the resistance values of the resistances 41 and 43 are equal and those of the resistances 42 and 44 are unequal. In the circuit arrangement of Figure 4, it is to be noted that the common connection of the resistance RT with the junction of the load L and the triac TC follows the teachings of the applicants co-pending Australian Patent Application No. PK2501. The circuit arrangement of Figure 5, in which similar parts to those of Figure 1 are denoted by like numerals or letters, is another example of the application of feed back to achieve the same result as that achieved by the circuit arrangement of Figure 4. The circuit arrangement of Figure 5 is intended to illustrate a circuit arrangement which is identical to that of Figure 1 except that feed back current is applied from the junction of the triac TC and the load L via a feed back resistance 51 to the junction of the resistance 1 and the sensing resistance RT. It will be understood that either as the case may be a positive or negative feed back may be obtained in the circuit arrangement of Figure 5. In a variation of the circuit arrangement of Figure 5, the feed back resistance 51 may be connected to the junction of the resistance RS and resistance 2. It will be understood that all else being equal, this variation will have a feed back of opposite sense to that of the circuit arrangement of Figure 5. It will be realized that a circuit arrangement on the basis of a single threshold form of the invention is readily conceivable which operates in a somewhat similar manner to the circuit arrangement permitted by the variation associated with the circuit arrangement of Figure 3. Such a single threshold form may, for instance, be provided by further modification to the circuit arrangements of the Figure 1 and of Figure 3 of such a kind that the comparator CP2 is eliminated and the latch LCH is replaced by a latch of known kind provided with a timing system not related to the capacitance 6 so that the latch nevertheless has an on period of fixed duration. In addition, the constant current source SCE is replaced by a diode so that each time the latch LCH is activated into the on state causing the switching unit SU to return to its position B, the capacitance 6 is rapidly discharged. Another simple variation of the circuit arrangement of Figure 1, which is equally applicable when the variation associated with the circuit arrangement of Figure 3 is also incorporated, is for the resistances RT and RS to be replaced by fixed resistances and for the resistances RT and RS to be respectively connected in series with the resistances R3 and R4. As previously indicated, an important feature of the present invention is the energization of the temperature sensing resistance by alternating current derived from the alternating supply source. The present specification describes how the resultant alternating current signal is utilized to provide a satisfactory input for a direct current input comparator system. This is achieved, in the case of the circuit arrangement of Figure 1 by way of an integration means in the form of the capacitance 6 and the circuitry associated there with which provides an interface between the current difference detector CDD and the comparators CP1 and CP2. It is useful to recognise that the transistors T1 and T4 conduct only when the polarity of the input signal at the terminals SA and SB is positive relative to the voltage of the terminal VEE. When the polarity of the input signal at the terminals SA and SB is negative, the transistors T1 and T4 will not conduct so that no current flows into or out of the capacitance 6 and during this time the charge on the capacitance 6 remains unchanged. Accordingly, a different current (i.e. a current which is the difference between the sensed alternating current flowing via the terminal SB and the reference alternating current flowing via the terminal SA) flows to or from the capacitance 6 via the terminal CAP for only part of the time (i.e. approximately only during positive half-cycles of the alternating supply voltage). The arrangement thus serves to extend the integration times of the capacitance 6 and the resultant integrating times are greater than would be obtained with a direct current energised circuit employing equivalent components values. A further embodiment of the invention will now be described with reference to Figure 6 of the accompanying drawings which illustrates systematically a significant modification of the integrated circuits unit IC, like parts to those of Figure 1 being denoted by like letters or numerals. In the circuit arrangement of Figure 6, the capacitance 6 is not charged by current supplied via the transistor T1 or discharged by the flow of current via the transistor T2. Instead, the terminal CAP is connected to a two-position switching unit 63 which is also connected via a constant current source 61 to the terminal VCC and via a constant current source 62 to the terminal VEE whereby the capacitance 6 is charged via the constant current source 61 when the switching unit 63 is in the position denoted by the letter X and is discharged via the constant current source 62 when the switching unit 63 is in the position denoted by the letter Y. The switching position of the unit 63 is controlled by the output of a current comparator 64 having one input 65 connected to the junction of the collector electrodes of the transistors T1 and T2. The other input 66 of the comparator 64 is connected to a suitable direct current reference source (not shown). The comparator 64 is of a known kind and its input 65 presents a low-impedance to the junction of the collector electrodes of the transistors T1 and T2 such that current flows via the input 65 into or out of the comparator 64 depending upon whether or not the current difference between the sensed alternating current supplied via the terminal SA and the reference alternating current supplied via the terminal SB is positive or negative. When the current difference is positive, the output of the comparator 64 switches the unit 63 to the position X which charges the capacitance 6 towards the upper threshold level and when the current difference is negative, the output of the comparator 64 switches the unit 63 to the position Y which discharges the capacitance 6 towards the lower threshold. A number of different design possibilities are available with the circuit arrangement of Figure 6. For example, the constant current sources 61 and 62 may be proportioned to supply current of equal magnitude and, in these circumstances, if the switch unit 63 is driven so that there is an equal amount of time in position X as in position Y over a given period of time as a result of the difference between the sensed alternating current and the reference alternating current changing from a positive difference to a negative difference then there will be equal amounts of time during which the capacitance 6 is charged and discharged so that there will be no net charge or discharge of the capacitance 6. On the other hand, if the switch unit 63 is driven so that the amount of time in the respective positions X and Y is unequal over a given period of time than the charge on the capacitance 6 will move towards one or the other of the two thresholds causing switch over of the latch LCH when the threshold in question is reached. The response time of the arrangement (e.g. the time taken for the voltage corresponding to the charge on the capacitance 6 to move from one threshold to the other) assuming a one hundred percent unbalance between the amount of time occupied by the switch unit 63 in the respective positions X and Y depends upon the size of the capacitance 6 and the upon the magnitude of the current supplied by the constant current sources 61 and 62. If required, the constant current sources 61 and 62 may be proportioned relative to each other so that the response time in one direction is less than that in the other. For the purposes of this description, the direct current source to which the input 66 is connected is such that the comparator 64 reacts, as described, to the current via the input 65 being positive or negative. Other possibilities are available whereby the source to which the input 66 is connected serves as a threshold requiring the magnitude of the current flowing via the input 65 to be of a given magnitude (in either a positive or negative direction) for the output of the comparator 64 to be activated to cause changeover of the switching unit 63. Still further possibilities are available in the nature of the switching unit 63. Such other possibilities and further possibilities should be considered depending upon the control characteristics that are desired. If desired, a completely different input threshold system for the comparator 64 may be used in lieu of that shown in Figure 6 by replacing the current difference detector CDD and the comparator 64 by a threshold circuit which compares the instantaneous magnitude of the alternating signal voltage developed across the sensing resistance RT with equal and opposite threshold voltage limits set by a reference voltage and controls the switch position of the unit 63 in such a manner that position X is occupied by the unit 63 whenever the signal voltage exceeds the limits and position Y is occupied by the unit 63 whenever the signal voltage is within the limits. In the foregoing description of the invention, reference is made to the average peak-to-peak magnitude of the sensed alternating current and to the average peak-to-peak magnitude of a reference alternating current. In Figure 2 (b), it is intended that the line 23 depicts a value corresponding with the average peak-to-peak magnitude of the reference alternating current flowing in the adjustable resistance RS at a given adjustment thereof, which value remains constant. On the other hand, in Figure 2 (b) it is intended that the line 22 depicts a value corresponding with the average peak-to-peak magnitude of the sensed alternating current flowing in the temperature sensitive resistance RT, which value changes with change in the temperature to which the resistance RT is exposed. As indicated previously, the line 24 in Figure 2 (c) depicts a value corresponding with the difference between the values represented respectively by the lines 22 and 23 of Figure 2 (b). However, although the line 25 in Figure 2 (d) depicts the voltage representing the charge on the capacitance 6, the line 25 does not represent, throughout its length, the integral of the value denoted by the line 24. Nevertheless, the portions of the line 25 between the instants tl and t2, between the instants t3 and t4, between the instants t5 and t6, between the instants t7 and t8 and between the instants t9 and t10 are intended to represent the integral of the value denoted by the line 24 within the corresponding portions thereof. The portions referred to in the preceding sentence correspond with intervals when the voltage on the capacitance 6 is effective as a control voltage. It will be appreciated that the invention is not limited to the embodiments described herein, but many further variations are possible for those skilled in the art without departing from the scope of invention. For example although the invention is described herein with the said sensing element in the form of a temperature sensing element, the invention is also applicable to other kinds of sensing elements, i.e. humidity dependent capacitance. Furthermore although the invention has been described with reference to the sensed alternating current decreasing with increasing temperature, the invention is also applicable in general to any applications in which the sensed alternating current increases with an increase or decrease as the case may be in a control parameter. As will be appreciated by the man skilled in the art modifications may be needed to the circuit arrangements to take into account such differences in different applications without necessarily departing from the scope of the invention.	A circuit arrangement comprising a load (L) supplied via a triac (TC) with current from an alternating voltage source (A, B) under control of a triac trigger control means (IC) in combination with a sensing element (RT), characterised in that the sensing element (RT) is energised by alternating current derived from the alternating voltage source (A, B) to produce a sensed alternating current and in that the triac trigger control means (IC) includes an integration means (6) for producing a control signal, triggering or otherwise of the triac (TC) being determined by the state of a latch (LCH) actuated in response to the magnitude of the control signal relative to one or more threshold levels (CP1, CP2), during at least one state of the latch (LCH) the control signal produced by the integration means (6) representing the integral of the difference between a value corresponding with the average peak to peak magnitude of the sensed alternating current and a reference value. A circuit arrangement as claimed in Claim 1 wherein the said control signal is produced by integration of the difference between the average peak to peak magnitude of the sensed alternating current and that of a reference alternating current. A circuit arrangement as claimed in either Claim 1 or Claim 2 wherein the said latch (LCH) is so arranged that actuation of the said latch in response to the magnitude of the said control signal is able to be carried out only when the latch is in a given state, such actuation being in response to the magnitude of the control signal relative to a single chosen threshold level, with actuation of the latch when in it's opposite state being produced by means other than in response to the said control signal. A circuit arrangement as claimed in Claim 3 wherein the said latch (LCH) is arranged to automatically return to the said given state at the end of a fixed time period in the said opposite state. A circuit arrangement as claimed in either Claim 3 or Claim 4 wherein the said latch (LCH) is connected to function as a cyclic switch controlling the triggering of the said triac (TC) in accordance with a duty cycle having a fixed time interval of continuous triac triggering and variable time interval of non-triggering or vice versa, the length of each variable time interval being determined by the time taken for the magnitude of the said control signal to reach the chosen threshold level. A circuit arrangement as claimed in either Claim 1 or Claim 2 wherein the said latch (LCH) has a reset state and a set state and changeover of the latch state from the set state to the reset state (or vice versa) is actuated by the magnitude of the said control signal exceeding a first threshold level whereas changeover of the latch state from the reset state to the set state (or vice versa) is actuated by the magnitude of the said control signal falling below a second threshold level. A circuit arrangement as claimed in Claim 6 wherein the said triac trigger control means (Id) is arranged so that the said latch (LCH) functions as a cyclic switch controlling the triggering of the said triac (Td) in accordance with a duty cycle having a fixed time interval of continuous triac triggering and a variable time interval of non-triggering or vice versa. A circuit arrangement as claimed in Claim 7 wherein the said triac control means (Id) includes a source of constant current (SCE) and is so arranged that the length of each variable time interval is determined, during one latch state by the time taken for the magnitude of the said control signal to reach one threshold level (for example the said first threshold level) and during the other latch state, the control signal produced by the integration means is determined by the said source of constant current and changes in magnitude at such a rate as to reach the other threshold level (for example the second threshold level) at the end of a fixed time interval. A circuit arrangement as claimed in Claim 6 wherein the said triac trigger control means (Id) is arranged so that the said latch functions as a cyclic switch controlling the triggering of the said triac in accordance with a duty cycle having a variable time interval of continuous triac triggering and a variable time interval of non-triggering. A circuit arrangement as claimed in Claim 9 wherein the said integration means comprises a capacitance (6) which is charged and discharged at a rate proportional to the difference in magnitude between the said sensed alternating current and the said reference alternating current, with the voltage corresponding to the charge on the said capacitance serving as the said control voltage whereby the respective durations of both variable time intervals, commencing from the instant of latch changeover, is determined by the time taken for the magnitude of the said control signal to reach the threshold level for the next latch actuation. A circuit arrangement as claimed in Claim 9 wherein the said triac trigger control means (Id) comprises comparator means (64) for comparing the said sensed alternating current with the said reference alternating current thereby producing a first output signal when the sensed alternating current exceeds the reference alternating current and a second output signal when the sensed alternating current is below the reference alternating current, and switching means (63) for coupling a first constant current source (61) and a second constant current source (62) to the said integration means (6) in response to the first output signal and the second output signal respectively. A circuit arrangement as claimed in any one of the preceding claims 2 to 10 in which the said sensed alternating current is derived from the junction of the said sensing element (RT) with a first fixed resistance (1) in series therewith thereby forming a first voltage divider network and the said reference alternating current is derived from the junction of an adjustable resistance (RS) with a second fixed resistance (2) in series therewith thereby forming a second voltage divider network, the first and second voltage divider networks being completed in parallel with each other. A circuit arrangement as claimed in Claim 12 in which the said first and the said second voltage divider networks are connected across the said alternating voltage supply source (A, B) A circuit arrangement as claimed in Claim 13 in which feedback is supplied to the said current sensing network via a feedback path extending from the junction of the said triac (TC) with the said load (L) either to the junction of the said sensing element (RT) with the said first resistance (1) or to the junction of the said adjustable resistance (RS) with the said second fixed resistance (2) in series. A circuit arrangement as claimed in Claim 12 in which the said first and the said second voltage divider networks are connected between one terminal (8) the said alternating voltage supply source and the junction of the said triac (TC) with the said load (L) the junction of the said sensing element (RT) with the said first fixed resistance (43) being connected via a third fixed resistance (41) the remaining terminal (A) of the said alternating voltage supply source and the junction of the said adjustable resistance (RS) with the said second fixed resistance (44) being connected via a fourth fixed resistance (42) also to the remaining terminals (A) of the said alternating voltage source, the relative values of the said first (43) and second (44) fixed resistance being such that with each change of state of the said latch (LCH) the current drive for the said sensing element (RT) and the said adjustable resistance (RS) is further out of balance than if the said first (43) and second (44) fixed resistance were of equal value.	PHILIPS ELECTRONICS NV; PHILIPS ELECTRONICS N.V.	CRAWFORD JOHN SIDNEY; KAY MALCOLM JOHN; TRACY PHILIPS ANTHONY; CRAWFORD, JOHN SIDNEY; KAY, MALCOLM JOHN; TRACY, PHILIPS ANTHONY
EP-0489463-B1	489,463	EP	B1	EN	19,941,109	1,992	20,100,220	new	H01J61	null	H01J61, H01J9, B22F5	H01J 61/78, H01J 61/72, H01J 61/067, H01J 61/70, H01J 9/02B	Low pressure discharge lamp	A low pressure discharge lamp having a pair of electrodes, each electrode consisting of a sintered mixture of 50%-90% by weight of W, 5-25% by weight of BaO or of a 1:1:1 by weight mixture of BaO, CaO and SrO, and 5-25% by weight of a metal oxide selected from the group consisting of the oxides of Y, Zr, Hf and the rare earths, each electrode having a porosity of less than about 10% and a resistance of greater than 1 ohm.	The invention relates to a low pressure discharge lamp comprising a closed discharge vessel in which two electrodes are arranged between which a discharge is maintained during operation. In the known low pressure discharge lamps, the electron emissive electrodes that are employed have a coil structure in which the electron emissive material is provided as a coating on a coiled tungsten wire. A problem with such an electrode is that it is difficult to provide an adequate control of the amount of emissive material provided on the coiled tungsten wire. As a result, it is very difficult to control the life distribution of the lamps so as to manufacture lamps having a narrowly controlled life distribution. This is because the lamp life is very sensitive to the quantity of emissive material provided on the electrode. Since it is almost impossible to uniformly control amounts of emissive material provided on a coated tungsten wire electrode it is difficult to manufacture lamps having an adequately narrow life distribution. Another problem exists in that fact that due to the physical nature of the electrode employing a tungsten coil, it is impossible to fabricate the electrode into a particularly desired shape. Further, fabricating an electrode in which the emissive material is loaded on to a double helix electrode, such as the ones presently employed, is a rather difficult operation and requires expensive equipment. It is an object of the invention to provide an improved low pressure discharge lamp having improved electrodes. According to the invention a lamp of the kind mentioned in the opening paragraph is characterized in that each electrode consists of a sintered mixture of 50%-90% by weight of W, 5-25% by weight of BaO or of a 1:1:1 by weight mixture of BaO, CaO and SrO, and 5-25% by weight of a metal oxide selected from the group consisting of the oxides of Y, Zr, Hf and the rare earths, each electrode having a porosity of less than about 10% and a resistance of greater than 1 ohm. By use of the sintered electrodes, it has been found that it is possible to more closely control the life expectancy of the lamp. Further, because of the greater ease of fabrication, the cost of the manufacturing electrodes and, therefore, the cost of the lamp is greatly reduced as compared with the a lamp employing a coiled electrode. Additionally the electrodes of the invention have relatively high resistance (greater than 1 ohm) thus requiring use of a minimum cathode current. Further, the lamps of the invention exhibit a relatively stable discharge. While the use of sintered electrodes in discharge lamps is known, the lamps in which sintered electrodes have been applied have been high pressure discharge lamps. Such a lamp is shown for example in U.S. Patent 4,303,848. However, while the low pressure discharge lamps of the invention pass a heater current through the electrodes before arc formation (hot cathode operation), therefore requiring the resistance of the electrodes to be high, no heater current is passed through electrodes employed in the high pressure lamps of this patent. Therefore for these lamps it is not of importance that the electrodes have a high resistance. In fact, preferably the electrodes have a low resistance. U.S. Patent 4,808,883 shows a discharge lamp containing an electrode formed of a semiconductor ceramic material. The electrode in this lamp, unlike the lamp of the invention, does not contain tungsten as the major ingredient but only in an amount up to 0.8 mol.%. U.S. Patent 3,766,423, shows low pressure mercury vapor discharge lamps containing hot cathode electrodes formed by mixing tungsten with oxides of barium or with mixtures of oxides of barium, calcium and strontium. However, no yttrium oxide is present. In addition, pressing and sintering is not carried out so as to produce an electrode having a porosity of less than about 10% in this patent. But sintering is carried out in such a manner that the electrode produced has a density gradient containing 80% voids in the surface of electrodes extending down 10% voids in the central portion of the electrode. As a result it has been found that such electrodes are very fragile and difficult to degas. While any metal oxide of the group consisting of the oxides of yttrium, zirconium and hafnium may be employed, it is found that best results are achieved when the metal oxide is Y₂O₃. Preferably, each electrode is made from a mixture of 50 to 80% by weight of tungsten, 10 to 25% by weight of yttrium oxide and 10 to 25% of barium oxide, the particle sizes of these ingredients being 0.05 - 10 µm. While the electrodes may have any desired shape they are conveniently rod-shaped with a length of at least 5 mm with a length of up to about 30 mm and preferably up to about 15 or 20 mm. Preferably the thickness of the rod is 0.5 - 2 mm. The electrodes are manufactured by pressing and sintering mixtures of powders of tungsten and the oxides or the tungsten powder may be first coated with the oxides by a sol-gel technique and the coated powders are then pressed and sintered. Pressing is generally carried out by isostatic pressing at a pressure of about 55 - 262 MPa (8,000 - 38,000 psi). Sintering is carried out in a reducing atmosphere preferably in an atmosphere containing up to about 5% of hydrogen in an inert gas such as helium at a temperature of about 1600°C - 2200°C for 5 minutes to 1 hour. While the electrodes may be directly pressed and sintered into bars, the electrodes may be first formed as sintered pellets, which pellets are then cut into bars of desired size. The electrodes are directly connected to the current lead-in wires, for example by point welding. Preferably the lamp is a low pressure mercury vapor discharge lamp containing a small amount of mercury and a noble gas at a pressure of 133 - 1333 Pa (1-10 torr). Example80 weight percent of tungsten of a particle size of 0.4 µm was coated with 10 percent by weight of yttrium oxide and 10 percent by weight of barium oxide. The tungsten powder was coated with the yttrium oxide and the barium oxide employing a sol-gel technique. In carrying out this technique the tungsten powder was dispersed in a mixture of yttrium isopropoxide and barium butoxide in organic solvents in concentrations so as to provide 10 percent by weight of yttrium oxide and 10 percent by weight of barium oxide. The mixture was then formed into a dispersion and the resultant dispersion was heated at a temperature of about 90°C to remove solvents. The resultant coated powder was then fired at a temperature of about 620°C for two hours in a nitrogen atmosphere containing about 2% of hydrogen. The powder was then formed into pellets (1.4 mm thick and 25 mm in diameter) by pressing at a pressure of about 131 MPa (19000 psi). The pellets were then sintered at 2000°C for about 1 hour in an atmosphere of 95% helium and 5% hydrogen. The resultant pellets were then cut into bars of dimensions of 0.9 x 1.0 x 18 mm. The resultant bars had porosities of less than 10% at a resistance of 2-4 ohms. A low pressure mercury vapour discharge lamp was manufactured comprising two electrodes, each of which consisted of a rod prepared by the abovementioned example. The rods were positioned so that their axes were perpendicular to the axis of the discharge vessel. The following tests were carried out with this lamp. Employing a DC power supply (600 V, 1 A) and employing a resistor as a ballast a lamp voltage and current were monitored for different heating currents while the lamp was in an arc mode and carrying the cathode current. The time between the measurements was about two minutes and the ambient temperature was about 22°C. The results are shown in the following table. The values shown clearly indicate that the discharge provided by this lamp was stable at a wide range of cathode current and lamp currents. The relationship between cathode current and cathode voltage is shown in the following table. This table shows that the cold resistance of the cathode was about 0.5 ohms and that the resistance of the cathode was about 1.31 ohms at 2.8 A. The lamp was again started and the lamp current ILA was about 400 mA and the cathode current was decreased from 2.2 to 0 A. The discharge was stable. The lamp current was reduced from 400 mA to 150 mA. At the latter current the discharge became unstable. The results are shown in the following table. The discharge was stable until the lamp current was reduced to 150 mA. Thus the discharge provided in the lamp was stable between a wide range of lamp currents. The sole figure of the drawings is a longitudinal-sectional view of a fluorescent low pressure mercury vapor discharge lamp of the invention employing sintered electrodes. The lamp has a closed glass discharge vessel 1 which comprises mercury and a noble gas, e.g. argon. Electrodes 2 and 3 are arranged in the vessel 1, between which electrodes a discharge is maintained during operation of the lamp. The electrodes are rod-shaped sintered electrodes according to the invention. The discharge vessel 1 is on its inner side provided with a luminescent layer 4. The luminescent layer 4 comprises at least one luminescent material (phosphor) which emits visible radiation upon excitation by mainly 254 nm radiation from the mercury discharge.	A low pressure discharge lamp comprising a closed discharge vessel (1) in which two electrodes (2,3) are arranged and between which a discharge is maintained during operation, characterized in that each electrode (2,3) consists of a sintered mixture of 50%-90% by weight of W, 5-25% by weight of BaO or of a 1:1:1 by weight mixture of BaO, CaO and SrO, and 5-25% by weight of a metal oxide selected from the group consisting of the oxides of Y, Zr, Hf and the rare earths, each electrode (2,3) having a porosity of less than about 10% and a resistance greater than 1 ohm. A low pressure discharge lamp as claimed in claim 1, characterized in that the metal oxide is Y₂O₃. A low pressure discharge lamp as claimed in claim 1 or 2, characterized in that each electrode (2,3) consists of a sintered mixture of 50-80% by weight of W, 10-25% by weight of Y₂O₃ and 10-25% by weight of BaO. A low pressure discharge lamp as claimed in claim 1, 2 or 3, characterized in that each electrode (2,3) is rod-shaped with a length of at least 5 mm. A low pressure discharge lamp as claimed in claim 1, 2, 3 or 4, characterized in that before sintering the particle size of W is 0.05-10 µm, the particle size of BaO is 0.05-10 µm and the particle size of Y₂O₃ is 0.05-10 µm.	PHILIPS NV; N.V. PHILIPS' GLOEILAMPENFABRIEKEN	GOLDBURT EFIM; HELLEBREKERS WIM; GOLDBURT, EFIM; HELLEBREKERS, WIM
EP-0489465-B1	489,465	EP	B1	EN	19,960,904	1,992	20,100,220	new	G01N33	G01N33, B01J13	C07C321, C07C323, G01N33, B22F1, B01J13	G01N 33/553, G01N 33/543M, B01J 13/00, G01N 33/58H	Ligand gold bonding	Gold sol coated with alkanethiols and alkanethiol derivatives, which provide groups on the sol available for the linking of binding moieties such as antibodies, antigens or ligands to the gold sol. Di- and tri-thiol compounds bound to gold sol also facilitate the adsorption of antibodies, antigens or ligands to the sol. The coating process, and test kits incorporating the coated sols are also included.	BACKGROUND:This invention relates to gold sol coated with alkanethiols and alkanethiol derivatives to provide groups on the sol available for the binding or linking of binding moieties such as antibodies, antigens, or ligands to the gold sol. In addition, the use of di- and tri-thiol compounds bound to gold sol facilitate the passive adsorption of these binding moieties. This invention also relates to gold sol coated with thiolated binding moieties, including antigens, antibodies, or carrier molecules, which can be attached to relevant ligands. Also included is the process for coating the gold sols with such thiol compounds, the use of coated sols in immunological and immunocytological diagnostic tests and test kits incorporating such coated gold sols. Test methods for the diagnosis of various diseases are constantly being improved. Currently, immunological methods are among the most sensitive methods used to detect the presence of antigens or antibodies in samples. These assays are well known to those skilled in the art of immunodiagnostics. Generally, an immunological assay consists of an assay wherein a monoclonal or polyclonal antibody is used to capture an antigen in the sample and a second antibody containing a label, such as a fluorescent compound or an enzyme, immunochemically reacts with the antigen-antibody complex. The resulting labelled antibody-antigen-antibody complex is detected. Variations on this basic assay are common, such as the use of only one reactive antibody in the test, the competitive inhibition method, or the use of particles as labels that allow an agglutination reaction to be read. Another variant is the use of microparticles coated with either an antigen or an antibody, which after formation of a complex with the analyte and a second appropriately labeled binding partner, gives a positive reaction. Gold sol microparticles are used in an assay method known as a sol particle immunoassay (SPIA). In this assay, a solution containing the gold sol coated with an appropriate binding partner, either an antibody or an antigen, is reacted with a sample to bind to its binding partner. In this process, complexes are formed that can be detected, usually due to their change in color. Uncoated gold sol particles, and other colloids, will undergo agglomeration when exposed to low concentrations of salt, and quickly precipitate out of solution. Therefore, the coating of gold sol with an appropriate binding partner serves two functions. The first is to provide appropriate immunological binding activity and the second is to protect against agglomeration, which would of necessity occur in buffers designed to optimize for immunological reactions. Since not all proteins or polymers will protect the gold sol completely from salt-induced agglomeration, an overcoating step is usually performed with a protein or polymer that is known to be capable of completely protecting the gold sol from salt-induced agglomeration. Such an overcoating step is a well known practice in adsorbing antibodies and antigens to plastic substrates and has been shown to increase the stability of the coated material. The overcoating also serves to reduce nonspecific interaction of the gold sol with sample components. This nonspecific interaction is a significant problem when using antibody coated latex particles in diagnostic assays, and is probably a manifestation of the nonspecific serum interference observed in many, if not all, immunoassays, regardless of format. In some cases it is permissible to change the overcoating protein or polymer to minimize interference in specific systems. Additives to the sol medium such as guanidine hydrochloride or urea are useful. Occasionally, non-specific interference can be pinpointed to serum heterophile activity and is eliminated by the addition of whole animal serum. A serious drawback in the passive adsorption of the desired binding partner to gold colloid has been that such direct coating is often unsuccessful. The physico-chemical mechanisms of passive polymer adsorption to colloids in general is a poorly understood process. Passive adsorption of antibodies to gold sol may result in a coated sol which is poorly protected from salt-induced agglomeration and which cannot be further protected by overcoating. It may also result in a coated sol with poor immunological activity, presumably due to the incorrect orientation of adsorbed antibody, or it may result in the antibody-induced agglomeration of the sol itself. Finally, the binding partner of choice may simply not bind to the gold sol. The net result of these problems is that few biological reagents useful in other diagnostic formats can be used in the production of gold colloid reagents of diagnostic quality. What is needed in the art is a method for covalently attaching binding partners, proteins, carbohydrates or ligands, to the gold sol so that the uncertainties of the passive adsorption characteristics or the necessity of making binding partner and good coating carrier conjugates for passive adsorption may be eliminated. In particular, such a sol would be significantly more useful if it were refractive to salt-induced agglomeration even in the absence of a coated binding partner. The ability to change the physico-chemical surface properties of the sol would, at the same time, make it possible to minimize the sometimes undefined sample-sol interactions responsible for non-specific interference in immunochemical diagnostic assays and background problems in immunocytochemical assays. What is also needed is the ability to facilitate the passive adsorption of biological polymers to gold sols. Thiolation of antibodies and polymers can increase their ability to bind to gold solo as evidenced by increased resistance to salt-induced agglomeration. Such a capability may prove useful for those antibodies which bind well to gold sols, but lose significant amounts of their activity in doing so as well as for antibodies which simply do not bind the gold sol in an underivatized state. An alternative method of changing the physico-chemical characteristics of the sol surface in order to facilitate antibody binding is the coating of the sol with di-thiol or tri-thiol compounds. Such an intermediate coating can significantly change the passive adsorption properties of antibodies to the coated sol. SUMMARY OF THE INVENTIONThis invention provides a process for coating microparticles of gold sol with alkanethiols, alkanethiol derivatives, and di- and tri-thiol compounds. Gold sols coated with alkanethiols or their derivatives are resistant to salt-induced agglomeration and contain chemical moieties for covalent polymer or ligand attachment. A particular hydrophobic-hydrophilic balance of the sol surface is obtained and nonspecific interactions of the sol with proteins generally are minimized. In particular, chemical groups distal to the n-alkane thiol moiety, such as methyl, hydroxyl, carboxyl, amino, sulfhydryl or carbonyl, are solvent exposed and serve as covalent attachment sites and may be hydrophobic-hydrophilic balance sites. Coating gold sol with small molecular weight di- and tri-thiol compounds does not protect the sol from salt-induced agglomeration, but changes the physico-chemical nature of the coated sol surface and facilitates the passive adsorption of antibody molecules. Also included in the present invention is the coated gold sol. The invention also includes coated gold sol particles additionally bound to binding moieties such as antibodies or antigens and diagnostic kits containing said gold sol particles. Lastly, the invention includes coated gold sols to which binding moieties are attached by adsorption, and uncoated gold sol where adsorption is facilitated through the thiolation of the binding moiety. DESCRIPTION OF THE DRAWINGSFigure 1 demonstrates the relative resistance to salt-induced gold sol agglomeration conferred by coating the gold sol with anti-gp160 antibody (GC-143) at various concentrations and pH values. Figure 2 demonstrates the relative resistance to salt-induced gold sol agglomeration conferred by coating a TTC coated gold sol with anti-gp160 antibody (GC-143) at various concentrations and pH values. Figure 3 demonstrates the ability of GC-143 to cause spontaneous agglomeration of a gold sol in the absence of any added salt at various concentrations and pH levels. Figure 4 demonstrates the ability of GC-143 to cause spontaneous agglomeration of a TTC coated gold sol in the absence of any added salt at various concentrations and pH levels. Figure 5 shows the immunological activity and specificity of GC-143 adsorbed on a gold sol in a SPIA assay. Figure 6 shows the immunological activity and specificity of GC-143 adsorbed on a TTC coated gold sol in a SPIA assay. Figure 7 demonstrates the ability of an underivatized monoclonal anti-HIV p24 antibody adsorbed to gold sol to protect the sol from salt-induced agglomeration. Figure 8 demonstrates the ability of thiolated monoclonal anti-HIV p24 antibody adsorbed to gold sol to protect the sol from salt-induced agglomeration. DETAILED DESCRIPTION OF THE INVENTIONThe process of coating microparticles consisting of gold sol to provide chemical linking groups to facilitate the further attachment of other groups is the basis of the present invention. Microparticles in the invention are generally defined as colloidal gold sol that range in size from about 20nm to about 200nm or more. The preferred range of microparticle is from about 60 to about 80nm. The most preferred size is about 65 to 75nm. Some of the coating chemicals used, such as alkanethiols and their derivatives and mixtures thereof also protect the gold sols from salt-induced agglomeration and may produce a particular hydrophobic-hydrophilic balance of the sol surface so that nonspecific interactions of the surface with extraneous proteins are minimized. Gold sol was produced by the hydroxylamine-mediated reduction of chloroauric acid in water onto seed gold particles. This procedure is described in the literature. (Turkevich, J. et al., Discussions of the Faraday Society, No. 11, p. 55-74 (1951)). Generally, chloroauric acid trihydrate dissolved in water is added to deionized water, to which is then added hydroxylamine hydrochloride. Seed gold particles are added and stirred. A small amount of acetone is added, and the mixture is stirred. K2CO3 is added until the pH reaches 7.0. The gold sol ranges in size from about 10nm to about 150nm in diameter depending on the amounts of gold particle added and the amount of chlorauric acid used, and is now ready to be coated with alkanethiols or thiol derivatives. Alkanethiols, their derivatives, and di- and tri-thiol compounds are the preferred compounds used to coat the gold sol particle and to provide chemical moieties or linking groups for covalent polymer or ligand attachment to the gold sol or for the modification of the hydrophilic/hydrophobic balance. The more preferred are the n-alkanethiols, while the most preferred compounds are alkanethiols of the formula CH3(CH2)nSH, where n equals 9 to 23. Derivatives of the alkanethiols are generally of the formula RCH2(CH2)nSH wherein R is OH, COOH, CHO, SH and NH2, and n is 9 to 23. The di- and tri-thiol compounds are generally compounds of low molecular weight. Some of them have been recognized as heavy metal chelators. Two examples are 2,3-dimercaptosuccinic acid and trithiocyanuric acid. To coat a sol with an n-alkanethiol, 0.10M of the alkanethiol and 1% Tween-20R (ICI Americas registered trademark, polyoxyethylenesorbitan monolaurate) in alcohol, preferably methanol, is freshly prepared. Approximately 1ml of this mixture is added to approximately 100ml of the prepared gold sol, and is stirred. The resulting mixture is allowed to set at room temperature for approximately 2 hours. Lower concentrations of the coating compound will effectively coat gold sol but the optimal coating times must be found empirically for each case. The sol mixture is washed into an approximately 1mM 3-[N-Morpholino]-2-hydroxypropane sulfonic acid (MOPSO), pH 7 buffer by centrifugation at 2000 x g for approximately 15 minutes at room temperature, and can be stored at 4°C until use. The above is an example of coating gold sol with an n-alkanethiol compound. This coating procedure is modified for the attachment of mixtures of n-alkanethiols and n-alkanethiol derivatives containing linking groups for the chemical conjugation of ligands, or polymeric compounds. For example, the inclusion of an hydroxy-n-alkanethiol to the coating mixture increases the hydrophilicity of the sol surface and decreases the non-specific interaction of the sol with serum proteins. The inclusion of a carboxyl-n-alkanethiol at a level of 10% of total thiol compounds present is sufficient to produce a sol with the desired density of conjugation moieties. The carbon chain length of the n-alkanethiol in these mixtures can be 2-4 carbons less than the carbon chain length of the n-alkanethiol derivatives in order to better expose the conjugation moieties to reduce steric hindrance associated with reaction of macromolecules with the sol surface. The coating solution of n-alkanethiol, n-alkanethiol derivative or mixtures of the two groups is generally made in alcohol, preferably methanol, with 1% Tween-20R. The total concentration of all the thiol compounds is generally no greater than 0.10M. In some cases, the optimal pH for coating thiol compounds is not 7. For example, in the case of trithiocyanuric acid coated sols, the sol is adjusted to pH 6 before the addition of the thiol compound to optimize the degree of resistance to salt-induced agglomeration conferred by a particular thiol compound mixture. The sols are generally allowed to coat in the presence of the thiol mixture for 2 hours, but optimal incubation times are determined empirically for each case. This is accomplished by testing the sols for their resistance to salt-induced agglomeration after incubation periods of varying length using a spectrophotometric assay. Gold sols have a characteristic violet color, which is exceedingly sensitive to the diameter of the sol particles. If sol particle agglomeration takes place, the effective size of the sol is greatly increased and the characteristic absorption maximum shifts from 540nm, which is violet, to higher wavelengths, with a blue to colorless sol color. In practice, 1ml of the coated sol aliquot is dispensed into a glass tube. One hundred microliters of 10% NaCl are added to the sol aliquot with mixing. The mixture is allowed to set at ambient temperature for 10 minutes and its absorbance at 540nm is compared to an identical sol aliquot to which 100 microliters of water have been added. A test aliquot that retains 90% or greater of the absorbance of the control aliquot is considered to be resistant to salt-induced agglomeration. Compounds tested are shown in Table 1 below. Compound(s) Relative Degree of Protection From Salt-Induced Agglomerationn-hexadecanethiol97% n-dodecanethiol93% n-hexadecane25% 1-hexadecanoic acid26% 12-mercapto-1-dodecanoic acid46% 11-mercapto-1-undecanol2,3-dimercapto succinic acid41%2,5-dimercapto-1,3,4-thiadiazole94%3-amino-5-mercapto-1,2,4-triazole<30% trithiocyanuric acid<30% n-dodecanethiol: 12 mercaptododecanoic acid (1:1)74% (4:1)76% (9:1)90% n-decanethiol:11-mercapto-1-undecanol: 12-mercapto dodecanoic acid (8:1:1)100% (6:3:1)83% The compounds found to be most successful in coating the gold sol and protecting it from salt-induced agglomeration were n-alkanethiols. N-alkanethiol derivatives such as 12-mercapto-1-dodecanoic acid were ineffective by themselves in conferring resistance to salt-induced agglomeration, but sols coated with mixtures of n-alkanethiols and their derivatives did confer complete protection from salt-induced agglomeration and contributed the other properties discussed above. The coated gold sol containing chemically conjugatable groups is then bound to binding moieties such as proteins, carbohydrates, antibodies, antigens, polymers, monomers or ligands using carbodiimide chemistry by well known methods. Binding moieties include any groups that are capable of being adsorbed or covalently attached to the coated gold sol. In some cases, carbodiimide chemistry is also used to conjugate a linker molecule such as 6-amino caproic acid to the sol prior to the indirect conjugation of the binding partner in order to relieve steric constraints on the binding partner and aid in its recognition by and of its complementary binding partner. In order to conjugate the binding partner or the linker molecule to the coated sol, the sol is incubated at ambient temperature in the presence of the substance to be coupled, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride(EDC), and N-hydroxysulfosuccinimide(SNHS), in a 10-25mM buffer at pH 7.0 for 2 hours. In some cases, sequential aliquots of EDC are added during the conjugation reaction in order to compensate for the hydrolysis of this compound in aqueous media. The choice of potentially useful conjugation chemistries is determined by the chemical moiety on the coated sol as well as by the type of moiety introduced on any given linker molecule. For example, amino groups on the sol-bound alkanethiol derivatives or attached linker molecules could be conjugated to polymers using homo- or hetero-bifunctional N-hydroxysuccinimide ester crosslinkers. Likewise, sulfhydryl groups on sol-bound alkanethiol derivatives or linker molecules could be conjugated to polymers using homo- or hetero-bifunctional maleimide crosslinkers. The range of possible conjugation schemes is very similar, if not identical to, the range of chemical schemes currently used in the preparation of diagnostic immunoconjugates. Classical crosslinking reagents compatible with the moieties on the sol, the alkanethiol derivatives or the chemical crosslinkers are needed to attach the appropriate binding partner to the sol. Immunoassays using the sol particle immunoassay (SPIA) method are performed as described in US Patent 4,313,734 to J. Leuvering. Briefly, gold sol coated with a binding moiety is incubated in the presence of a test sample containing the opposite binding partner. If the opposite binding partner is present in the sample, cross linking of the coated sol will result and the absorbance at the absorption maximum of single gold sol particles will decrease dramatically. The adsorption properties of polymeric compounds to gold sols may be facilitated by the thiolation of the binding partner. Both polyclonal and monoclonal antibodies were thiolated by reaction with N-succinimidyl S-acetylthioacetate (SATA). The resulting protected sulfhydryl groups were exposed by reaction of the proteins with hydroxylamine hydrochloride. This is a well known chemical procedure for introducing sulfhydryl groups into protein. The thiolated proteins were then adsorbed to gold sols at pH's 6, 7, 8 and 9 at protein concentrations ranging from 5µg/ml to 100µg/ml. The degree of resistance to salt-induced agglomeration was determined as described above. Thiolation of antibodies by this method significantly improved their ability to protect gold sol from salt-induced agglomeration over non-thiolated antibodies, as shown in Figures 7 and 8, and described in Example 12. An alternative method of facilitating the adsorption of antibodies to gold sol is the inclusion of an intermediate coating between the gold sol and the binding partner in order to change the physico-chemical properties of the sol surface such that adsorption of the antibodies is increased. Di- and tri-thiols are used for such a purpose. Trithiocyanuric acid (TTC) is an example of such a compound. Gold sol was coated with TTC in a procedure similar to that described above for the n-alkanethiol compounds but with different concentrations of TTC and Tween-20R. These concentrations were determined empirically. The ability of antibody to confer resistance to salt-induced agglomeration of the washed sol was determined after incubation of the antibody and the coated sol at various pH's and protein concentrations in the previous paragraph. The coated microparticles of this invention may be covalently bound to antigen or antibodies and sold in a test kit for use in immunodiagnostics. The antigen or antibody will be specific for the opposite binding partner sought to be detected, and the other components of the kits may include diluents, buffers, labeling reagents and laboratory equipment that will also be specific for the particular test to be performed. EXAMPLESExample 1. Preparation of Gold Sol.For preparation of the seed sol used in the final gold sol preparation, 10ml of 1% HAuCl4 trihydrate was added to 900 ml of water and stirred well. 10ml of 1% sodium citrate was added to the mixture and stirred well. With vigorous stirring, 10ml of 0.075% sodium borohydride was added (made by dissolving sodium borohydride in the sodium citrate solution) and stirred well for 5 minutes. The mixture was filtered through a 0.22 micron filter and stored at 4°C. The sol should age at least 24 hours before use. For preparation of the final gold sol, 8ml of 2% HAuCl4 trihydrate (in water) was added to 900ml of water. With continuous stirring, 4ml of freshly prepared 5% hydroxylamine hydrochloride was added (in water). Immediately thereafter, 22.33 microliters of seed sol was added and stirred vigorously for 30 minutes. 1 microliter of acetone was added for each milliliter of sol produced and stirring continued for 10 minutes. 0.2M K2KCO3 was added until the desired pH was obtained. The appropriate volume of seed sol added was determined by the following relationship: Volume of seed required for desired sol size = Volume of seed required for sol of given size times the cube root of (Diameter of sol obtained from a given amount of seed sol divided by diameter of the desired particle). Example 2. Coating of Gold Sol with n-Alkanethiol.Gold sol was prepared as described in Example 1. A solution of 0.1M 1-dodecanethiol in methanol and 1% Tween-20R was freshly prepared. For every 100ml of gold sol to be coated, 1ml of the thiol-methanol solution was added dropwise with stirring to the gold sol. The mixture was allowed to set at ambient temperature with occasional swirling for 2 hours. The coated gold sol was recovered by centrifugation at 2000 x g for 15 minutes at ambient temperature with subsequent resuspension in 1mM MOPSO, pH 7.0. This centrifugation and resuspension was repeated 3 times. The resultant sol was resuspended in the same buffer and stored at 4°C prior to use. Example 3. A n-Alkanethiol and n-Alkanethiol Derivative Mixture Coated Gold Sol.Gold sol was prepared as described in Example 1. A solution of 0.09M 1-dodecanethiol, 0.01M 12-mercapto-1-dodecanoic acid in methanol and 1% Tween-20R was freshly prepared. For every 100m of gold sol to be coated, one ml of the thiol mixture-methanol solution was added dropwise with stirring to the gold sol. The mixture was allowed to set at ambient temperature with occasional swirling for 2 hours. The coated gold sol was recovered in a manner identical to the previous example Example 4. n-Alkanethiol Derivative Gold Sol Coating and Subsequent Lack of Protection from Salt-Induced Agglomeration.Gold sol was prepared as described in Example 1 and adjusted to ph 7 with K2CO3. A solution of 0.10M 12-mercapto-1-dodecanoic acid and 1% Tween-20R in methanol was freshly prepared. For every 100ml of gold sol to be coated, 1ml of the thiol-methanol solution was added dropwise with stirring to the gold Sol. The mixture was allowed to set at ambient temperature with occasional swirling for 1 hour. To duplicate 1ml aliquots of the coated sol were added either 100µl of water or 10% NaCl. The aliquot to which water was added was considered the control. The aliquot to which 104 NaCl was added had lost 54% of its optical density after 10 minutes. This is interpreted as evidence that the gold sol was not protected from salt-induced agglomeration by being coated with the 12-mercapto-1-dodecanoic acid. Example 5. Preparation of a Gold Sol Coated with a Mixture of n-Alkanethiol and n-Alkanethiol Derivatives.Gold sol was prepared as described in Example 1 and adjusted to pH 7 with K2CO3. A solution of 0.004M N-decanethiol, 0.0005M 11-mercapto-1-undecanol, 0.0005M 12-mercapto-1-dodecanoic acid, 0.08M NaCl and 1% Tween-20R in methanol was freshly prepared. For every 100ml of sol to be coated, 1ml of the thiol-thiol derivative solution was added dropwise with stirring and the mixture was allowed to set overnight at ambient temperature. The coated sol was assayed for protection from salt-induced agglomeration as in Example 4. The coated sol retained 100% of its optical density at 540nm after the addition of 10% NaCl. This is believed to show that the coated sol is fully protected from salt-induced agglomeration. Example 6. Bovine Serum Albumin (BSA) Conjugation to Coated Gold Sol.Four ml of the coated gold sol described in Example 3 with an optical density at 540nm of 25.0 was mixed with 4.3ml of 10mM MOPSO, pH 7.0. To this mixture was added sequentially with stirring, 0.2ml of 25mg/ml BSA, 1.0ml of 30nm SNHS, and 0.5ml of 0.1M EDC. The BSA, SNHS and EDS were prepared in 10mM MOPSO, pH 7.0. The reaction was rocked for 2 hours at ambient temperature. The reaction was quenched by an additional hour of rocking after the addition of 1ml of 1.0M ethanolamine (adjusted to pH 7.0 with HCl), pH 7.0 in 10mM MOPSO. An equal volume of 10mM MOPSO, 0.15M NaCl, 0.5% Tween-20R, 1.0mg/ml casein, at pH 7.0 was added to the reaction mixture and the mixture was allowed to set for 1 hour. This blocking or overcoating step protects the unreacted bare areas of the gold sol surface from nonspecific interaction with other biopolymers. The BSA conjugated coated sol was recovered by centrifugation at 2000 x g at ambient temperature for 15 minutes and subsequent resuspension in the same buffer. This centrifugation and wash was repeated 3 times. The sol was centrifuged as above and resuspended in 10mM MOPSO, pH 7.0. This step was repeated twice. The BSA conjugated coated sol was stored at 4°C prior to use. Example 7. SPIA of BSA Conjugated Gold Sol.The BSA conjugated gold sol from Example 5 was diluted in 0.1M MOPSO, 0.15M NaCl, 1.0% polyethylene glycol 8000, pH 7.0 to obtain an optical density at 540nm of 1.0. Polyclonal anti-BSA antibody and normal rabbit immunoglobulin(IgG) were diluted in 10mM MOPSO, pH 7.0 to 12 microliters/ml. To separate 1ml aliquots of BSA conjugated sol were added 100 microliters of the diluted anti-BSA or normal rabbit IgG, or 10mM MOPSO buffer with mixing. The mixtures were transferred to cuvettes and the optical densities at 540nm were monitored over time and shown in Table 2. The results in Table 2 demonstrate that there is immunologically recognizable BSA on the surface of the sol and that the decrease in optical density is not due to non-specific interaction of rabbit serum with the sol. Example 8. SPIA of BSA Negative Control Conjugated Gold Sol.A negative control BSA conjugated coated sol was prepared exactly as in Example 5 above except that no EDC was added to the conjugation reaction. An identical volume of 10mM MOPSO, pH 7.0 buffer was included instead. The purpose of this sol was to demonstrate in SPIA assays that the BSA activity observed was covalent in nature. Comparison of results in Tablee 2 and 3 demonstrate that although a significant portion of the BSA activity on these sols may be passively adsorbed, an equally significant portion is covalently bound. SAMPLE BSA CONJUGATED COATED SOL DECREASE IN O.D. 540nm AT 60' Anti-BSA0.401 Rabbit IgG 0.029 Buffer0.031 SAMPLE BSA NEGATIVE CONTROL CONJUGATED GOLD SOL DECREASE IN O.D. 540nm AT 60' Anti-BSA0.238 Rabbit IgG0.063 Buffer0.050 Example 9. Improvement in Coating Properties of Antibody on TTC Coated Gold Sol.Gold sol was prepared as described in Example 1, except that its pH was adjusted to 6.0 with K2CO3. A saturated solution of TTC in methanol was freshly prepared. A solution of 10% Tween-20R in methanol was added until the final Tween-20R concentration was 2.5%. Four ml of this solution was added to 200ml of the above sol with stirring and the mixture was allowed to set at ambient temperature for 2 hours with occasional swirling. The coated sol was harvested as in Example 2. Separate aliquots of the coated sol were diluted to an optical density of 2.0 and simultaneously adjusted to pH 6, 7, 8 and 9 with 10mM (2-[N-morpholino]ethanesulfonic acid) (MES), 10mM MOPSO, 10mM (N-[2-hydroxethyl]-piperazine-N-[3-propanesulfonic acid]) (EPPS), and 10mM (2-[N-cyclohexylamino]-ethanesulfonic acid) (CHES), respectively. In parallel, a gold sol was prepared as in Example 1 and separate aliquots were adjusted to pH 6, 7, 8 and 9 with K2CO3. A purified human anti-HIV polyclonal antibody was diluted to 1.0, 0.5, 0.25, 0.10 and 0.05mg/ml in each of the above buffers. To parallel 1.0ml aliquots of each of the above sols and each pH was added 100µl of antibody solution at the corresponding pH with mixing. The mixtures were allowed to set at ambient temperature for 30 minutes. One hundred µl of 10% NaCl was added to each sol mixture with agitation. After an additional 10 minutes, the optical density at 540nm of each mixture was measured, as shown in Figures 1 - 4. The adsorption of the antibody on the TTC coated sol resulted in a broader pH range at which protection from salt-induced agglomeration occurred. Also, protection from salt-induced agglomeration took place at lower antibody concentrations on the TTC coated sol. In the absence of NaCl addition, the antibody caused spontaneous agglomeration of the uncoated sol. The antibody-induced spontaneous agglomeration was much less apparent on the TTC coated sol. Collectively, these observations show that the adsorption of this antibody on TTC coated gold sol is greater than that seen on uncoated sol. Example 10. Improvement in SPIA Activity of Antibody Adsorbed on TTC Coated Gold Sol.One hundred ml of gold sol was prepared as in Example 1 and the pH was adjusted to 9.0 Two and one-half milliliters of 2mg/ml of the human anti-HIV (GC-143) in 10mM CHES, pH 9.0 was added with stirring and the mixture was allowed to set at ambient temperature for approximately 2 hours with occasional swirling. Five ml of 1mg/ml nonfat dry milk was added to the mixture with stirring and the mixture was allowed to set at ambient temperature for an additional hour. The coated sol was centrifuged at 2000 x g for 15 minutes at ambient temperature and resuspended in 10mM CHES, 0.5% BSA, 300mM mannitol, 0.01% sodium aside, at pH 9.0. The centrifugation and resuspension step was repeated 3 times. The sol was finally resuspended in the same buffer and stored at 4°C prior to use. A TTC coated sol prepared as in Example 9 was diluted with 10mM CHES at pH 9.0 to obtain 60ml of sol with an optical density of 2.0, the same approximate optical density of the gold sol prepared in Example 1. Six ml of 0.5mg/ml human anti-HIV dissolved in 10mM CHES, pH 9.0 was added with stirring and the mixture was allowed to set at ambient temperature for 1 hour, then overnight at 4°C. Six ml of 1mg/ml nonfat dry milk was added with stirring and the mixture was allowed to set at ambient temperature for 1 hour. The coated sol was harvested as above and stored identically. Aliquots of each sol were diluted to an optical density at 540nm of 2.0 with 0.1M MOPSO, 0.15M NaCl, 1% PEG 8000, 0.25% BSA, at pH 7.0. To replicate aliquots of each diluted sol were added a) one hundred µl buffer, b) one hundred µl of 10µg/ml HIV gp160, or c) one hundred µl of a mixture of 5µg/ml HIV gp160 and 5µg/ml human anti-HIV which had been pre-incubated for 90 minutes at ambient temperature, as shown in Figures 5 and 6. It is apparent that the GC-143 TTC coated sol is more immunologically active than its uncoated sol counterpart and that its use in the SPIA assay results in a more sensitive assay. Therefore, by functional criteria as well, the GC-143 TTC coated sol is also better than the uncoated sol counterpart. Example 11. Thiolation of Monoclonal Anti-HIV p24 using N-succinimidyl-S-acetylthioacetate (SATA).One ml of monoclonol anti-HIV p24 at 1.46mg/ml in 50mM NaPO4, 1mM ethylenediamine tetraacetic acid (EDTA), pH 7.5 was mixed with 0.02ml of 5mg/ml SATA in dimethylsulfoxide (DMSO) and allowed to react at ambient temperature for 2 hours. The reacted antibody was separated from the reaction components by gel filtration through a desalting column in the same buffer. One quarter mg of the reacted gel filtered antibody was diluted to 1ml with the same buffer and 100µl of 0.05M NaPO4, 25mM EDTA, 0.5M NH2OH.HCl, at pH 7.5 was added with mixing. The reaction was allowed to set for 1.5 hours at ambient temperature. The deprotected antibody was gel filtered through a desalting column into the original buffer to remove unreacted reagents. Example 12. Improvement of Coating Properties of Thiolated Monoclonal Anti-HIV p24.Gold sol was prepared as described in Example 1 except that separate aliquots of the sol were adjusted to pH 6, 7, 8 and 9 with K2CO3. In parallel, separate aliquots of the underivatized and derivatized monoclonal anti-HIV p24 (see Example 11) were adjusted to 250, 200, 150, 100 and 50 µg/ml. For each of the above, the relative ability of derivatized and underivatized antibody to protect the gold sol from salt-induced agglomeration was made exactly as described in Example 9 (see Figures 7 and 8). It is apparent from Figures 7 and 8 that the thiolation of this monoclonal antibody resulted in improved coating characteristics as judged by a) the fact that the derivatized antibody did not spontaneously agglomerate the sol, b) the decreased dependence of antibody protection against sol agglomeration on pH, and c) the lower relative amounts of derivatized antibody required to protect from salt-induced sol agglomeration in the presence of salt as compared to the underivatized antibody sol.	Microparticles comprising gold sol coated with at least one compound selected from the group consisting of alkanethiol, alkanethiol derivatives, low molecular weight di-thiol and tri-thiol compounds. Microparticles according to claim 1, wherein said compound is at least one alkanethiol. Microparticles according to claim 1, wherein said compound is a mixture of at least one alkanethiol and at least one alkanethiol derivative. Microparticles according to claim 1, wherein said alkanethiol is a n-alkanethiol of the formula CH3(CH2)nSH, and n equals a whole number from 9 to 23 inclusive. Microparticles according to claim 1, wherein said alkanethiol derivative comprises the formula RCH2(CH2)nSH, where R is selected from the group consisting of OH, COOH, CHO, SH and NH2, and n is 9 to 23. Microparticles according to claim 1, wherein said compound is a low molecular weight di-thiol compound. Microparticles according to claim 1, wherein said compound is a low molecular weight tri-thiol compound. Microparticles according to claim 1, wherein said gold sol has a diameter of from 10nm to 150nm. Microparticles according to claim 1 which are resistant to salt-induced agglomeration, whereby no more than 10% of the optical density at 540 nm of a suspension of said sol is lost after 10 minutes in the presence of 1.0% NaCl. Microparticles according to claim 1, wherein said microparticles are covalently linked to a binding moiety. Microparticles according to claim 10, wherein the binding moiety is selected from the group consisting of proteins, carbohydrates, antigens, antibodies, ligands, polymers and monomers. Microparticles according to claim 1, additionally comprising a bridging compound which is covalently attached to said compound and to which is covalently linked a binding moiety. Microparticles according to claim 1, wherein additionally a binding moiety is passively adsorbed. A process for coating gold sol microparticles comprising: a) mixing gold sol microparticles with an alcohol solution of at least one compound selected from the group consisting of alkanethiol, alkanethiol derivatives, low molecular weight di-thiol and tri-thiol compounds thereby producing coated gold sol microparticles; b) centrifuging said coated sol; and c) resuspending the coated gold sol in buffer. A process for coating gold sol microparticles according to claim 14, wherein said alcohol solution additionally contains surfactant. A process for coating gold sol microparticles according to claim 15, wherein said compound is a mixture of alkanethiol and alkanethiol derivatives. A process for attaching a binding moiety to gold sol microparticles comprising: a) coating laid gold sol according to claim 14 to produce a coated gold sol; b) incubating said coated gold sol and binding moiety to attach the binding moiety to said coated sol; c) blocking nonspecific sites on the coated gold sol of step b; d) centrifuging said coated gold sol of step c; and e) resuspending the coated gold sol of step d in buffer. A process for attaching a binding moiety to gold sol microparticles comprising: a) coating gold sol according to the process of claim 15; b) incubating a mixture of the gold sol, appropriate chemical crosslinkers and binding moiety to attach the binding moiety to the coated gold sol; c) quenching said mixture; d) blocking nonspecific sites on the coated gold sol of step b; e) centrifuging the coated gold sol of step d; and f) resuspending in buffer. A process for attaching a binding moiety to gold sol microparticles comprising: a) coating gold sol microparticles according to the process of claim 16; b) incubating a mixture of said coated gold sol, appropriate chemical crosslinkers and binding moiety to attach the binding moiety to the coated gold sol; c) quenching said mixture; d) blocking nonspecific sites on said gold sol of step b; e) centrifuging said gold sol of step d; and f) resuspending in buffer. A process for attaching a binding moiety to gold sol microparticles comprising: a) coating gold sol microparticles according to the process of claim 15; b) incubating said coated gold sol with a binding moiety; c) blocking nonspecific sites on said coated gol sol of step b; d) centrifuging said coated gold sol of step c; e) resuspending said gold sol of step d in buffer. A process for attaching a binding moiety to gold sol microparticles comprising: a) modifying said binding moiety by chemical thiolation; b) incubating the thiolated binding moiety of step a with gold sol microparticles; c) blocking nonspecific sites on the gold sol of step b; d) centrifuging the gold sol of step c; and e) resuspending the gold sol of step d in the buffer. A diagnostic kit for use in immunoassays comprising microparticles according to claim 1, and a buffer solution.	AKZO NOBEL NV; AKZO NOBEL N.V.	HSIEH YUNG-AO; SHIGEKAWA BRIAN LAYNE; HSIEH, YUNG-AO; SHIGEKAWA, BRIAN LAYNE
EP-0489466-B1	489,466	EP	B1	EN	19,941,026	1,992	20,100,220	new	F24F11	F04D25	F04D25	F04D 25/14	Centrifugal actuating device for pushing or pulling an element to be operated	A centrifugal device (17), in particular for operating shutters (20) disposed facing a fan (15), comprises a first end plate (23) connected to the end of a shaft (16) for rotating the fan (15). Facing said first plate (23) is a second end plate (24) rotatingly supporting, on an axis substantially coinciding with the shaft (16), a fastening element (19) for a control rod (18) which operates the mechanism when the two plates move away from and towards each other. The plates being linked to each other by at least three centrally articulated arms (26, 27) provided with counterweights (29) close to the central joint (28), on rotation of the shaft the centrifugal force acting on the counterweights (29) causing the central joints (28) to move apart from each other.	The problem of pushing or pulling mechanical devices or apparatus in relation to a rotatory movement is well-known in many fields. For this purpose, actuating devices have been proposed comprising counterweights disposed on elements articulated so as to move a sleeve sliding on a shaft coaxial to the axis of rotation under the effect of the centrifugal thrust on the counterweights. One particular problem, in the field of ventilating and aerating systems consists of automatically opening shutters when the fans positioned immediately behind them are turned on. Known centrifugal devices for automatically opening shutters comprise a shaft, an extension of the drive shaft of the fan, onto which is secured a linkage system which, when operated by the centrifugal force generated by rotation of the fan on two suitable opposing counterweights, causes a collar to shift axially along said shaft and in turn push open the shutters disposed in front of the fan. (see for example US-A-4,217,816 and US-A-2,468,366). Despite the fact that they achieve their purpose, the known devices present serious drawbacks. In fact, in numerous fields the speeds of rotations are extremely variable. For example, the fans must be able to rotate at different speeds, within a very wide range, depending upon the delivery of air required at any given moment. To enable the actuating device to operate even at very low speeds the counterweights necessarily have to be very large. However, at higher speeds with heavy counterweights the device must be extremely well-balanced. Even the slightest imbalance of the counterweights gives rise to very strong vibrations, which can cause considerable damage to the entire structure of the fan. In practice, devices such as the ones described above do not lend themselves to use, for example, whenever there are very wide variations in the speed of rotation, since they require excessively precise adjustment which is not always easy to obtain due to inevitable machining tolerances. Moreover, their strength and reliability are limited by the vibrations that they themselves generate. The scope of this invention is to obviate the aforementioned problems by providing a centrifugal actuating device, in particular for automatically opening shutters placed in front of a fan, which is self-centering and therefore intrinsically unaffected by imbalance and normal machining tolerances. This scope is achieved, according to the invention, by providing a centrifugal device as claimed in claim 1. The innovatory principles of this invention and its advantages with respect to the known technique will be more clearly evident from the following description of possible exemplificative embodiments applying such principles, with reference to the accompanying drawings, in which: figure 1 shows a schematic partial cross-sectional side view, in a non-operative position, of a fan with shutters fitted with an opening device made according to the innovatory principles of this invention; figure 2 shows a schematic partial cross-sectional side view of the device of figure 1 in an operating position; figure 3 shows an enlarged partial cross-sectional side view of the opening device of figure 1 in an non-operative position; figure 4 shows a view similar to that of figure 3 but with the opening device in an operating position; figure 5 shows a front view of the device as shown in figure 4; figure 6 shows a front view of a first possible embodiment of an automatic opening device applying the innovatory principles claimed herein; figure 7 shows a partial cross-sectional side view, in an operating position, of a second possible embodiment of an automatic opening device according to the invention; figure 8 shows a view similar to that of figure 7 but with the opening device in a non-operative position. With reference to the figures, a ventilating device 10 comprises a casing 11 inside which rotate, by means of a motor 12 and a belt drive 13, radial blades of a fan 15. Disposed at the end of the shaft 16 of the blades 15 is an automatic opening device 17, connected to shutters 20 by means of a control rod 18 secured to its operating end 19. In the non-operative position, shown in figure 1, the shutters, which are pivoted at the ends, are in a vertical position so as to substantially fit together with one another to close the air outlet 21 of the fan. In the open position, shown in figure 2, the shutters are held in a horizontal position by the device 17, thereby opening the air outlet 21. As can be clearly seen in figure 2, the shutters are interconnected by means of an element 22, so that when just one of them is operated the others are simultaneously and parallely shifted. Figure 3 shows the opening device 17 in its non-operative position of figure 1. As can be seen in figure 3, the device 17 comprises a first end plate 23 secured to the end of the shaft 16 so as to rotate with it. A second opposing plate 24 supports, by means of a bearing 25, in a direction substantially coaxial to the shaft 16, the operating end 19 pivoted to the control rod 18. Pivoted to the sides of the two end elements or plates 23, 24 are respective arms 26, 27, with a central joint on pivot pins 28. As can be seen in figure 5, the arms pivoted to each end element are for example four in number, one for each side of the end elements. In this way, the element 24 can only move away from or towards the element 23 in a direction substantially coinciding with the axis of rotation of the fan, thus shifting from the position of figure 3 to the position of figure 4. Disposed close to each pin 28 reciprocally pivoting the arms 26 and 27 are counterweights 29 composed, for example, of metal disks. Thus, on rotation of the shaft 16 and, consequently, the device 17, its transition from from the position of figure 3 to the position of figure 4 is caused by the centrifugal force on the counterweights 29, the plane passing through the central joints always substantially lying between the two plates. Since the base or end plate 23 is the only connection between the device 17 and the shaft 16, the same centrifugal force acting on the counterweights 29 tends to keep them in a balanced position with respect to the axis of rotation due to the movements and deflections peculiar to the device itself. The device 17 is consequently self-centering and does not therefore require any fine adjustment. Contrary to the known technique, it is consequently possible to use even very heavy counterweights 29 without any danger whatsoever of causing vibrations during rotation. The device is thus able to operate just as efficiently at low speeds as it does at high speeds. By providing counterweights 29 proportionate to the force required to open the shutters 20 it is possible to obtain a device 17 which opens the shutters even when the blades 15 revolve at very low speed. To reclose the shutters, it is sufficient to take advantage of the momentum produced by their own weight around their axis of rotation (if necessary, providing suitable ballasting). It is obvious that the arms connected to the end elements need not necessarily be four in number. It is sufficient to ensure the rigidity of the device apart from the possibility of movement between the two positions of figure 3 and figure 4. For example, figure 6 shows a device 17' (for convenience, identical numbering but with the suffix prime and subsequently second will be used to indicate parts similar to those of the preceding figures) having only three arms 26', 27' disposed at 120° from each other around generically triangular end elements 23', 24'. Figures 7 and 8, on the contrary, show a device 17'' having a different reciprocal disposition between the end elements 23'', 24'' and the arms 26'', 27''. With this different disposition, in which the central joints of the arms have a common plane always outside the space between the plates, the maximum distance of the counterweights 29'' from the axis of rotation is made to match the maximum reciprocal distance between the end plates 23'', 24''. Figure 7 shows this device in the shutter opening position, while in figure 8 it is shown in the non-operative position. This way of operating is useful whenever it is necessary to open the shutters by pushing instead of by pulling as in the case of the device shown in figures 1 and 2. In installing the device 17'', the control rod 18'' will, of course, be secured to the shutters in the opposite position with respect to that shown in figure 1, as will be obvious to any expert technician. It will be clear at this point that the intended scopes are achieved by providing a device for automatically opening and closing shutters coupled to fans, which is structurally simple and self-centering, to enable it to operate efficiently and without vibrations within a wide range of operating speeds. Both the end plates and the arms can advantageously be moulded from suitably sturdy plastic. Moreover, as can be clearly seen in figures 3-5, the two end plates can be made identical in shape as can each pair of arms. In this way, two moulds are sufficient to obtain all the main parts of the device. The proportions between the various parts of the device can differ from those shown, just as the shape of the arms and the end plates can likewise differ.	A centrifugal device comprising first (23) and second (24) plates, between themselves being a plurality of centrally articulated arms (26, 27) supporting counterweights (29) close to a central joint (28) of the arms, on the rotation of the device the centrifugal force acting on the counterweights (29) to cause the central joints (28) to move apart from each other, thereby the first and second plates moving respect to each other to operate a mechanism connected to said device, characterized by the fact that the first plate (23) is connected to one end of a shaft (16) rotating the device, and the second plate (24) is disposed in spaced, confronting relation to said first plate and said one end of said shaft and rotatingly supporting thereon, on an axis substantially coaxial with the shaft (16), a fastening element (19) for a control rod (18) which operates the mechanism when the two plates (23, 24) move away from and towards each other, the centrally articulated arms being at least three and the plates being linked to each other solely by said centrally articulated arms (26, 27). Centrifugal device as claimed in claim 1, characterized by the fact that the plane passing through the central joints (28) is substantially always contained between the two plates (23, 24), the plates (23, 24) being in the position where they are closest to each other when the counterweights (29) are in the position where they are furthest away from each other. Centrifugal device as claimed in claim 1, characterized by the fact that the plane passing through the central joints (28) is substantially always outside the space between the two plates (23, 24), the plates (23, 24) being in the position where they are furthest away from each other when the counterweights (29) are in the position where they are furthest away from each other. Centrifugal device as claimed in claim 1, characterized by the fact that the arms (26, 27) are three in number disposed according to the vertices of an equilateral triangle. Centrifugal device as claimed in claim 1, characterized by the fact that the arms (26, 27) are four in number disposed according to the vertices of a square. Ventilating apparatus comprising a fan with blades (15) pointing substantially in a radial direction from a central rotating shaft (16), shutters (20) being disposed facing said fan which are movable from a position in which they open to a position in which they close an air outlet (21) of the fan, characterized by the fact that connected between the shaft (16) driving the blades (15) and said shutters (20) is a centrifugal device (17) made according to any of the previous claims, the drive shaft of the centrifugal device coinciding with the drive shaft of the fan, and the control rod being connected to move the shutters to and from the aforesaid two positions.	GIGOLA ANTONIO; GIGOLA, ANTONIO	GIGOLA ANTONIO; GIGOLA, ANTONIO
EP-0489467-B1	489,467	EP	B1	EN	19,950,726	1,992	20,100,220	new	G08B3	G08B26, G08B5	G08B26, G08B3	G08B 3/10B1C, G08B 26/00B2	System for detecting the presence in a rack of a portable unit suitable for transmitting or receiving a signal having an assigned identification number	In a system for detecting the presence in a rack of a portable unit suitable for transmitting or receiving a signal having an assigned identification number said portable unit comprises a detection means which detects the placing of the portable unit in, or its removal from, a compartment. If said detection means detects placing of the portable unit in a compartment the portable unit transmits a presence report signal which is received by a receiving means of a detection device of the rack in reponse to which a control circuit of the detection device stores a presence datum in a location of a memory indicating the presence of the portable unit in the rack. Removal of the presence datum out of the memory can be caused in several ways. According to one solution the portable unit detects said removal and transmits an absence report signal ARS in response to which the control circuit of the detection device removes said present datum from the memory. According to a second solution the portable unit, if placed in a compartment, transmits continuously or intermittently a hold signal HS. If the detection device of the rack does not receive the holdsignal HS during a predetermined period of time it removes the present datum. According to a third solution the compartment has a detection means, e.g. a switch, which can detect the removal of the portable unit from the compartment. If the detection means detects such removal the controle device of the rack removes the present datum out of the memory. According to a fourth solution the detection device of the rack scans each compartment in which the presence of a portable unit has been detected by transmitting a scanning signal to each of these portable units. If the detection device does not receive a response signal from a scanned portable unit within a predetermined period of time it removes the presence datum for this portable unit out of the memory. For both the first and second of said solutions the initiative for storing or removal a present datum in the memory lies with the portable unit. With both of said third and fourth solutions the initiative for storing a presence datum lies with the portable unit and the initiative for removing the presence datum out of the memory lies with the detection device of the rack.	The invention relates to a presence detection system according to the preamble of Claim 1. The portable unit may be, for example, a pager unit of a paging system, a transponder, an alarm transmitter or an electronic key. A presence detection system of the abovementioned type is described in Dutch Patent Application 90.01318 with was filed on 11 June 1990 in the name of the Applicant (at that time: Ericsson Paging Systems B.V.) and was not laid open at the instant of filing of the present application. In said previously described system, at least the compartments of a rack in which a portable unit has been placed are scanned for the presence of a portable unit on the initiative of, and actively by the control circuit of the detection device. For all the variants of the system described earlier, it is necessary that each compartment has a transmitting means and each portable unit has a receiving means for transmitting a scanning signal to the control circuit of the portable unit from the control circuit of the detection device. In addition, each portable unit has to have a transmitting means and each compartment has to have a receiving means for transmitting a response signal which the control circuit of the portable unit transmits to the control circuit of the detection device in response to the receipt of the scanning signal. According to a variant of the previously described system, all the compartments of the rack are continuously and sequentially scanned by the detection device. According to another variant, each compartment has, in addition, a detection means for detecting the presence of a portable unit in the compartment. In this second variant, the detection device transmits a scanning signal via the compartment to the portable unit only after detection of the presence of a portable unit in the compartment. For both cases, there is only one type of response signal. Said response signal contains the identification number or identification datum assigned to the portable unit. The previously described presence detection system has the drawback that quite a large number of means are necessary to detect the presence/absence of a portable unit in a compartment and to determine the identity of the portable unit placed in a compartment. The object of the invention is to eliminate the drawback of the previously described presence detection system. This object is achieved for the presence detection system according to the invention described in the preamble of Claim 1 by means of the measures of the characterising part of Claim 1. As a result of this, when a portable unit is placed in a compartment, the portable unit takes the initiative of reporting with its identification number to the detection device that it is in a compartment. As a result of this, the portable units and the racks can be relatively simple. The receiving means of the rack can be common to all the compartments of the rack, it being possible for the report signal to be transmitted radiographically, inductively or optically. As an alternative, each compartment of the rack can have its own receiving means, the report signal being transmitted between a compartment and a portable unit present therein, and the report signal can also be transmitted as an alternative via contacts of the compartment and the portable unit which touch one another after placing the portable unit in the compartment. Such contacts may be contacts mounted on the bottom of the compartment and oppositely situated contacts of the portable unit, but they may also be wiper contacts running in the plug-in direction of the portable unit, the connection between the contacts being maintained while the portable unit is being moved over a certain distance. The contacts may be contacts of a storage battery charging current circuit, the portable unit detecting the flow of a storage battery charging current or the connection to an external storage battery charging voltage source in order to detect the presence of the unit in a compartment, and the portable unit may modulate the storage battery charging current for transmitting the report signal. The presence detection system may detect in various ways whether a certain portable unit is being removed from the compartment. According to a first embodiment, the control circuit of each portable unit monitors removal thereof from a compartment and if this occurs, the portable unit transmits an absence report signal. On receiving said absence report signal, the control circuit of the detection device removes a presence datum from the memory which was previously stored in the memory for the portable unit. Depending on the type of transmission path between a portable unit and a compartment and/or to increase the reliability, the absence report signal may contain the identification number of the portable unit. In addition, the presence report signal and the absence report signal may be identical, possibly with the exception of a section which characterises each of said signals. According to another embodiment of the system, a portable unit, after transmitting a presence report signal, continuously or periodically transmits a hold signal and the control circuit of the detection device monitors the receipt of such a hold signal and if it has not received a hold signal for a predetermined time, removes the presence datum stored in the memory for the portable unit. If the contacts mentioned are used as transmission paths for the presence report signal, said contacts can also be used to transmit the hold signal, as a result of which no other transmission or detection means are necessary and the detection system is relatively simple. According to yet another embodiment, each compartment of a system has a detection means for detecting the presence of a portable unit in the compartment and, after receiving a presence report signal from the compartment, the detection device monitors the presence of the portable unit by means of the detection means, the detection device removing, on detecting the absence of the portable unit in the compartment, a presence datum from the memory which was previously stored for the unit. In this case, a simple detection system is also obtained in which, with respect to the previous embodiment, a portable unit only needs to transmit a signal when it is placed in a compartment, and this results in current saving and counteracts any interference with other signals. According to yet another embodiment of the system, each compartment has a transmitting means and each portable unit has a corresponding receiving means for transmitting a scanning signal from the control circuit of the detection device to a portable unit placed in the compartment after the detection device has received a presence report signal from the portable unit, and after receiving a scanning signal, the portable unit transmits a response signal and the detection device removes a presence datum from the memory which was previously stored for the portable unit if the device has not received a response signal for a predetermined time. Because as regards the detecting of the removal of a portable unit from a compartment, the same type of means are used and the scanning signal and the response signal have the same function as in an embodiment of the system according to the said NL 90.01318, reference is made to the description of the said NL 90.01318 for a more detailed explanation thereof, although this is not deemed necessary for a person skilled in the art. Other characteristics and advantages of the invention will become clear from the explanation, which follows below, of some embodiments of the invention with reference to the attached drawings. In the drawings: Figure 1 shows diagrammatically a compartment of a rack with a portable unit placed therein; Figure 2 shows a diagram of a pager as portable unit of a paging system and of the detection system according to the invention; Figure 3 shows a diagram of an embodiment of a detection system according to the invention; Figure 4 shows a flow chart of an operation of the control circuit of the pager of Figure 2 relating to presence detection; Figure 5 shows a flow chart of an operation of a control circuit of the rack when the portable unit operates according to the operation of Figure 4; Figure 6 shows an embodiment of a detection device of the detection system according to another operation of the control circuits of the portable units and of the detection device relating to the presence detection of a portable unit in a compartment; Figure 7 shows a flow chart of the operation of a portable unit for use in the circuit of Figure 6; Figure 8 shows a flow chart of the operation of the control circuit of the detection device for the circuit of Figure 6; Figure 9 shows a replacement section for the flow chart of Figure 8 for a different operation of the portable unit; Figure 10 diagrammatically shows another embodiment of a compartment of a rack with a portable unit placed therein; Figure 11 shows a flow chart for the operation of a portable unit when compartments are used as shown in Figure 10; and Figure 12 shows a replacement section for the flow chart of Figure 8 when compartments are used as shown in Figure 10 and portable units operate according to Figure 11. Figure 1 shows diagrammatically an embodiment of a compartment 1 of a rack (not shown) having a number of similar compartments, it being possible to place a portable unit 2 in each compartment 1. In the embodiment of Figure 1, each compartment 1 has two contacts 3a, 3b which are connected via a conductor bundle 15 to the terminals of a voltage source (not shown) of the rack. Each portable unit 2 has two contacts 6a, 6b which, after the portable unit 2 is placed in a compartment 1, touch the contacts 3a and 3b, respectively, and which are connected to the terminals of a storage battery or storage battery supply circuit (27 in Figure 2) of the portable unit 2. After the portable unit 2 has been placed in a compartment 1, the voltage source of the rack will charge the storage battery of the portable unit 2. The base 7 of each compartment 1 has a light-transmitting opening 8 below which a photosensitive device, in particular a photosensitive diode 9, is mounted. The diode 9 is connected with a suitable orientation of its polarity in series with a resistor 10 to the contacts 3a, 3b of the compartment 1. If the photosensitive diode 9 receives light, a voltage across the resistor 10 alters. This voltage is tapped off by a conductor 11 which is a conductor of the conductor bundle 15 and which is connected to the junction of the diode 9 and the resistor 10. As shown diagrammatically and with small dashes, the portable unit 2 has a light-transmitting opening 13 in its bottom 12 behind which a light-emitting device, in particular a light-emitting diode or LED 14 is mounted. When the portable unit 2 has been completely or partly placed in a compartment 1, the photosensitive diode 9 is able to receive the light emitted by the light-emitting diode 14. The portable unit 2 of the presence detection system according to the invention can be any portable unit which is suitable for the wireless reception and/or transmission of a transmission signal which contains an identification number assigned to the portable unit and stored in a register of the unit. The portable unit is, for example, a pager of a paging system. Figure 2 shows a diagram of a pager 18 as portable unit 2. The pager 18 comprises an aerial 19, a receiving circuit 20 which is connected to the aerial 19 and to a decoder 21 which is connected to a comparator 22 and a control circuit 23 which is connected to a register 24, operating means, such as switches, 25, a signal generator 26, the light-emitting diode 14 and a storage battery or storage battery supply circuit 27. The register 24 is also connected to the comparator 22 and contains an identification number or identification datum assigned to the pager 18. The signal generator may be an optical and/or acoustical and/or electromechanical signal generator. The paging system furthermore comprises a central station (not shown) with operating means and a transmitter for assembling a call message containing the identification number of the pager 18 and for transmitting a transmission signal containing the call message. The aerial 19 and the receiving circuit 20 of the pager 18 are suitable for receiving and demodulating the transmission signal transmitted by the central station. After receiving a calling message, the receiving circuit 20 supplies it to the decoder 21 which separates the identification number and other data from the message. The comparator 22 compares the identification number received with an identification number stored in the register 24 and, in the event of equality, supplies an enable signal to the control circuit 23 for the further processing of the other data received, which may be presented by means of the signal generator 26. Figure 3 shows a diagram of a detection device for applying the invention. A rack has a number of compartments 1 which are connected via conductor bundle 15 to a control circuit 28. For the embodiment of a compartment 1 as shown in Figure 1, the conductors connected to the contacts 3a and to the contacts 3b of the various compartments 1 may, however, also be connected directly to one another. A control circuit 28 then needs to receive only two conductors from all the compartments 1 for connection to the storage battery charging voltage source and as many conductors 11 as there are compartments 1. The control circuit 28 is connected to a memory 29, a section of which is suitable for the storing a presence datum therein for each portable unit 2, 18 which has been placed in a compartment 1. The memory 29 may have a separate location for each portable unit 2, 18 or a location can be assigned to each compartment for storing an identification number after the associated portable unit 2 has been placed in a compartment 1 and possibly a compartment number and a rack number if the compartments 1 are spread over a number of racks. To apply the invention, these different ways of storage are unimportant. The control circuit 28 may be a microprocessor. The control circuit 28 and the memory 29 may be mounted in each rack. The control circuit 28 and the memory 29 may also be assigned to a group of racks. Furthermore, one or more control circuits 28 can be connected to a common control circuit (not shown) for example of the central station in order to store and remove the presence data in a common memory connected to the common control circuit. The memories 29 connected to the control circuits 28 may possibly then be omitted. The connections and communication rules necessary for this are deemed to be readily embodiable for a person skilled in the art and are therefore not described further here. Instead of a photosensitive device, such as the diode 9, of the compartment 1 and instead of a visual light-emitting device, such as the diode 14, of a portable unit 2, 18, radiographic (high-frequency) or inductive (low-frequency) transmitting and receiving means may be used. If an inductive transmission path is used, a coil of the compartment 1 and a coil of the portable unit 2, 18 are preferably directed in the plug-in direction of the portable unit 2 in the compartment 1 in order to increase the distance over which the portable unit 2 is moved and transmission of the signal between the coils is possible. It is pointed out that, in the figures of all the flow charts explained hereafter, Y represents an answer YES and N an answer NO to a question asked in an adjacent block. Figure 4 shows a flow chart of a first operation of a portable unit 2, 18 according to the invention. After initialisation, indicated by block 30, the control circuit 23 detects that the portable unit 18 is, according to block 31, being placed in a compartment 1. The control circuit 23 is able to detect this in the case of the embodiment of the portable unit 18 shown in Figure 2 because, after the unit 2 has been placed in compartment 1, the contacts 6a, 6b touch the contacts 3a, 3b, connected to a voltage source, of the compartment 1 and because a control input of the control circuit 23 is connected to a contact 6a (or to a terminal (not shown) of the storage battery supply circuit 27). If the control circuit 23 detects the placing of the unit 18 in a compartment 1, it emits a presence report signal PRS, otherwise it proceeds with block 33 to test the removal of the unit 18 from the compartment 1. If the control circuit 23 detects that the portable unit 18 is being removed from the compartment 1, it emits, according to block 34, an absence report signal ARS, otherwise it returns to block 31. After blocks 32 and 34, block 31 is returned to. Figure 5 shows a flow chart of the operation of the control circuit 28 of the detection device of the detection system according to the invention for an operation of a portable unit 18 according to the flow chart of Figure 4. After initialisation, indicated by block 35, of the control circuit 28, the control circuit 28 detects, according to block 36, whether it has received a presence report signal PRS. If this is the case, it determines, according to block 37, the identification number from the presence report signal PRS and writes the presence datum for the identification number determined into the memory 29. Otherwise, block 38 is proceeded to. If the control circuit 28 has received, according to block 38, an absence report signal ARS, it determines, according to block 39, the identification number from the absence report signal ARS and removes the presence datum for the identification number determined from the memory 29, otherwise block 36 is returned to. After the blocks 37 and 39, block 36 is returned to. It will be clear that in the case of an operation of the presence detection system according to Figures 4 and 5, the rack can also be designed with a single common receiving means for receiving the report signals instead of a separate receiving means for each compartment 1. The transmission strength of the transmission means for the report signal of a portable unit 2, 18 and the receiving sensitivity of the common receiving means are then preferably adjusted so that a good transmission of the report signals can only take place in the vicinity of the rack in order to avoid interference with report signals of other racks. Figure 6 shows a diagram of another embodiment of the detection system according to the invention. In this embodiment, the portable units 2, 18 have, instead of the light-emitting diode 14, a resistor 40 which is connected between the control circuit 23 and the contact 6a. The rack has a storage battery charging voltage source 41, one terminal of which is connected to the contacts 3b of the compartments 1 of the rack. The contact 3a of a rack 1 is connected to the other terminal of the voltage source 41 via a resistor 42 associated with the compartment 1 having said contact 3a. The contacts 3a of the different compartments 1 are connected to respective inputs of a multiplexer 43. An output of the multiplexer 43 is connected to an input of the control circuit 28′ via a capacitor 44. The multiplexer 43 has control inputs which are connected to outputs of the control circuit 28′ for selecting one of the inputs of the multiplexer 43 which is connected to the output of the multiplexer 43. It will be clear that when a portable unit 2, 18 is placed in a compartment 1 in a rack having a detection device according to Figure 6, a modulation signal which is supplied to the resistor 40 by the control circuit 23 of the portable unit 2, 18 loads the voltage source 41 as a function of the modulation and, as a result of this, the voltage at the respective input of the multiplexer 43 alters as a function of the modulation. The capacitor 41 transmits only the alternating voltage component of the input signals of the multiplexer 43. The control circuit 28′ is, according to a manner known per se, suitable for demodulating and decoding the alternating voltage signal received from a compartment 1. Figure 7 shows a flow chart for an operation of a portable unit 2, 18 if a detection system according to Figures 1 and 2 or according to Figure 6 is used. After initialisation, indicated by block 45, the portable unit 2, 18 determines, according to block 46, whether it is being placed in a compartment 1 of a rack. If this is the case, it emits, according to the block 47, the presence report signal PRS just as in the diagram of Figure 4, otherwise it determines, according to block 48, whether it is still in the compartment 1 and if this is the case, it emits, according to block 49, continuously or periodically a hold signal HS, otherwise block 46 is returned to. The hold signal HS may be a simple signal which is identical for all portable units 2, 18, for example, a sine-wave signal having a frequency of 10 kHz. However, the hold signal HS may, still more simply, consist of a constant voltage such that an associated, essentially constant voltage drop consequently occurs across each of the resistors 40 and 42, respectively. The output of the multiplexer may then also be connected, as shown by a broken line, to another input of the control circuit 28' which detects said constant voltage drop. If the voltage source 41 supplies a, for example, positive voltage to the contact 3a via the resistor 42, the output of the control circuit 23 which is connected to the resistor 40 may have a low level with the exception of when the (modulation of the) presence signal is being emitted. If a portable unit 2, 18 is being placed in a compartment 1, the control input, connected to the contact 6a, of the control circuit 23 will then go from a low level to a high level, as a result of which the control circuit 23 is able to detect the placing. By including a diode between the contact 6a and the input, connected thereto, of the storage battery supply circuit 27, it is possible to prevent the resistor 40 from accidentally discharging the storage battery of the unit 2, 18 during normal use of the portable unit 2, 18. After the blocks 47 and 49, block 46 is returned to. Figure 8 shows a flow chart of an operation of a detection device of the detection system according to the invention in the case of an operation of the portable units 2, 18 according to the flow chart of Figure 7. After initialisation, indicated by block 50, the detection unit determines, according to block 51, whether the presence report signal is being received. If this is the case it proceeds to block 52, otherwise to block 53. According to block 52, the detection device determines, after receiving a presence report signal PRS, from which compartment i said signal was received. In the diagram of Figure 6, this can be deduced in a simple way from the selection address supplied by the control circuit 28' to the multiplexer 43. If each compartment 1 were to have a separate receiving means, this can of course also be determined in a simple manner. Furthermore, the detection device determines the identification number from the presence report signal PRS received. It then writes a presence datum and the compartment number i for the identification number detected into the memory 29. Because the number of compartments 1 of the detection system in each embodiment is limited and possibly a portably unit 2, 18 may be located therein, in an alternative embodiment, a separate location can be assigned to each compartment 1 in the memory 29, in which location only the presence datum for the detected identification number needs to be stored. As stated, the presence datum may be formed by the identification number itself. If, according to block 53, the detection device has received no hold signal HS from the compartment i for a predetermined time, it proceeds to block 54, otherwise it returns to block 51. According to block 54, the detection device searches for the location assigned to compartment i in the memory and then determines the identification number of said location and removes the presence datum for the identification number from the memory 29. Depending on the design of the detection device, with or without multiplexer, and depending on the type of hold signal HS, continuous or intermittent, the detection device for block 53 also possibly comprises an integrator function for each compartment 1. After the blocks 52 and 54, block 51 is returned to. Figure 9 shows a replacement section for the diagram of Figure 8, in which block 55 of Figure 9 replaces block 53 of Figure 8. According to block 55, the detection device determines whether it has received an absence report signal ARS from a compartment i. Such an operation of the detection device can be used if, in contrast to the operation according to Figures 4 and 5, the absence report signal does not contain an identification number of a portable unit 2, 18. If an absence report signal ARS is not (no longer) being received from compartment i, block 54 is proceeded to, otherwise block 51 is returned to. Figure 10 shows an embodiment of a compartment 1′ which differs with respect to the embodiment of compartment 1 of Figure 1 in that the compartment 1′ has a switch 56 which switches over when a portable unit 2, 18 is placed in, or removed from, the compartment 1′. The bundle of conductors 15' has in accordance with this at least one conductor more than the bundle 15 of Figure 1. Figure 11 shows a flow chart of the operation of a portable unit 2, 18 used in a detection system having compartments 1′ according to Figure 10. After initialisation, indicated by block 57, the portable unit determines, according to block 58, whether it is being placed in a compartment and if this is the case, it emits, according to block 59, a presence report signal PRS. If, according to block 58, no placing of the portable unit 2, 18 in a compartment 1′ is detected, and also after block 59, block 58 is returned to. Figure 12 shows a replacement section for the flow chart of Figure 8, in which block 60 of Figure 12 replaces block 53 of Figure 8. If, according to block 60, the detection device for compartment i detects that a portable unit 2, 18 previously present in the compartment 1′ is being removed from the compartment 1′, it proceeds to block 54, otherwise block 51 is returned to. In order to ensure, in the event of any interference, a good transmission of the presence report signal PRS and possibly of the absence report signal ARS (with identification number), the portable unit 2, 18 may repeat, within the scope of the invention, once or several times the emission of such a report signal. It is pointed out that modern portable units of the type mentioned above are based on microprocessor techniques and often comprise an ASIC (Application Specific Integrated Circuit) with which both analog and digital functions can be fulfilled. It is therefore assumed that a person skilled in the art will be able to embody the flow charts shown in the drawings for the various operations of a portable unit in such a system without substantial problems. The diagrams for the various operations of the detection devices also appear readily capable to be embodied for a similar system for a person skilled in the art. An explanation of a physical embodiment of such a system is therefore omitted. The detection devices explained may be independent devices for indicating therewith, by means of presentation means which are not shown, the presence or absence of particular portable units 2, 18 in compartments 1, 1′ of one or more racks. The detection device 28, 28′ may, however, also be connected by using connections and communication rules known per se to a central station where the presence or absence of portable units 2, 18 in racks is being monitored. Such a central station may be a central calling station of a paging system. The central station may in that case be equipped for checking, after receiving an instruction to emit a call message having a particular identification number of a portable pager 18, whether said pager 18 is or is not in a compartment 1, 1′ and for preventing the emission of the call message in the event of presence in a compartment 1, 1′. Although the term identification number is used in the description and claims for indicating identity (individual identity or group identity), it is pointed out that this is understood to mean any type of datum with which such an identity can be represented.	Presence detection system for detecting the presence of a portable transmission unit in a compartment of a rack of one or more racks which each have a number of compartments, in which presence detection system each portable unit has a control circuit and a transmission circuit and a register connected to the control circuit for the wireless reception or transmission of a transmission signal which contains an identification number assigned to the portable unit and stored in the register, and also a signalling means which is connected to the control circuit and of which an output signal is dependent on the presence of a portable unit in a compartment and a transmission means which is connected to the control circuit and which is intended for transmitting, depending on the output signal of the signalling means, a report signal which may contain the identification number of the portable unit, and furthermore comprising a detection device having a control circuit to which there are connected a receiving means which is suitable for receiving a report signal originating from a portable unit which is in the vicinity of a rack and a memory in which the control circuit stores, or from which the control circuit removes, a datum about the presence of a portable unit in a compartment depending on report signals received from portable units, characterised in that the signalling means of a portable unit is a detection means which detects the placing of the portable unit in, or its removal from, a compartment, in that, when the portable unit is placed in a compartment, the control circuit of each portable unit controls the transmission means of the portable unit in order to transmit a presence report signal which is a report signal with the identification number of the portable unit, and in that, when a presence report signal is received, the control circuit of the detection device stores a presence datum in a location of the memory assigned to the portable unit having the identification number of the report signal. Presence detection system according to claim 1, characterised in that, when the portable unit is removed from a compartment, the control circuit of each portable unit controls the transmission means of the portable unit in order to transmit an absence report signal, and in that, on receiving an absence report signal from a portable unit from which it has previously received a presence report signal, the control circuit of the detection device removes a presence datum from the memory stored for the portable unit in the memory. Presence detection system according to claim 2, characterised in that the absence report signal transmitted by a portable unit contains the identification number of the portable unit. Presence detection system according to claim 3, characterised in that the presence and absence report signals transmitted by a portable unit differ from one another in a section which characterises the type of report signal and which indicates the presence or absence of the portable unit in a compartment. Presence detection system according to claim 1, characterised in that a portable unit transmits a hold signal while it is present in a compartment after transmitting a presence report signal and in that, if the detection device has not received a hold signal for a predetermined time after receiving a presence report signal from a portable unit, the device removes a presence datum from the memory stored for the portable unit in the memory. Presence detection system according to claim 5, characterised in that the portable unit intermittently transmits the hold signal while it is present in a compartment after transmitting the presence report signal. Presence detection system according to claim 5 or 6, characterised in that the hold signal contains the identification number of the portable unit. Presence detection system according to claim 1, characterised in that each compartment has a detection means for detecting the presence of a portable unit in the compartment, and in that if, after receiving a presence report signal of a portable unit placed in a compartment from the detection means of the compartment, the detection device receives a signal which indicates the absence of the portable unit in the compartment, the detection device removes a presence datum from the memory previously stored for the portable unit. Presence detection system according to claim 1, characterised in that the detection device has a number of transmission means, one for each compartment, in that the control circuit of the detection device transmits a scanning signal via the transmitting means of a compartment from which the device has previously received a presence report signal from a portable unit placed in the compartment, in that each portable unit has a receiving means which is suitable for receiving a scanning signal, in that, on receiving a scanning signal, the control circuit of the portable unit controls the transmitting means of the portable unit in order to transmit a response signal, and in that, if the detection device has not received a response signal for a predetermined time after transmitting a scanning signal via a transmitting means of a compartment from which it has previously received a presence report signal from a portable unit, the device removes a presence datum from the memory stored for the portable unit in the memory. Presence detection system according to claim 1, characterised in that the detection means of a portable unit comprises two detection contacts mounted on the outside of the unit and in that each compartment has a conductor which, when a portable unit is placed in the compartment, short-circuits the detection contacts of the portable unit. Presence detection system according to claim 1 or 8, characterised in that a detection means comprises a switch which switches when a portable unit is placed in, and is removed from, a compartment. Presence detection system according to claim 1 or 8, characterised in that a detection means comprises a circuit which detects a connection between a storage battery or storage battery supply circuit of a portable unit and a storage battery charging source of the rack. Presence detection system according to claim 1, characterised in that the transmitting means of a portable unit is a light-emitting device, and in that the receiving means of the rack is a photosensitive device which is suitable for receiving the light emitted by the light-emitting device of a portable unit in the vicinity of the rack. Presence detection system according to claim 1, characterised in that the transmitting means of a portable unit is an inductive device, and in that the receiving means of a rack is an inductive device which is suitable for receiving a signal emitted by the inductive device of the portable unit in the vicinity of the rack. Presence detection system according to claim 1, characterised in that the transmitting means of a portable unit is suitable for modulating a storage battery charging current which a storage battery charging source of the rack supplies to a portable unit which has been placed in a compartment of the rack, and in that the receiving means of the rack is suitable for detecting a modulation of a storage battery charging current.	ERICSSON RADIO SYSTEMS BV; ERICSSON RADIO SYSTEMS B.V.	VAN DER AREND ADRIANUS GERARDU; ZIJLSTRA GAUKE KLAAS; VAN DER AREND, ADRIANUS GERARDUS ANTONIUS; ZIJLSTRA, GAUKE KLAAS
EP-0489469-B1	489,469	EP	B1	EN	19,960,911	1,992	20,100,220	new	G06K11	G06F3	G06F3	G06F 3/01F, G06F 3/033P4, G06F 3/033P1	A data input device for use with a data processing apparatus and a data processing apparatus provided with such a device	A mouse or trackball comprising a rotationally-symmetrical member (sphere or cylinder). The sphere or cylinder can be braked by means of baking means which receive an appropriate control signal from a data processing apparatus such as a computer. Mechanical feedback to the operator is thus realised. In accordance with the invention, the mouse or trackball also comprises acceleration means which are capable of positively accelerating the sphere or cylinder in a desired direction. The mechanical feedback is thus substantially improved.	FIELD OF THE INVENTION The invention relates to a data input device for use with a data processing apparatus, said device comprising a housing that contains a physical member having at least one axis of rotational symmetry and allowing rotational manipulation around any said axis with respect to said housing, said device having sensing means for upon said manipulation feeding a sensing signal to said data processing apparatus for thereupon moving a display indicium according to an aggregation of said manipulation on a display means, said device having control means for in response to said sensing signal braking said rotational manipulation. One general realization is as a so-called graphical input device, colloquially called mouse or trackball, which is used to enter commands to a data processing computer or the like. The commands could relate to effecting cursor motions, where activating the cursor at a predetermined position would initiate or stop a specific computer action. Various other user interface features of such device have been in use. The physical member may have a single axis of rotational symmetry, such as a cylinder. This can likewise be used in the context of a computer. The data processing apparatus may form part of a user appliance not specifically devoted to the data processing per se, such as a radio broadcast tuner. The rotating cylinder could then activate shifting the actually receiving frequency through a prespecified frequency band. Now, although the principal application of the invention is envisaged with a digital data processing apparatus, it may as well be used with apparatus based on analog signalization, such as the above radio broadcast tuner. For brevity, reference is generally had to a data processing apparatus. For use with a computer, a two-dimensional device of this kind is known from United States Patent Specification 4,868,549 (Affinito et al.) and from IBM Technical Disclosure Bulletin, vol. 32, no. 9B, February 1990, New York US, pages 230-235, 'Mouse ball-actuating device with force and tactile feedback'. The references describe a mouse for use in a video display system, for example a personal computer (PC). The mouse serves for the input of coordinates into the system, thus enabling a cursor to be moved across a display screen of the video system. The mouse housing comprises a sphere which performs a rotary motion when the mouse is moved by hand. Via two wheels which are in mechanical contact with the sphere and which are arranged at an angle of 90° with respect to one another, a motion of the mouse can be detected and measured in an x-direction as well as a y-direction by rotation of the wheels. Motion sensors are coupled to the shafts of the wheels, thus enabling a motion of the wheels to be transferred to the video system. The mouse disclosed in the reference also comprises braking means enabling the braking of the wheel in the x-direction as well in the y-direction during motion of the wheels. The motion of the mouse can thus be hampered in a given direction by at least one electromagnet or by introduction of a friction which may be greater or smaller in a given direction. In addition to a customary visual feedback (for example, the position of a cursor on an image display screen), the operator also experiences a resistive mechanical feedback by the frictional force on the mouse. The inventors of the present invention have discovered that the feedback effected on the rotational manipulation of the device can be made more sophisticated, thereby allowing a wider range of useful applications. SUMMARY TO THE INVENTIONAmongst other things it is an object of the present invention to increase the range of feedback functionality, so that the machine-generated force can effect a richer tactility to the data input device. A data imput device according to a first aspect of the invention is defined in appended claim 1. The positive and negative accelerations may have a fixed value each, such as +A and -B, respectively wherein A and B could be mutually equal or, alternatively, differ from each other. Also, the range of values may be greater. The effective value of the acceleration can depend on where on the screen the indicium, usually the cursor, is actually located. In this respect, the present invention differs from such realizations in remote handling or robotry, where the description of the remote object to be handled would control the feedback. Also, the invention differs from realization pertaining to a data input device on the basis of a joystick or the like. With such joystick, a force extended on the joystick will move it away from a home position, and the physical offset of the joystick so produced is integrated in time to attain the intended movement of an on-screen indicium. Feedback there would be effected as a force exerted on the joystick. In the present invention, any motion of the rotationally symmetric member translates directly to a movement of the on-screen indicium. Therefore, the force is directly dependent on the on-screen position, and in fact, a non-zero force may be present when the position of the indicium is stationary. It would be possible that the indicium be propelled by the system, so that the system would apply kinetic energy to the physical member. This would be unthinkable in the case of a joystick. Generally, the kinematic functionality of a joystick is widely different from that of mouse/trackball devices. Another known document, NTIS TECH NOTES, May 1990, SPRINGFIELD, VA US, page 413, B.HANNAH et al.: 'Force-Feedback Cursor Control.', discloses a force-feedback hand-held controller which is used to move a cursor on a screen. The controller, whose structure is not disclosed, is inspired from controllers developed for controlling remote manipulators on robots. Positive and negative force feedbacks according to the position of the cursor are apparently provided to the user's hand. However, unlike a mouse, the controller is moved in a three-dimensional space rather just than in a plane, which apparently means that the cursor is not moved according to the rotational manipulation of a physical member with respect to a surrounding housing as in the invention. Advantageously said positive and negative accelerations derive from a potential field mapped on said display means. The potential field can be mapped as a bit pattern or as a set of potential functions. This would allow to realize preferred positions or regions on the display with respect to other positions or regions. The potential may be determined for every pixel or for a subset of all pixels. In the latter case, an operator bit pattern may access the so defined pixels for on the basis of their respective potentials and positions relative to the position of the indicium, calculate an instantaneous sign and value of the acceleration. It would be clear that, for example, motion in an x-direction can now be combined with an acceleration in a y-direction. Advantageously, said positive and negative accelerations are at least codetermined by an actual velocity of said rotational manipulation. An example would be that during fast motion, the generation of the accelerations is suspended. Only during slow motion, they would be present. This would guide the human user during access of a displayed feature that has fine granularity, for so improving effective dexterity. Gross movements would not need such assistance. Moreover, the machine generated force and the operator generated force are now mutually uncoupled. Advantageously said sensing means allow for detecting an actual total force on said member in at least one coordinate direction. This feature would greatly improve the flexibility of the feedback mechanism. The detection of such actual total force is by itself a conventional embodiment. Advantageously said sensing means allow for detecting an instantaneous velocity of said member with respect to the housing. Likewise, this feature improves verbability of the data input device and its use. Velocity measurement can be realized in a variety of ways. Advantageously said accelerations are multivalued. They may have a finite set of values, or even have a continuous range of values. Sometimes a D/A conversion is necessary. Advantageously, said device is provided with assigning means for assigning to the member a predetermined virtual rotational inertia. Such inertia is represented by an acceleration that adds to the physical inertia. It has proven to be an excellent device for data input, for training, or for testing operators as to their capacities on a motoric level. The inertia need not be time-uniform and/or spatially uniform. A particular advantage of virtual inertia that is greater than actual physical inertia is that the latter now could be made as small as technically feasible. This may be used to construct the physical member as a lightweight element, making it better suitable for portable and/or miniature devices. Another embodiment of a device in accordance with the invention is characterized in that the device comprises at least one electromechanical motor for implementing the braking means as well as the acceleration means. The braking means and the acceleration means can be simply implemented by way of electromechanical motors. The motor can be accelerated by application of an excitation current, but it is also possible for the motor to be braked. This depends on the excitation current itself (for example, a positive or negative excitation current), but also on the instantaneous direction of rotation of the motor. The invention also relates to a data processing apparatus comprising display means and a data input device according to the foregoing. Various other aspects of the invention are recited in dependent Claims. BRIEF DESCRIPTION OF THE DRAWINGSThe invention will be described hereinafter with respect to a preferred embodiment, thereby also disclosing its various effects and advantages, with reference to the drawing; therein Fig. 1 shows a prior art device, Fig. 2 shows an embodiment of a device in accordance with the invention, Fig. 3 shows a further embodiment of a device in accordance with the invention, Fig. 4 shows a diagram in accordance with the invention in which the acceleration force is shown as a function of a position coordinate, and Fig. 5 shows an example of an image on a display screen, together with a path along which the member of the device will experience more or less force. DETAILED DESCRIPTION OF A PREFERRED EMBODIMENTFig. 1 shows a prior art device. The device comprises a rotationally-symmetrical member (sphere) 10 whereto wheels 11 and 12 are mechanically coupled by friction. A shaft 23 is attached to the wheel 11 and a position sensor (YPOS) 14 and a brake (YBRAKE) 16 are coupled to said shaft. The position sensor 14 is connected, via a data line 20, to a processor 17 in order to supply the processor with a y coordinate of the sphere 10. It is also possible to supply the processor 17 with a time-variation quantity of the y coordinate instead of the absolute y coordinate. The brake 16 is connected, via a data line 21, to the processor 17 so that the brake 16 can be controlled by the processor. To the wheel 12 there is attached a shaft 22 whereto a position sensor (XPOS) 13 and a brake (XBRAKE) 15 are coupled. Via a data line 18, the position sensor 13 is also connected to the processor 17 in order to supply the processor with in this case the x coordinate or a time-variation of the x coordinate of the sphere 10. The brake 15 is connected to the processor 17 via a data line 19 so that the brake 15 can also be controlled by the processor. As alternative to the construction shown, various other realizations have been in use that would also lend themselves for applying the improvements of the present invention. The data lines 18 to 21 are in principle capable of carrying analog or digital signals. The coupling to the processor 17 will usually be digital, so that the processor 17 or the position sensors 13 and 14 and the brakes 15 and 16 could comprise analog-to-digital (A/D) converters or digital-to-analog (D/A) converters should the components 13, 14, 15 and 16 operate on an analog basis. For brevity, the internal structure of the processor and the attached display have not been shown. Also, the housing of the device, that could make it a trackball device (sphere on its upper side extending slightly) or, alternatively, a mouse device (sphere slightly extending on the lower side for being brought in frictional contact with a surface) is not shown for brevity. The device shown in Fig. 1 operates as follows. During a rotation of the sphere, either the wheel 11 or the wheel 12 or the wheel 11 as well as the wheel 12 will also rotate due to the friction between the wheels and the sphere. A rotary motion of one of the shafts 22 and 23 is detected by the position sensors 13 and 14, respectively, and applied to the processor 17. On the basis of this data the processor can determine the position of the sphere and, on the basis thereof, it can determine whether the brakes 14 and/or 15 are capable of exerting a braking effect on the sphere when the sphere in motion. In the rest state of the sphere, the frictional force will be equal (and hence proportional) to any operator force exerted on the sphere. This is a substantial drawback of such a device because, when the sphere is actually in an xy position which is undesirable, the operator receives a frictional force feedback only if the sphere is in motion. Fig. 2 shows an embodiment of a device in accordance with the invention. The device comprises a number of components which correspond to components of the device shown in Fig. 1, i.e a sphere 30, wheels 31 and 32, position sensors 33 and 34, brakes 35 and 36, a processor 37, shafts 46 and 47, and data lines 38, 39, 41 and 42. In accordance with the invention, the device shown in Fig. 2 also comprises the acceleration means 45 (XACC) and 44 (YACC) and the data lines 40 and 43. Under the control of the processor 17, the shaft 46 and/or 47 can be accelerated by excitation of the components 45 and/or 44. This means that a force can be exerted on the sphere also during standstill of the sphere. As a result, the operator of the device may experience a distinct force feedback also in the rest state of the sphere. It is even possible for the sphere from the rest state to start rotating in a predetermined direction after having been released by the operator. Such a mechanical feedback by means of brakes and acceleration means, therefore, is not only passive as the device in Fig. 1, but also active. As a result, an operator of a device will receive a substantially improved mechanical feedback so that the total feedback, determined by the feedback via the display screen and the mechanical feedback to the operator, will also be improved. Fig. 3 shows a further embodiment of a device in accordance with the invention. The device comprises a number of components which correspond to components of the device shown in Fig. 2, i.e. a sphere 50, wheels 51 and 52, position sensors 53 and 54, a processor 57, shafts 62 and 63, and data lines 58 and 60. The device shown in Fig. 3, however, differs from the device shown in Fig. 2 in that the functions of the brake 35 (XBRAKE) and the acceleration means 45 (XACC) and the brake 36 (YBRAKE) and the acceleration means 44 (YACC) are taken over by the motor 55 (XMOTOR) and the motor 56 (YMOTOR), respectively. The motors 55 and 56 are controlled by the processor 57 via the data lines 59 and 61, respectively. Control via these data lines for the relevant motor 55 or 56 may imply on the one hand that the relevant motor is braked, but may also imply that the relevant motor is accelerated. Thus, both braking and accelerating can be implemented by means of a single component 55 (XMOTOR) or 56 (YMOTOR), respectively. In the above Figs. 1 to 3 a sphere is shown as an example of a rotationally-symmetrical member. The sphere allows for motion in two directions, i.e. an x-direction and a y-direction perpendicular thereto. However, it is also possible to choose a cylinder instead of a sphere. Contrary to a sphere, a cylinder has only one degree of freedom, i.e. a variation is possible exclusively in the x-direction or exclusively in the y-direction. This may suffice for given applications. A cylinder offers the advantage that only a single position sensor, a single brake and a single acceleration element are required, the latter two being again combinable in a single element. Moreover, no coupling wheel would be necessary inasmuch as the cylinder could be mounted directly on an axis. Fig. 4 shows a diagram in accordance with the invention illustrating the acceleration force as a function of a position coordinate (x). For simplicity, this example concerns only the x-coordinate, but a control may also be present for the y-direction. The x-coordinate is plotted in the horizontal direction and the force acting on the sphere in the device shown in the Figs. 2 and 3 is plotted in the vertical direction. As appears from the Figure, no force acts on the sphere in the x-path between X2 and X3. In practice this may mean that the sphere is positioned in a desirable area, which can be interpreted as the cursor being situated in a desired position on the image display screen or within a desired position area. Along the path between X1 and X2 the sphere experiences an acceleration force which may vary according to the curves 70, 71 or 72. The shape of the curves is merely given by way of example and it will be evident that in principle any other shape is feasible because this task is performed by the processor. Such shapes could therefore be according to a straight line, parabola, convex as well as concave curves, curves in the shape of an S, and they could even have corners so that a broken line occurs. Moreover, the amount of force exerted may be small, so as to make the user feel small preferences. Alternatively, the force may be higher, even to such a degree that particular positions would appear forbidden . For the three curves the acceleration force F in the x-direction x < X2 is positive and is negative in the x-direction x > X4. In the present example this means that the sphere experiences a positive force which is directed in the positive x-direction when the sphere is situated in the x-path to the left from X2. The sphere thus experiences an accelerating force. The maximum force amounts to F1 and can be determined as desired or as can be technically simply realised. The sphere experiences a force directed in the negative x-direction if the sphere is situated in the x-path to the right of X3. This means that the sphere is braked during motion to the right and that it is pushed back when in the rest state. The maximum negative force amounts to F2. This value can again be adjusted as desired. It would be obvious that integrating the x-dependent force shown in Fig. 4 with respect to the x-coordinate produces an x-dependent potential field. Such potential field may also be two-dimensional. It may be static or time-dependent as determined by computer control. In other situations, the force cannot be described as being governed by a single potential field, for example, in that it is controlled by actual cursor velocity, or by a history of the cursor movement, hysteresis, etcetera. Fig. 5 shows an example of an image 80 on a display screen, together with paths along which the member of the device will experience more or less force. The shaded area 81 is an area in which the presence of the cursor (sphere) is not desired, i.e. when the sphere is present in the area 81 it will experience a force in the direction of the area 82. The area 82 is an area in which the presence of the sphere is desired, i.e. the cursor (sphere) will not experience a force in this area. For simplicity, the force exerted on the device is determined only by the position where the cursor leaves the area 82 and then remains constant so as to push the cursor back, in either one of the +x, -x, +y, -y, directions, respectively. In a more complicated set-up, the force derives from a potential field, the potential generally increasing with the distance to the desired area. By way of example, a start is made at S. As an indication for the x and y position of the sphere a cursor can be displayed on the image 80. Thus, the operator receives a visual feedback as regards the actual x and y position of the member (the sphere). The cursor can have any reasonable shape, for example an arrow or a dash. Now, the cursor is moved in the positive x-direction until it reaches the point P1. Along this path the sphere of the device will not experience an opposing (braking) or stimulating (accelerating) force, because the cursor (and hence also the sphere) is situated in the desired area. At the point P1 the sphere will experience an opposing force if the operator attempts to move the sphere (cursor) beyond the point P1 in the x-direction. In accordance with the invention, this opposing fee force consists not only of a braking force during movement of the sphere in the positive x-direction, but also of an accelerating force. This means that if the sphere (cursor) were to be situated to the right of P1, the sphere would experience an accelerating force in the negative x-direction. The sphere does not experience a force along the path 83 between P1 and P2, because it moves on the desired area. When it arrives at the point P2, motion in the positive y-direction will be impeded on the one hand by a braking force from the braking means during motion of the sphere in the positive y-direction, and on the one hand by an accelerating force in the negative y-direction. Along the path 83 between the points P2 and P3 the sphere will not experience any force either. Furthermore, there is shown the case when the operator has the cursor leave the desired area at point P3. All along the trajectory between points P3 and P5, there is effected an accelerating force in the negative y-direction, as has been symbolized at point P4 by arrow F. At the boundary between the desired area 82 and the undesired area 81, the force increases from a value zero to a value unequal to zero. The variation of the force as a function of the x-coordinate or the y-coordinate can be as shown in Fig. 4. The point P1 in Fig. 5 then corresponds, for example to the x-coordinate X3 in Fig. 4. When the sphere is moved in the positive direction at the point P1, it will experience a force which will point in the direction of the negative x-direction as can be seen in Fig. 4 for x > X3. Alternatively, near to the border of undesired area 81 the force may increase according to one of the other curves 70 and 71 (Fig. 4). It may also be that the braking and accelerating forces in accordance with the invention are not exclusively dependent on the instantaneous x,y position of the sphere or cursor. These forces may also be determined by the instantaneous speed of the sphere. Thus, a kind of mass or rotational inertia can be simulated; this could be useful for various applications. The control signals required can be simply generated by the processor by way of an appropriate arithmetic algorithm, because the processor can determine the position coordinates of the sphere, and also its speed in the x- and y-directions, on the basis of position sensors. In accordance with the invention it is also possible to determine the speed of the sphere by means of additional speed sensors. Generally, a better measuring accuracy can thus be obtained. In accordance with the invention it is also possible to provide the device with a force sensor for detecting the total force acting on the member. On the basis of this information the data processing apparatus can drive the braking means and/or the acceleration means more or less. Because the magnitude of the drive is known, the operator force exerted by the operator can be simply deduced. On the basis of the deduced operator force it is subsequently possible to change the desired drive of the braking means and/or the acceleration means. To those skilled in the art it will be evident that the above example is given merely to illustrate the invention. In addition to the possibility of following a desired path, the use of the invention in accessing a menu is also feasible. The sphere (cursor) is then quasi-guided to a desired selection box. It will also be evident that the acceleration means in accordance with the invention may be adjusted so that a sphere can start its own motion from standstill when the sphere is present in an inhibited area, but in that case, the acceleration forces should be adjusted that any oscillatory motion should be damped. The device in accordance with the invention preferably comprises a trackball. A trackball is a well-known device in which a sphere (ball) is retained in a holder. Sometimes a trackball is to be preferred over a so-called mouse, notably when the available desk surface is only limited, because the mouse need be moved across a surface. A trackball, however, occupies a steady position and can also be integrated, for example in a keyboard. When a trackball is used the operator often experiences difficulty in drawing straight lines on the display screen by rotation of the sphere. This is because the drawing of a straight line implies linear driving of the sphere. In practice, however, a trackball is usually loosely operated by the operator, the wrist of the operator's hand resting on a solid base, for example a desk top. Motions of the operator's hand or fingers, however, do not describe a straight line in such cases but rather an approximation of a circular curve. In such circumstances, the invention could be used by making horizontal motion on the screen preferred to vertical motion, for so allowing easy pointing to successive words on a single line of text. This would mean that each line of text has a preferred area in the form of a narrow strip. Contiguous lines are separated by strips of undesired area that would cost some extra force to traverse. The magnitude of such force could be made adjustable. Also, the processor itself could assign those preferred/undesired strips exclusively to filled text area. Various other layouts of preferred/undesired areas would be feasible. They could also be shown to a user by appropriate shading or colours.	A data input device for use with a data processing apparatus, said device comprising a housing that contains a physical member (30, 50) having at least one axis of rotational symmetry and allowing rotational manipulation by a user around any of said at least one axis with respect to said housing, said device having sensing means (33, 34, 53, 54) for upon said manipulation feeding a sensing signal to said data processing apparatus for thereupon moving a display indicium according to an aggregation of said manipulations on a display means, said device having control means (35, 36) for in response to said sensing signal braking said rotational manipulation, characterized in that said control means control both positive and negative accelerations with respect to said rotational manipulation as governed by said data processing apparatus according to a position signal of said display indicium on said display means. A device as claimed in Claim 1, wherein said positive and negative accelerations derive from a potential field mapped on said display means. A device as claimed in Claim 1 or 2, wherein said positive and negative accelerations are at least codetermined by an actual velocity of said rotational manipulation. A device as claimed in Claim 1, 2 or 3, wherein said physical member is spherical. A device as claimed in any of Claims 1 to 4, wherein said sensing means allow for detecting an actual total force on said member in at least one coordinate direction. A device as claimed in any of Claims 1 to 5, wherein said sensing means allow for detecting an instantaneous velocity of said member with respect to the housing. A device as claimed in any of Claims 1 to 6, wherein said accelerations are multivalued. A device as claimed in any of Claims 1 to 7, provided with assigning means for assigning to the member a predetermined virtual rotational inertia. A device as claimed in any of Claims 1 to 8, realized as a trackball device. A device as claimed in any of Claims 1 to 8, realized as a mouse device. A device as claimed in any of Claims 1 to 10, characterized in that the device comprises at least one electromechanical motor (55, 56) for providing the positive as well as the negative accelerations. A data processing apparatus comprising display means and a data input device as claimed in any of Claims 1 to 10.	KONINKL PHILIPS ELECTRONICS NV; KONINKLIJKE PHILIPS ELECTRONICS N.V.	ENGEL FREDERICK LOUIS; HAAKMA REINDER; ITEGEM JOZEPH PRUDENT M VAN; ENGEL, FREDERICK LOUIS; HAAKMA, REINDER; VAN ITEGEM, JOZEPH PRUDENT MARIA
EP-0489471-B1	489,471	EP	B1	EN	19,950,913	1,992	20,100,220	new	G06M9	null	G06M9, G06M1	G06M 1/10B, G06M 9/00	Device for counting a number of flat objects, such as letters, forming a stack	Device for counting essentially flat objects, such as letters, in the stacked state. The object edges in a side plane of the stack form, when illuminated, a pattern of light and dark bars which can be detected with the aid of bar code reader 30 known per se. The device comprises a stack bed 20 formed by two mutually perpendicular support plates 23 and 24 which are open upwards for receiving a stack 21 of letters 22. The letters 22 are all placed in the base with one letter edge against the supporting face 23, so that said bar pattern is visible in a strip-type opening 27. The bar code reader 30, mounted in a holder 29 can be moved with its scanning head 31 along the letter edges visible in the strip-type opening 27 over the entire length of the stack by means of a guide rod 28. A signal corresponding to the bar code is presented via a connection line 32 to analysis means and the number of letters in the stack derived therefrom is displayed on a number display 34. Reset means, which can be operated by means of a reset button 35, offer the possibility of counting stacks separately or cumulatively.	A. Background of the invention1. Field of the inventionThe invention is in the field of counting objects. More particularly, the invention relates to a device for counting essentially flat objects, such as letters, forming a stack, comprising: a stack base provided with a flat section in which an at least strip-type opening is cut out which extends over the entire length of the stack base, in which stack base the objects can each be positioned with an object side essentially resting against said flat section, illumination means for illuminating, by a beam, the stack in said opening, pick-up means for picking up a reflection signal from the stack over the entire length in said opening, analysis means for analysing the reflection signal and deriving therefrom the number of objects in the stack, presentation means for presenting the number derived by the analysis means. 2. Prior artSenders of items of mail have the facility of presenting large numbers of items of mail in large batches to the postal service. It is usual for special rates to apply to such batch mail. On presentation, the presenter should state the numbers and the weight classes of the batch mail presented. Since carrying out counts is very labour-intensive, the stated numbers and weight classes have until now been monitored only by random tests. A more intensive check has, however, been found to be necessary. Batch mail can in general be divided into two groups, viz. a first group consisting of items of mail having essentially the same weight and the same dimensions, and a second group consisting of items of mail of differing weight and/or differing dimensions. Batch post of the first group can in general be quantified fairly simply and with sufficient accuracy in terms of number by means of weighing. The determination of the number of items of mail in a batch of the second group can be carried out with sufficient accuracy only by counting. Such counting has until now been carried out by hand and is consequently very time-consuming. There is therefore a need for a new device with which such counting can be carried out much more simply and rapidly while retaining a sufficient degree of accuracy. Such batch mail is usually delivered in reasonably ordered bundled stacks. The letters of the second group differ quite a lot in relation to dimensions but are, however, generally reasonably flat objects having at least one straight side. Such letters can be ordered in a stack so that said straight sides of all the letters lie essentially in one flat plane. In addition, such letters do not have a rectangular cross section at said straight side but a cross section usually tapering to a point, so that, at the side of said flat plane, the stack has an essentially serrated or ribbed cross section, each rib or serration representing a letter. If such a stack is then illuminated at the side of said flat plane, a pattern of alternating light and dark bars becomes visible. By counting, for example, the number of light bars in the said pattern, the number of letters in the stack can then be determined. Such a counting principle for counting the number of objects in a stack of usually uniform sheet-type objects is known per se, for example, from references [1], [2], [3] and [4] mentioned under C. (See below). In particular, reference [1] shows solutions to the problem for cases where high speed and high reliability are needed and difficult materials are involved, such as thin paper, glass and metals with crystalline or granular edge characteristics. In those cases either complicated measures are needed to maximise band width of the sensor used in the application, or special arrangements of the light source, lens elements and sensor have to be used. Since the applications described in said publications are fairly specific, even if it were commercially obtainable as such, the equipment with which the counting technique can be carried out has the drawback that it could nevertheless only be used for the counting problem described above after the necessary adaptations and extensive tests. B. Summary of the inventionThe invention meets the abovementioned requirement. For this purpose, it provides a novel device for counting a number of essentially flat objects, such as letters, forming a stack, in which use is made of the counting principle known from the technology cited above. A device according to the invention is characterised in that the illlumination means and the pick-up means are together formed by bar code scanning means known per se. The object of the invention is to provide such a device in a preferred embodiment which does not have the drawback mentioned. In practice, it has in fact been found that the bar-type pattern indicated above, which is visible on illuminating the stack of letters at the side of said plane can be treated as a bar code, which is currently used in all kinds of forms, for example for identifying articles for sale, and for which all kinds of scanners are now commercially available in order to be able to read such codes. In particular, if a scanner with a fixed scanning beam is used, the invention offers a simple and cheap device with which the number of objects in the stack can be counted rapidly and with low labour intensity. C. References[1]US-A-3 813 523 (MOHAN et al.); [2]US-A-3 964 041 (HINDS); [3]US-A-3 835 306 (BILLS et al.); [4]US-A-3 422 274 (COAN); [5]Solid State Scan Modules, Specifications Part No. 1188 DQ, Symbol Technologies Inc. 1987; [6]LP 1500 Series Hand-held contact-scanning wands, Specifications Part No. 887 GA, Symbol Technologies Inc. 1987. [7]F30 Fixed Position Bar Code Reader, DATALOGIC S.p.A., Bologna, Italy, Febr. 1989, (BC-041 81100019). D. Brief description of the drawingThe invention will be explained in greater detail by means of a description of an exemplary embodiment, reference being made to a drawing, wherein: Figure 1:shows an outline diagram of a device according to the invention; Figure 2:shows a view of a preferred embodiment of the device according to the invention. E. Description of an exemplary embodimentThe principle of the invention can be applied to any type of essentially flat objects which can be positioned in a stack in such a way that at least some of their object edges form a common, essentially flat side plane of the stack. However, for the sake of convenience, the description will be limited below to letters which have the usual, essentially rectangular appearance but which may vary, however, in dimensions such as thickness. In order not to complicate the drawing unnecessarily, however, the letters in the figures have in fact been shown with uniform dimensions. Figure 1 shows an outline diagram of a device for counting a number of letters in the stacked state. In this figure, a part of a stack 1 of letters 2 has been drawn in cross section. The stack comprises N letters starting from a foremost letter 2′ up to and including the rearmost letter 2″. In the stacked position, the N letters 2 each form, with one of their letter edges 3, an essentially flat side plane 4 (broken dotted line) of the stack over the entire length of the stack, that is to say starting from the foremost letter 2′ up to and including the rearmost letter 2″. A scanner 5 scans the stack 1 in the side plane 4 at least over the entire length by means of a scanning beam 6, for example laser light, and picks up a reflection signal 7 therefrom. Said reflection signal will in general fluctuate in light intensity, the maxima being the consequence of strong reflection at the letter edges 3 essentially in the side plane 4, while the minima are caused by absorption and large lateral scattering in the space between the consecutive letter edges 3. The scanner 5 converts the reflection signal 7 into a corresponding electrical signal which is then presented to a signal processor 8. The signal processor 8 processes the reflection signal to a form suitable for further analysis, for example a digital form, and presents it to a signal analyser 9. Said analyser determines, for example by counting the number of maxima in the processed reflection signal, the number N of letters in the stack 1. Said number N is then transmitted to, for example, a number display 10 for visually showing the number N. In principle, any type of pick-up having an associated light source and which picks up a reflection signal from the side plane 4 of the stack which is then processed and analysed can be chosen instead of said scanner 5 (with associated signal processor 8). Thus, the pick-up may be a video camera which, for example, picks up an image of the entire side plane 4 of the stack 1 from which a part is separated by an associated video signal processor and is processed in such a way that it is comparable with the abovementioned processed reflection signal. This would, however, be an expensive design of the invention. Specifically, it has been found experimentally that a side plane 4 of a stack in which the letters are positioned as described above can be regarded as a bar code pattern which can be scanned with the standard, commercially available scanning equipment. Such scanning equipment comprises in fact the functions of the scanner 5 and the processor 8 taken together or embodied in a scanning part and a processing part. A bar code scanned by the scanning part is usually delivered by the processor part as a digital signal for further processing. The number, for example, of light bars in a pattern can therefore simply be counted by counting all the 'zero'/'one' junctions or all the 'one'/'zero' junctions in the digital signal. A microprocessor can easily be programmed for this purpose. There are two types of scanning apparatuses available commercially; one having a movable scanning beam and one having a fixed scanning beam. A scanner having a movable scanning beam is known, for example, from reference [5] mentioned under C. Said known scanner has a horizontal 90° beam sweep, with which, in theory a stack of letters having a length of up to 20 cm could be scanned starting from a fixed position, for example at a distance of 10 cm. However, it has been found that only stacks containing approximately 20 letters can be counted with sufficient accuracy. This is the consequence of the fact that more to the side, viewed from the centre of the sweeping beam, the scanning signal is always scattered more at the letter edges, so that the maxima are increasingly difficult to distinguish from the minima in the reflection signal received therefrom. This limitation can be eliminated by using a scanner having a fixed scanning beam and setting it in relative movement along the side plane 4 of the stack 1 during the scanning. This embodiment is explained in greater detail below with reference to Figure 2. Scanners having a fixed scanning beam are known, for example, from references [6] and [7]. Figure 2 shows a view of a device according to a preferred embodiment. A stacking base 20 for receiving a stack 21 of letters 22 consists of two supporting plates 23 and 24 which are supported on either side by two vertical stands 25 and 26. The stacking plates 23 and 24 have an essentially orthogonal position with respect to each other and in the upward direction leave a space free which has a right-angled cross section for receiving the stack 21. In the stack 21, each letter 22 is arranged as much as possible in accordance with such a right-angled cross section, so that the letter edges of the letter touch the supporting plates 23 and 24 in doing so. In the downward direction, the supporting plates leave a narrow strip 27 free, at least in the plane of one of the supporting plates, in this case supporting plate 23, through which a fraction of the letter edges of the letters 22 in the stack 21 is visible. The stands 25 and 26 also support a guide rod 28 which is fitted so as to run parallel to the narrow strip 27 under the stacking base 20. Fitted on said guide rod 28 is a holder 29 which can be moved along the guide rod at an otherwise fixed spatial orientation. A pen-type scanner 30 is incorporated so as to be adjustable in its longitudinal direction in the holder 29. The scanner has a scanning head 31 which is adjusted at a fixed distance from the letter edges of the letters 22 visible in the strip 27. The scanner 30 has a flexible connecting line 32 for supply and signal transmission to a small box 33 in which a microprocessor (not shown) and a visual number display 34, for example, having three figures as shown. The small box 33 may furthermore be provided with a reset button 35 with which the display can be set to zero. The signal connection line 32 has at least a length which makes it possible for the holder 29 with the scanner 30 to be displaceable over the entire length of the guide rod between the two stands 25 and 26. A stack placed in the stacking base 21 can be supported on either side by means of displaceable side supports (not shown). The device is used as follows. A stack 21 of letters 22 is placed, for example by hand, in the stacking base 20, as shown in Figure 2. The stack is, if necessary, shaken a little by hand in order to ensure that the letter edges of the letters 22 rest as well as possible against the supporting face 23 at the side where the scanner 30 is situated. The holder 29 with the scanner 30 is set to a starting position if this has not already been assumed. A starting position for the scanner is any position in which the scanner 30 is situated either between the plane of the stand 25 and the foremost letter 22′ in the stack or between the last letter 22″ in the stack and the plane of the stand 26. The holder 29 is then displaced from a starting position along the guide rod 28 from one side of the stack, past the stack to a final position at the other side of the stack, in which process the scanner 30 scans the letter edges of the stack in the strip 27 during the displacement and picks up a reflection signal and processes it to a digital signal that is then delivered via the connection line 32 to the microprocessor in the small box 33. The microprocessor is programmed in such a way that, for example, all the 'zero'/'one' junctions in the digital signal are counted and then this number is presented by the display 34, after which said number can be read off by operating staff. The counted stack can then be replaced by a new stack which is again scanned in the manner described. The microprocessor may, moreover, be so programmed that, if the display 34 is not reset with the reset button 35 when an already counted stack is replaced by a fresh stack still to be counted, the number of counted letters in the new stack is added to the number of letters counted until that time in one or more consecutive, already counted stacks. This has the advantage that the number of letters can be determined in a simple way in stacks which are too extensive to be counted in one go. Obviously, the displacement of the holder 29 along the guide rod 28 can also be brought about with the aid of electromechanical drive means known per se.	Device for counting a number of essentially flat objects (2;22), such as letters, forming a stack (1;21), comprising: a stack base (20) provided with a flat section (4;23) in which an at least strip-type opening (27) is cut out which extends over the entire length of the stack base, in which stack base the objects can each be positioned with an object side essentially resting against said flat section, illumination means for illuminating, by a beam (6), the stack in said opening, pick-up means (5,8;30) for picking up a reflection signal (7) from the stack over the entire length in said opening, analysis means (9;33) for analysing the reflection signal and deriving therefrom the number of objects in the stack, presentation means (10;34) for presenting the number derived by the analysis means, characterised in that the illumination means and the pick-up means are together formed by bar code scanning means known per se. Device according to Claim 1, characterised in that the scanning means consist of a scanner having a fixed scanning beam and in that guide means (28) are provided along which the scanner can be passed along the stack in said opening, from a preset position. Device according to Claim 1, characterised in that the scanning means consist of a scanner having a sweeping scanning beam which is positioned at a fixed preset distance from the said opening.	NEDERLAND PTT; KONINKLIJKE PTT NEDERLAND N.V.	DEN DUNNEN THIERRI; POIESZ ALBERT JACOB GERARD; DEN DUNNEN, THIERRI; POIESZ, ALBERT JACOB GERARD
EP-0489472-B1	489,472	EP	B1	EN	19,971,029	1,992	20,100,220	new	C07C51	null	C07C51, B01J31, C07C69, C07C53, C07C67, C07B61	C07C 67/38, C07C 51/14	Carbonylation process and catalyst composition	A process for the carbonylation of an olefinically or acetylenically unsaturated compound with carbon monoxide in the presence of a nucleophilic compound having a removable hydrogen atom and a catalyst system comprising a) a source of palladium, b) a phosphine of general formula PR¹R²R³, wherein R¹, R² and R³ independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, and c) a source of anions being the conjugated base of an acid having a pKa < 3, characterized in that the reaction medium at least initially is a multi-phase liquid reaction medium, and that the catalyst system comprises a component b) or c) having an amphiphatic structure, and catalyst compositions particularly suitable for said process.	The invention relates to a process for the carbonylation of olefinically or acetylenically unsaturated compounds, and more in particular to such a process conducted in the presence of a nucleophilic compound having one or more removable hydrogen atoms, and a palladium catalyst, and to certain catalyst compositions particularly suited to said process. Processes for the carbonylation of olefinically unsaturated compounds, hereinafter referred to as olefins, or of acetylenically unsaturated compounds, hereinafter referred to as acetylenes, with carbon monoxide in the presence of a nucleophilic compound containing one or more removable hydrogen atoms, such as for instance an alcohol or a carboxylic acid, and a palladium catalyst are known, and have been described e.g. in EP 0055875, 0106379, 0168876 and 0186228, as are the products which may be prepared by such a process. Generally such processes are conducted by introducing the various reactants into the reactor and allowing the reaction to proceed under the desired reaction conditions. With some of these processes the presence in the reaction medium of a suitable solvent was found to have a beneficial effect, e.g. by promoting the solubility and/or miscibility of the reactants and/or by reducing the viscosity of the reaction medium; the desirability for a solvent to be present as well as the nature of such a solvent being largely determined by the nature of the reactants. Sometimes the reaction medium of such a process comprises two immiscible liquid phases. This can for instance be the case with the preparation of the full esters of polyhydric alcohols via the carbonylation of olefins in the presence of such a polyhydric alcohol, as the latter are frequently solid compounds having a high melting point and moreover do not dissolve readily or at all in the olefin reactant. Such polyhydric alcohols may then be employed as a solution in a highly polar solvent, which solutions generally result in the formation of a two-phase liquid reaction medium with the olefin reactant. Another example of immiscible reactants, is the use of a very polar liquid reactant, such as a polyethylene glycol or water, which would normally result in a two-phase medium when combined with most of the olefins or acetylenes. On the other hand it is also possible that the two-phase liquid reaction medium has been intentionally created. This would for instance be the case when a liquid compound wherein only one the reactants will dissolve is added to the reaction medium, this non-mutual solvent being present to facilitate the catalyst retrieval at the end of the reaction. The nature of said solvent being governed by the nature of the catalyst system as well as by that of the reaction product. It has been observed that the presence of a two-phase liquid reaction medium in a process as described hereinbefore, could however result in a reduction of the reaction rate as well as in the degree of conversion, and occasionally in hardly any reaction at all. In UK Patent Application GB 2 023 589 A a process has been described for the continuous preparation of the full esters of mono- or polypentaerythritol via the carbonylation of olefins having at least 4 carbon atoms, in the presence of such a polyhydric alcohol and a cobalt-based catalyst, and wherein the formation of an inhomogeneous reaction medium can be avoided by a phased addition of the olefin reactant, i.e. initially adding only a part of the olefin reactant to the reactor together with all the polyol and catalyst, and subsequently adding the residual amount of olefin to a middle section of the reactor. A general disadvantage of said carbonylation process is the use of a cobalt carbonyl catalyst, which catalyst is generally known to have a lower activity and selectivity than a palladium-based catalyst as described e.g. in EP 0106379, and will moreover require more severe reaction conditions, i.e. higher temperatures and/or pressures. A further disadvantage envisaged is, that the relative amounts of olefinic material to be introduced at the beginning and in the middle section of the reactor will vary strongly with the molecular weight of the olefin and the nature of the polyhydric alcohol, and will thus have to be determined separately for each combination of reactants. Finally it does not solve the problem when the two-phase liquid reaction medium has been created intentionally. US-A-3,530,155 relates to hydrocarboxylation of olefins by contacting the olefin with a catalyst comprising a platinum or palladium complex with an aromatic phosphine, water and carbon monoxide. The phosphines described to be suitable are arylphosphines or mixed alkylarylphosphines, optionally substituted with an alkyl or chloro group. The problems inherent to a multi-phase liquid reaction medium have not been mentioned. The problem underlying the present invention is developing a process for the carbonylation of olefins or acetylenes in the presence of a nucleophilic compound having one or more removable hydrogen atoms, wherein the combination of said reactants or the presence of one or more selected solvents results in the formation of a reaction medium having > 1 liquid phase, hereinafter referred to as multi-phase reaction medium, and which process does not suffer from one or more of the disadvantages as mentioned hereinbefore. As a result of extensive research and experimentation a process was developed which enables the carbonylation of olefins or acetylenes with carbon monoxide in the presence of an organic nucleophilic compound having one or more removable hydrogen atoms, in a multi-phase liquid reaction medium, by employing a palladium-based catalyst system which includes selected organic anions. The invention thus provides a process for the carbonylation of an olefinically or acetylenically unsaturated compound with carbon monoxide in the presence of a nucleophilic compound having a removable hydrogen atom and a catalyst system comprising a) a source of palladium, b) a phosphine of general formula PR1R2R3, wherein R1, R2 and R3 independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, and c) a source of anions being the conjugated base of an acid having a pKa < 3, wherein the reaction medium at least initially is a multi-phase liquid reaction medium, and in which the catalyst system comprises a component b) having an amphiphatic structure. In the context of the present invention the term the reaction medium is at least initially a multi-phase liquid reaction medium refers to a reaction medium which is at least a multi-phase liquid reaction medium at the beginning of the reaction and during the early stages thereof. The term amphiphatic structure means that such molecules are composed of groups of opposing solubility tendencies, typically an oil-soluble hydrocarbon chain and a water-soluble ionic group. The source of palladium (catalyst component a) preferably is constituted by cationic compounds such as for example the salts of palladium with, for instance, nitric acid, sulphuric acid or alkanecarboxylic acids having not more than 12 carbon atoms. Moreover, palladium complexes may also be used, for instance palladium acetylacetonate, tetrakis(triphenylphosphine)palladium, bis(tri-o-tolylphosphine)palladium acetate or bis(triphenylphosphine)palladium sulphate. Metallic palladium may be used if the catalyst composition comprises an acid component. Palladium acetate is a preferred palladium compound for the catalyst composition of the present invention to be based upon. The groups R1, R2 and R3 of the phosphine of general formula PR1R2R3 (catalyst component b) each represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group. In general such alkyl groups will have up to 20 carbon atoms, any cycloalkyl groups will have from 5-7 carbon atoms in the ring structure and any aryl group will have up to 18 carbon atoms in the ring structure. Conveniently any aryl group may be an anthryl, naphthyl or, which is preferred, a phenyl group. The heterocyclic ring may be a single heterocyclic ring or may be a part of an optionally substituted larger, condensed ring structure as exemplified by pyridyl, pyrazinyl, quinolyl, isoquinolyl, pyrimidyl, pyridazinyl, indolizinyl, cinnolinyl, acridinyl, phenazinyl, phenanthridinyl, phenanthrolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl and quinazolinyl groups. Preferred substituted phosphines are triphenylphosphines carrying one or more substituted phenyl groups. The phosphine component b of the catalyst system constitutes the catalyst component having an amphiphatic structure, in which case it has a group R1, R2 or R3 substituted with an ionic group providing water-solubility tendency to the otherwise oil-soluble phosphine ligand. Preferred ionic substituents are sulphonic, phosphonic, phosphinic and carboxylic acid groups and their salts. More preferred substituents are sulphonic acid groups or the alkali metal or ammonium salts thereof, sodium sulphonate type substituents being especially preferred. Examples of preferred triarylphosphines wherein one or more of groups R carry a specified substituent include sodium 4-(diphenylphosphino)benzenesulphonate, phenyl-bis-(sodium 4-sulphonatophenyl)phosphine. Examples of preferred alkyl(diaryl)phosphines include sodium 2-(diphenylphosphino)ethanesulphonate and sodium 3-(diphenylphosphino)propanesulphonate. These substituted phosphines can be obtained by processes as described in EP-A-280380. The source of anions (catalyst component c) can be any compound or system which is capable of generating anions of the type as required. Preferably the source of anions is the acid of which the anions are the conjugated base, or a salt of said acid. Preferred salts are alkali or alkaline earth metal salts. Should the anion source be an acid, then said acid can simultaneously act as an acid promoter for the catalyst system. Acids having a pKa < 3 ((measured in water at 18 °C) and providing anions in the catalyst compositions for use in the process of the invention preferably have a non-coordinating anion, by which is meant that little or no co-valent interaction takes place between the palladium and the anion. Typical examples of such anions are PF - / 6, SbF - / 6, BF - / 4 and ClO - / 4. Acids preferably used are, for instance, sulphonic acids and those acids that can be formed, possibly in situ, by interaction of a Lewis acid such as, for example, BF3, AsF5, SbF5, PF5, TaF5 or NbF5 with a Brønsted acid such as, for example, a hydrohalogenic acid, in particular HF, phosphoric acid or sulphuric acid. Specific examples of the last-named type of acids are fluorosilicic acid, HBF4, HPF6 and HSbF6. Typical sulphonic acids that can be used are fluorosulphonic acid, chlorosulphonic acid, p-toluenesulphonic acid and trifluoromethanesulphonic acid; the last too acids being preferred. The anion component c of the catalyst system may have an amphiphatic structure in which case it comprises a hydrophobic moiety providing oil-solubility tendency to the otherwise water-soluble anion. More particularly, the anion may have a hydrocarbyl moiety being free of olefinic and or acetylenic unsaturation and containing at least 10 carbon atoms. Preferred types of acids of which the anions, as described hereinbefore are amphiphatic, are selected from the group of acids consisting of sulphonic acids, phosphonic and phosphinic acids; sulphonic acids being especially preferred. Very suitable sulphonic acids having at least 10 carbon atoms include alkylsulphonic acids, especially linear alkylsulphonic acids, alkarylsulphonic acids such as alkylbenzenesulphonic acids, alkyltoluenesulphonic acids and alkylxylenesulphonic acids, and hydroxyalkylsulphonic acids e.g. α- or β-hydroxyalkylsulphonic acids. Sulphonic acids as mentioned hereinbefore are readily available in the form of the corresponding sulphonates, and especially the alkali metal sulphonate, as such compounds are well known for their detergent properties. Frequently such sulphonates occur as a mixture of isomers and/or a mixture of compounds having a slight variation in the number of carbon atoms per molecule. With latter type of sulphonates it is desirable that the average number of carbon atoms per anion is at least 10 and preferably at least 15. In view of its availability as a single compound, sodium 4-octadecyl-p-xylenesulphonate is a preferred sodium sulphonate for use as anion source in the process of the present invention. An example of a suitable mixed sulphonic acid is a 4-(C12-15 alkyl)-p-xylenesulphonic acid. It was mentioned hereinbefore, when employing a salt as anion source, that the corresponding acid may be obtained therefrom by interaction with the acid promoter, for which it is preferred that the pKa of the acid promoter ≤ the pKa of the acid on which said salt is based. In one embodiment of the invention, the catalyst system comprises both an amphiphatic phosphine component b, such as phenyl-bis-(sodium 4-sulphonatophenyl)phosphine and an amphiphatic anion component c, such as sodium 4-octadecyl-p-xylenesulphonate. The quantity of palladium compound, as used as catalyst component in the process of the invention, is not critical. Preference is given to the use of quantities in the range between 10-5 and 10-1 gram atom palladium per mol of olefinically or acetylenically unsaturated compound. In general the amount of phosphine ligand to be employed in the catalyst composition for use in the process of the present invention is not critical and may vary over wide ranges, which ranges may sometimes also be related to the type of phosphine ligand. For example, diphosphines will generally be employed in a quantity of 0.5-100 mol per gram atom of palladium, and phosphines containing heterocyclic groups as described hereinbefore will generally be employed in a quantity of 2-500 mol per gram atom of palladium, whereas triphenylphosphines are preferably used in a quantity of at least 5 mol per gram atom of palladium. Other monophosphines may conveniently be employed in a quantity in the range of from 0.5-50 mol per gram atom of palladium. In the process of the present invention it is preferred that the anions, in particular the anions having a hydrocarbyl moiety containing at least 10 carbon atoms, are present in an amount which corresponds with ≥ 2 eq. of anion per gram atom of palladium. In the process according to the invention acids may be used as promoters, in particular acids having a non-co-ordinating anion, by which is meant that little or no co-valent interaction takes place between the palladium and the anion. Typical examples of such anions are PF - / 6, SbF - / 6 ,BF - / 4 and C10 - / 4 and the further anions mentioned hereinbefore in connection with the anion component c of the catalyst system. A special class of acids for use in the process of the present invention are those which can simultaneously act as promoter and as anion source. Hence the anion of such acids may have a hydrocarbyl moiety containing at least 10 carbon atoms and preferably at least 15, and constitute the amphiphatic catalyst component in accordance with the invention. Acids meeting these requirements have been discussed and exemplified hereinbefore. When employing such an acid which can act as promoter and as anion source, the presence of a separate anion source in the present process is not essential. With the process of the present invention it is preferred that the acid promoter is present in an amount which corresponds with > 2 equivalents H+ per gram atom of palladium. The olefinically or acetylenically unsaturated compound may be an unsubstituted or substituted linear, branched or cyclic compound preferably having 2-30, and in particular 2-20, carbon atoms and preferably 1-3 double, respectively triple bonds. The unsaturated compounds may be substituted, for instance, with one or more halogen atoms or cyano, ester, alkoxy, hydroxy, carboxy or aryl groups. If the substituents are not inert under the reaction conditions, the carbonylation reaction may be accompanied with other reactions. Examples of suitable olefinic compounds are ethene, propene, butene-1, butene-2, isobutene, cyclopentenes, the isomeric pentenes, hexenes, octenes and dodecenes, 1,5-cyclooctadiene, cyclododecene, 1,5,9-cyclododecatriene, allyl alcohol, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, acrylamide, N,N-dimethyl acrylamide, vinyl chloride, allyl chloride, acrolein, oleic acid, methyl allyl ether and styrene. Examples of suitable acetylenes include propyne, 1-butyne, 2-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 2-octyne, 4-octyne, 5-methyl-3-heptyne, 4-propyl-2-pentyne, 1-nonyne, phenylethyne and cyclohexylethyne. The nucleophilic type reactants having one or more removable hydrogen atoms include water, mono- and polyhydric alcohols, such as for example mono- and polypentaerythritol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, hydroquinone, pyrogallol, ethylene glycol and polyethylene glycol, as well as mono- or polycarboxylic acids i.e. aliphatic, cycloaliphatic or aromatic carboxylic acids having e.g. up to 20 carbon atoms and optionally carrying one or more inert substituents such as for example halogen atoms, and cyano, ester, alkoxy and aryl groups. Examples of suitable mono- or polycarboxylic acids include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, pivalic acid, valeric acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid , hexadecanoic acid, octadecanoic acid, benzoic acid, o-,m- and p-phthalic acid and o-,m- and p-toluic acid, adipic acid, glutaric acid and sebacic acid. A further group of potentially suitable nucleophilic compounds of the type as described hereinbefore include compounds such as hydroxysulphonates and primary and secondary amines. Data regarding the combination of olefins or acetylenes and nucleophilic reactants which will result in a multi-phase liquid reaction medium, under the conditions required for conducting the carbonylation in the process of the present invention, may be obtained from the technical literature, in so far not already known by those skilled in the act. It will be appreciated that not only the nature of the olefin and alcohol reactant per se but also the ratio wherein they are to be employed, may be decisive for the formation of a multi-phase liquid reaction medium. When employing a nucleophilic reactant, having a relatively high melting point and which does not dissolve in the olefin reactant, such as for example a mono- and polypentaerythritol, 1,1,1-trimethylolethane, hydroquinone and pyrogallol, said compound may be employed as a solution. Suitable solvents which may be employed for the preparation of such solutions include sulfolane, dimethyl sulphoxide and diisopropyl sulphone. It is also possible that the phase containing the olefin or acetylene reactant may contain a solvent or diluent, e.g. to reduce the viscosity thereof, which solvent or diluent will generally be a hydrocarbon type of solvent or diluent. It was mentioned hereinbefore that the multi-phase liquid reaction medium should at least be present in the early stages of the reaction, as it is conceivable that the multi-phase liquid reaction medium will gradually be converted into a single-phase liquid reaction medium as the reaction progresses and the amount of reaction product increases, thus enabling the reaction to further proceed in a homogeneous liquid reaction medium, and in the presence of the catalyst system as described hereinbefore. Without wishing to be bound by any theory it is believed that an important feature of the process of the present invention lies in the presence in the catalyst systems of amphiphatic components as specified hereinbefore. It is believed that the observed reduction in reaction rate, when conducting the carbonylation of olefins or acetylenes with carbon monoxide in a multi-phase liquid reaction medium in the presence of nucleophilic reactant and a conventional carbonylation catalyst according to the prior art, is related to a non-uniform catalyst distribution, i.e. the catalyst system being predominantly present in the nucleophilic reactant-containing phase. However, when employing a catalyst system which includes an amphiphatic component, such as an anionically substituted phosphine, the presence of said amphiphatic components will result in the catalyst system being preferentially orientated at the interface of the phases, thereby increasing the reaction rate. Simultaneously the relatively high concentration of catalyst at the interface may also have a beneficial influence on the local miscibility of the phases. It can furthermore be expected, when the multi-phase liquid reaction medium has been converted to a single-phase or homogeneous liquid reaction medium, that the reaction will proceed as if a conventional catalyst system had been present, i.e. one which does not include a specific phosphine or anion source as described hereinbefore. In fact the catalyst systems as described hereinbefore may conveniently be also employed in a carbonylation process which is conducted in a homogeneous liquid reaction medium. In the process according to the invention the carbon monoxide may be used pure or diluted with an inert gas, such as nitrogen, noble gases or carbon dioxide. Generally the presence of more than 10 %v of hydrogen is undesirable, since under the reaction conditions it may cause hydrogenation of the olefinic compound. Generally preference is given to use to carbon monoxide or a carbon monoxide-containing gas which contains less that 5 %v of hydrogen. The carbonylation according to the invention is preferably carried out at a temperature in the range between 50 and 200 °C, in particular between 75 and 150 °C. The overall pressure preferably lies between 1 and 100, in particular 20 and 75 bar gauge. The process according to the present invention may be carried out batchwise, continuously or semi-continuously. Catalyst systems comprising a palladium compound, a phosphine of general formula PR1R2R3, wherein R1, R2 and R3 independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, and a source of anions being the conjugated base of an acid having a pKa < 3, which anions preferably have a hydrocarbyl moiety free of olefinic and/are acetylenic unsaturation and containing at least 10 carbon atoms, in which catalyst system component b) has an amphiphatic structure are novel. A further novel catalyst system provided by the invention is based on a palladium compound, a phosphine of general formula PR1R2R3 , wherein R1, R2 and R3 independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, at least one of which carries a substituent selected from the group consisting of sulphonic, phosphonic, phosphinic and carboxylic acid groups, or a salt thereof, and a source of anions having a hydrocarbyl moiety being free of olefinic and or acetylenic unsaturation and containing at least 10 carbon atoms, and being the conjugated base of an acid having a pKa < 3. The novel catalyst systems may further comprise an acid promoter. Although a wide range of products may be prepared by the process of the present invention, the nature of said products will be closely related to the nature of the reactants. For example, when employing water, a hydroxy compound, a carboxylic acid or an amine as the nucleophilic reactant, the reaction product will contain respectively an acid, an ester, an anhydride or an amine moiety, which moieties will furthermore be characterized by the presence of an α-β-olefinically unsaturated group when the coreactant is an acetylenically unsaturated compound. This olefinically unsaturated group will be absent when the coreactant is an olefinically unsaturated compound. The nature of product will not only be governed by the type of reactant but also by the functionality of the reactants and the molar ratio wherein they are employed. The functionality of the nucleophilic reactant is determined by the number of hydrogen atoms which can be removed under the conditions of the present process, whereas the functionality of the olefinically or acetylenically unsaturated compound is determined by the number of such unsaturated groups per molecule. The compounds prepared according to the process of the present invention may conveniently be isolated from the reaction mixture by known techniques, such extraction or distillation. A preferred group of compounds to be prepared by the process of the present invention are the full esters of pentaerythritol and especially those esters wherein the hydrocarbylcarbonyl groups contain 3-19 carbon atoms. Such full esters are valuable products for use as lubricants, detergents and plasticizers. Other products which may be prepared by the present process may be used as precursors for the preparation of e.g. fine chemicals. The invention will be further illustrated with the following examples for which the following information is provided: Abbreviations:Pd(OAc)2 Palladium acetate PTSA paratoluenesulphonic acid Phosphine Type D : Phenyl-bis(sodium m-sulphonatophenyl)phosphine Anion sourceI : Sodium 4-octadecyl-p-xylenesulphonate Example IA solution of 10 mmol of pentaerythritol in 50 ml sulfolane and the indicated amounts of palladium acetate, phosphine, PTSA, anion source and olefin were introduced into a magnetically stirred 250 ml stainless steel (Hastelloy C, trade mark) autoclave. Subsequently the reactor was closed and the air evacuated therefrom, whereupon 60 bar of carbon monoxide was introduced. This was followed by heating the reactor contents to 110 °C. After maintaining the reactor contents at 110 °C for the required period of time, the reactor contents were cooled to 20 °C, and analysed by means of high performance liquid chromatography to establish hydroxyl conversion. In the process, pentaerythritol polyesters with carboxylic acids having one more carbon atom than the precursor olefins are formed; at 100 % hydroxyl conversion the product is constituted by the tetraester, whereas at lower hydroxyl conversion mixtures further containing tri-, di- and monoesters are obtained. The analytical data have been presented in Table 1, which also gives the relevant process details. From the results presented in Table 1, it can be observed that the presence of the anion source enables a 100 % hydroxyl conversion to be obtained. With the experiments wherein a 100 % conversion was obtained the residence time in the reactor at 110 °C should not be interpreted as being the required reaction time, as it only indicates that the corresponding result was achieved within that time. The actual reaction time could well be considerably shorter. Example Pd(OAc)2 mmol Phosphine PTSA mmol Anion source α-olefin conv. OH eq. % Time at 110 °C h Type mmol Type mmol Type ml I0.5D64I4C87010015 Example IIInto a 250 ml stainless steel (Hastelloy C) autoclave were introduced 40 ml diethylene glycol dimethyl ether, 10 ml water, 0.1 mmol palladium acetate, 2 mmol paratoluenesulphonic acid, 4 mmol of phenyl-bis-(sodium 4-sulphonatophenyl)phosphine and 20 ml cyclopentene. Subsequently the reactor was closed and the air removed by pressuring/depressuring cycles with carbon monoxide, which was followed by carbon monoxide addition at a pressure of 40 bar and heating to 110 °C. After a reaction time of 5 h the reactor contents were cooled to room temperature (approx. 20 °C) and analyzed via gas liquid chromatography which showed an olefin conversion of 75 % to cyclopentane carboxylic acid with a selectivity of 100 %). Example IIIThe procedure of Example II was repeated except that 4 mmol of sodium 4-octadecyl-p-xylenesulphonate was also introduced into the reactor which resulted in an olefin conversion after 5 h reaction of 85 %. Comparative ExperimentThe procedure of Example II was repeated with the exception that the sulphonate-containing phosphine was replaced with 5 mmol of triphenyl-phosphine. After 5 h the olefin conversion was < 5 %.	A process for the carbonylation of an olefinically or acetylenically unsaturated compound with carbon monoxide in the presence of a nucleophilic compound having a removable hydrogen atom and a catalyst system comprising a) a source of palladium, b) a phosphine of general formula PR1R2R3, wherein R1, R2 and R3 independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, and c) a source of anions being the conjugated base of an acid having a pKa < 3, in which process the reaction medium is at least initially a multi-phase liquid reaction medium, and in which the catalyst system comprises a component b) having an amphiphatic structure. A process as claimed in claim 1, wherein the catalyst system further comprises a component c) having an amphiphatic structure. A process as claimed in claim 1 or 2, wherein the catalyst component having an amphiphatic structure is an anionic surfactant. A process as claimed in any one or more of claims 1-3, wherein the nucleophilic compound having a removable hydrogen atom is water, an alcohol or a carboxylic acid. A process as claimed in any one or more of claims 1-4, wherein the anions have a hydrocarbyl moiety being free of olefinic and or acetylenic unsaturation and containing at least 10 carbon atoms. A process as claimed in claim 5, wherein the anions are the conjugated bases of acids selected from the group consisting of sulphonic, phosphonic, phosphinic and carboxylic acids having a pKa < 3. A process as claimed in claim 6, wherein the sulphonic acid is an alkylsulphonic acid or an alkarylsulphonic acid. A process as claimed in claim 7, wherein the alkarylsulphonic acid is a C12-20 alkyl p-xylenesulphonic acid. A process as claimed in any one or more of claims 1-8, wherein the catalyst system comprises an acid promoter. A process as claimed in any one or more of claims 1-9, wherein the phosphine of general formula PR1R2R3 has at least one group R1, R2 or R3 carrying a substituent selected from the group consisting of sulphonic, phosphonic, phosphinic and carboxylic acid groups, or a salt thereof. A process as claimed in claim 10, wherein the phosphine is a triarylphosphine or an alkyl(diaryl)phosphine. A process as claimed in claim 11, wherein the substituents are sulphonic acid groups or the alkali metal or ammonium salt thereof. A process as claimed in claim 12, wherein the substituent is a sodium sulphonate group. A catalyst composition based on a) a palladium compound, b) a phosphine of general formula PR1R2R3, wherein R1, R2 and R3 independently represent an optionally substituted alkyl, cycloalkyl, aryl or N-heterocyclic group, and c) a source of anions being the conjugated base of an acid having a pKa < 3, in which catalyst system component b) has an amphiphatic structure. A catalyst composition according to claim 14, in which the source of anions has a hydrocarbyl moiety being free of olefinic and/or acetylenic unsaturation and containing at least 10 carbon atoms. A catalyst composition according to claim 14 or 15, wherein the phosphine of general formula PR1R2R3 has at least one group R1, R2 or R3 carrying a substituent selected from the group consisting of sulphonic, phosphonic, phosphinic and carboxylic acid groups, or a salt thereof. A catalyst composition as claimed in any one or more of claims 14-16, comprising an acid promoter.	SHELL INT RESEARCH; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.	DRENT EIT; KOENDERS PETER; DRENT, EIT; KOENDERS, PETER
EP-0489473-B1	489,473	EP	B1	EN	19,990,224	1,992	20,100,220	new	C08G67	null	C08G67	C08G 67/02, B01J 31/24, L01J531:80, B01J 31/02C, B01J 31/24B2, L01J31:04, L01J231:10	Process for the preparation of polyketones	Novel catalyst compositions which contain a Group VIII metal and a phosphorus bidentate ligand with the general formula (R²)(R⁴)P-R³-P(R²)(R⁴) in which R² and R⁴ are identical or different optionally polar substituted monovalent aliphatic hydrocarbyl groups and in which R³ is a divalent organic bridging group which in the bridge connecting the two phosphorus atoms contains four atoms, of which at least two are carbon atoms and among which no two atoms are present which together form part of a single cyclic structure. They are particularly suited to the preparation of polymers of carbon monoxide and C₃+ α-olefins.	The invention relates to a process for the preparation of polymers of carbon monoxide with one or more α-olefins having at least three carbon atoms per molecule.It is known that linear polymers of carbon monoxide with ethene in which polymers the units from carbon monoxide and ethene are present in a substantially alternating order can be prepared by contacting the monomers at elevated temperature and pressure with a catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand with the general formula (R1)2P-R-P(R1)2 in which R1 represents an optionally polar substituted monovalent aromatic hydrocarbyl group and R is a divalent organic bridging group. This bridging group R preferably contains, in the bridge connecting the two phosphorus atoms, three atoms, of which at least two are carbon atoms and among which no two atoms are present which together form part of a single cyclic structure. It appeared that phosphorus bidentate ligands in which such a bridge occurs provide catalyst compositions having the highest polymerization rate. An example of such a phosphorus bidentate ligand is 1,3-bis(diphenylphosphino)propane.A drawback of the alternating carbon monoxide/ethene copolymers is that they have a very high melting point. The processing of these polymers should take place in the molten state with the material being at a temperature which is at least 25°C above the melting point. It has been found that these polymers are not as resistant to the high temperatures required in their processing, as a result of which discoloration and decomposition can take place. As a solution for this problem the applicant found, as proposed in EP-A-213671, that the melting point of these polymers can be considerably reduced by incorporating in the monomer mixture from which they are prepared, a relatively small quantity of one or more α-olefins having at least three carbon atoms per molecule (indicated for short as C3+ α-olefins). The more C3+ α-olefins are incorporated in the monomer mixture, the lower the melting point of the polymers obtained. It was also found that the previously mentioned catalyst compositions which exhibited the highest polymerization rate in the polymerization of carbon monoxide with ethene because they contained a phosphorus bidentate ligand with three atoms in the bridge, also exhibited the highest polymerization rate in the polymerization of carbon monoxide with ethene and additionally one or more C3+ α-olefins.The applicant recently carried out an investigation in order to find out to what extent, with the use of the above-mentioned catalyst compositions, linear polymers of carbon monoxide with one or more C3+ α-olefins (i.e. without ethene) can be prepared in which the units from carbon monoxide and C3+ α-olefins occur in a substantially alternating manner. It was found that such polymers can indeed be prepared in this way, but that the catalyst compositions exhibited only a low polymerization rate in comparison with their previously observed rate in the polymerization of carbon monoxide with ethene and optional, additional, C3+ α-olefin(s). Just as had previously been observed in the polymerization of carbon monoxide with ethene and in the polymerization of carbon monoxide with ethene and additionally with one or more C3+ α-olefins, it was also established in the polymerization of carbon monoxide with one or more C3+ α-olefins that catalyst compositions containing a phosphorus bidentate ligand with three atoms in the bridge exhibit the highest polymerization rate. As described in EP-A-376364, continued research by the applicant into this subject showed that the polymerization rate of the previously mentioned catalyst compositions for the polymerization of carbon monoxide with one or more C3+ α-olefins could be raised by replacing the optionally polar substituted monovalent aromatic R1 hydrocarbyl groups in the phosphorus bidentate ligand by optionally polar substituted monovalent aliphatic R2 hydrocarbyl groups. In view of the observed relationship between the polymerization rate and the number of carbon atoms in the bridge of the phosphorus bidentate ligand, in the polymerization of carbon monoxide with all sorts of α-olefins using catalyst compositions containing a phosphorus bidentate ligand in which the optionally polar substituted monovalent hydrocarbyl groups linked to phosphorus were aromatic, it would be logical to assume that the same relationship would hold for such catalyst compositions containing bidentate ligands in which the hydrocarbyl groups linked to phosphorus are aliphatic, i.e. that the highest polymerization rate is achieved using ligands in which the bridge contains three atoms. An example of a phosphorus bidentate ligand of this type with the general formula (R2)2P-R-P(R2)2 is 1,3-bis(di-n-butylphosphino)propane.In the course of continued research into this subject it has now been surprisingly found that the activity of the last mentioned catalyst compositions for the polymerization of carbon monoxide with one or more C3+ α-olefins can be raised by selecting as the bridging group R in the phosphorus bidentate ligand, a divalent organic bridging group R3 which is a tetramethylene group. It was further found that an increase of the activity of the catalyst compositions by selecting as the phosphorus bidentate ligand with the general formula (R2)2P-R-P(R2)2, a phosphorus bidentate ligand with the general formula (R2)2P-R3-P(R2)2, also occurs in the polymerization of carbon monoxide with ethene and additionally with one or more C3+ α-olefins. In complete contrast with this it has been found that a selection of this kind in the polymerization of carbon monoxide with ethene leads to a decrease in the polymerization rate. Finally it was found that the activity of catalyst compositions containing a phosphorus bidentate ligand with the general formula (R2)2P-R3-P(R2)2 in the polymerization of carbon monoxide with one or more C3+ α-olefins and optionally also with ethene can be raised further by replacing therein at each of the two phosphorus atoms one of the R2 groups by an optionally polar substituted aliphatic hydrocarbyl group differing in carbon number from R2. Corresponding with the previously observed anomalous behaviour of the catalyst compositions containing a phosphorus bidentate ligand with the general formula (R2)2P-R3-P(R2)2 in the polymerization of carbon monoxide with ethene, it was now also found in this polymerization that a replacement of this kind led to a decrease in the polymerization rate. Evidently, the favourable effects on the polymerization rate obtained with the above-described modifications of the phosphorus bidentate ligand are only obtained if the catalyst composition is used for polymerizing a monomer mixture containing C3+ α-olefins.EP-A-121965 and EP-A-181014 disclose catalyst compositions which contain a Group VIII metal and 1,4-bis(dicyclohexyl-phosphino)butane. However, nothing is disclosed as regards the performance of these compositions in the copolymerization of carbon monoxide with one or more C3+ α-olefins and optionally also with ethene.EP-A-384517 is concerned with the preparation of stereoregular polymers of carbon monoxide and an α-olefin having at least three carbon atoms, by using in the palladium containing catalyst composition an asymmetric phosphorus bidentate ligand, such as a ligand of which the bridge connecting the phosphorus atoms participates in a ring structure. This documents discloses the use of (-)-4,5-bis(dibutylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane, which is a ligand which contains a single ring structure in the bridge. The working examples in EP-A-384517 indicate that the use of ligands with such bridging groups leads to a drastic reduction in the polymerisation rate of carbon monoxide with propene (cf. example 5 vs. example 2). The patent application relates to a process for the preparation of polymers in which process a mixture of carbon monoxide with one or more C3+ α-olefins and optionally also with ethene is contacted at elevated temperature and pressure with a catalyst composition containing a Group VIII metal and a phosphorus bidentate ligand with the general formula (R2)(R4)P-R3-P(R2)(R4) in which R2 and R4 are identical or different optionally polar substituted monovalent aliphatic hydrocarbyl groups and in which R3 is a tetramethylene group.In this patent application, Group VIII metals are understood to be the noble metals ruthenium, rhodium, palladium, osmium, iridium and platinum, as well as the iron group metals iron, cobalt and nickel.In the catalyst compositions according to the invention the Group VIII metal is preferably chosen from palladium, nickel and cobalt. Palladium is particularly preferred as Group VIII metal. The incorporation of the Group VIII metal in the catalyst compositions preferably takes place in the form of a salt of a carboxylic acid, in particular in the form of an acetate. In addition to a Group VIII metal and a phosphorus bidentate ligand, the catalyst compositions used in the process according to the invention preferably also contain an anion of an acid with a pKa of less than 4 and in particular an anion of an acid with a pKa of less than 2. Examples of acids with a pKa of less than 2 are mineral acids such as sulphuric acid and perchloric acid, sulphonic acids such as methanesulphonic acid, trifluoromethanesulphonic acid and para-toluenesulphonic acid, and halocarboxylic acids such as trichloroacetic acid, difluoroacetic acid and trifluoroacetic acid. A sulphonic acid such as para-toluenesulphonic acid or a halocarboxylic acid such as trifluoroacetic acid is preferred. The anion can be introduced into the catalyst compositions either in the form of a compound from which the desired anion splits off or in the form of a mixture of compounds from which the desired anion is formed by mutual reaction. As a rule, the anion is incorporated in the catalyst compositions in the form of an acid. If desired, the anion can also be included in the catalyst composition in the form of a main group metal salt or a non-noble transition metal salt of the acid in question. If an anion of a carboxylic acid is chosen, its incorporation in the catalyst composition can take place in the form of the acid or in the form of a derivative thereof, such as an alkyl or aryl ester, an amide, an imide, an anhydride, an ortho-ester, a lactone, a lactam or an alkylidene dicarboxylate. The anion is preferably present in the catalyst compositions in a quantity of 1-100 and in particular 2-50 mol per g.atom Group VIII metal. As well as by its application as a separate component, the anion of an acid with a pKa of less than 4 can also be present in the catalyst compositions by the use of, for example, palladium trifluoroacetate or palladium para-tosylate as Group VIII metal compound.In addition to a Group VIII metal, a phosphorus bidentate ligand and optionally an anion of an acid with a pKa of less than 4, the catalyst compositions used in the process according to the invention can also contain an organic oxidizing agent. Examples of suitable organic oxidizing agents are 1,2- and 1,4-quinones, aliphatic nitrites such as butyl nitrite and aromatic nitro compounds such as nitrobenzene and 2,4-dinitrotoluene. 1,4-benzoquinone and 1,4-naphthoquinone are preferred. The quantity of organic oxidizing agent employed is preferably 5-5000 and in particular 10-1000 mol per g.atom Group VIII metal.In the catalyst compositions used in the process according to the invention the phosphorus bidentate ligand is preferably present in a quantity of 0.5-2 and in particular 0.75-1.5 mol per g.atom Group VIII metal. In the phosphorus bidentate ligands with the general formula (R2)(R4)P-R3-P(R2)(R4) the R3 bridging group is the tetramethylene group. In the phosphorus bidentate ligands the R2 and R4 groups preferably each contain not more than 10 carbon atoms. As has been explained above, phosphorus bidentate ligands can be used in the catalyst compositions used in the process according to the invention in which the R2 and R4 groups are identical. Advantageous results are obtained according to the invention by using catalyst compositions containing a phosphorus bidentate ligand in which the R2 and R4 groups are identical, such as 1,4-bis(di-n-butylphosphino)butane. There is preference for the use of phosphorus bidentate ligands in which the R2 and R4 groups differ from each other in carbon number. Very advantageous results are obtained according to the invention by using catalyst compositions containing a phosphorus bidentate ligand in which the R2 and R4 groups are alkyl groups differing from each other in carbon number, one being methyl, such as 1,4-bis(methyl, n-butylphosphino)butane.The polymerization according to the invention is preferably carried out by contacting the monomers with a solution of the catalyst composition in a diluent in which the polymers are insoluble or almost insoluble. Lower alcohols such as methanol are very suitable as diluent. If desired, the polymerization can also be carried out in the gas phase. As regards the C3+ α-olefins used in the polymer preparation according to the invention, there is preference for α-olefins with a maximum of 10 carbon atoms per molecule. There is further preference for the use of monomer mixtures in which besides carbon monoxide and optionally ethene only one C3+ α-olefin is present. Examples of suitable C3+ α-olefins are propene, pentene-1 and 4-methylpentene-1. The process according to the invention is particularly very suitable for the preparation of copolymers of carbon monoxide with propene and for the preparation of terpolymers of carbon monoxide with ethene and with propene.The quantity of catalyst composition used in the preparation of the polymers can vary within wide limits. Per mol of olefin to be polymerized, a quantity of catalyst composition is preferably used which contains 10-7-10-3 and in particular 10-6-10-4 g.atom Group VIII metal.The preparation of the polymers is preferably carried out at a temperature of 25-150°C and a pressure of 2-150 bar and in particular at a temperature of 30-130°C and a pressure of 5-100 bar.The invention is illustrated further by the following examples.Example 1A carbon monoxide/ethene copolymer was prepared as follows. Into a stirred autoclave with a volume of 100 ml from which the air had been driven by purging with nitrogen, a catalyst solution was introduced consisting of: 40 ml methanol,0.05 mmol palladium acetate,0.055 mmol 1,3-bis(diphenylphosphino)propane, and0.1 mmol para-toluenesulphonic acid.After forcing in a 1:1 carbon monoxide/ethene mixture to a pressure of 40 bar, the contents of the autoclave were heated to 90°C. During the polymerization the pressure was kept constant by forcing in a 1:1 carbon monoxide/ethene mixture. After 1 hour the polymerization was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried.17.7 g copolymer was obtained. The polymerization rate was 3300 g copolymer/(g palladium.hour).Examples 2-5Example 1 was repeated with the difference that instead of 1,3-bis(diphenylphosphino)propane the bidentate ligand listed in Table I was used. The obtained yields (in g copolymer) and polymerization rates (in g copolymer/(g palladium.hour) are listed in Table I as well. Ex.ligandyieldrate11,3-bis(diphenylphosphino)propane17.7330021,4-bis(diphenylphosphino)butane13.3248031,3-bis(di-n-butylphosphino)propane5.4101041,4-bis(di-n-butylphosphino)butane4.075051,4-bis(methyl,n-butylphosphino)butane1.8330Example 6A carbon monoxide/ethene/propene terpolymer was prepared as follows. Into a stirred autoclave with a volume of 100 ml from which the air had been driven by purging with nitrogen, a catalyst solution was introduced consisting of: 40 ml methanol,0.05 mmol palladium acetate,0.055 mmol 1,3-bis(diphenylphosphino)propane, and0.1 mmol paratoluenesulphonic acid.After adding 9.3 g propene, the temperature was raised to 90°C, after which a 1:1 carbon monoxide/ethene mixture was forced in until a pressure of 40 bar was reached. During the polymerization the pressure was kept constant by forcing in a 1:1 carbon monoxide/ethene mixture. After 1 hour the polymerization was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was filtered off, washed with methanol and dried. 13.9 g terpolymer was obtained. The polymerization rate was 2590 g terpolymer/(g palladium.hour).Examples 7-13Example 6 was repeated with the differences that sometimes instead of 1,3-bis(diphenylphosphino)propane one of the bidentate ligands also used in Examples 2-5 was used, and that the amount of propene (in g) listed in Table II was forced in instead of 9.3 g. The obtained yields (in g terpolymer) and polymerization rates (in g terpolymer/(g palladium.hour) are listed in Table II as well. Ex.ligand of Examplepropenenotesyieldrate61 9.313.925907 2 10.3 6.1 11408110.529.454809210.217.2320010311.51.215011410.04.788012412.35.8108013512.26.42000Example 14A carbon monoxide/propene copolymer was prepared as follows. Into a stirred autoclave with a volume of 100 ml from which the air had been driven by purging with nitrogen, a catalyst solution was introduced consisting of: 40 ml methanol,0.05 mmol palladium acetate,0.055 mmol 1,3-bis(di n-butylphosphino)propane, and0.1 mmol para-toluenesulphonic acid.After adding 10.7 g propene, the temperature was raised to 60°C, after which carbon monoxide was forced in until a pressure of 40 bar was reached. During the polymerization the pressure was kept constant by forcing in carbon monoxide. After 3 hours the polymerization was terminated by cooling the reaction mixture to room temperature and releasing the pressure. The polymer was isolated by evaporation of the reaction mixture.2.5 g copolymer was obtained. The polymerization rate was 160 g copolymer/(g palladium.hour).Examples 15-18Example 14 was repeated with the differences that instead of 1,3-bis(di-n-butylphosphino)propane the bidentate ligand also used in Example 4 or 5 was used, and that the amount of propene (in g) listed in Table III was forced in instead of 10.7 g. The obtained yields (in g copolymer) and polymerization rates (in g copolymer/(g palladium.hour) are listed in Table III as well. Ex.ligand of Examplepropenenotesyieldrate14310.72.51601548.46.138016412.0(,)2.75101759.78.249018512.2(,)4.1760Example 19A carbon monoxide/propene copolymer was prepared in substantially the same way as in example 14, but with the following differences: a) the polymerization was carried out in an autoclave with a volume of 300 ml instead of 100 ml,b) a catalyst solution was used consisting of 120 ml methanol instead of 40 ml and 1,4-bis(methyl, n-butylphosphino)butane instead of 1,3-bis(di n-butylphosphino)propane,c) 27.0 g propene was introduced into the autoclave instead of 10.7 g, d) the reaction temperature was 70°C instead of 60°C, ande) the reaction time was 1 hour instead of 3 hours. 6.4 g copolymer was obtained. The polymerization rate was 1190 g copolymer/(g palladium.hour).Example 20A carbon monoxide/propene copolymer was prepared in substantially the same way as in example 14, but with the following differences: a) the polymerization was carried out in an autoclave with a volume of 300 ml instead of 100 ml,b) a catalyst solution was used consisting of: 120 ml methanol,0.1 mmol palladium acetate,0.11 mmol 1,4-bis(di n-butylphosphino)butane, and0.2 mmol para-toluenesulphonic acid,c) 23.0 g propene was introduced into the autoclave instead of 10.7 g,d) the reaction temperature was 80°C instead of 60°C, ande) the reaction time was 1 hour instead of 3 hours. 7.5 g copolymer was obtained. The polymerization rate was 710 g copolymer/(g palladium.hour).Of the examples 1-20, examples 11-13 and 15-20 are according to the invention. In these examples carbon monoxide/propene copolymers and carbon monoxide/ethene/propene terpolymers were prepared using catalyst compositions containing a Group VIII metal and a phosphorus bidentate ligand with the general formula (R2)(R4)P-R3-P(R2)(R4). Examples 1-10 and 14 are included in the patent application for comparison.Examples 1-5 relate to the preparation of carbon monoxide/ethene copolymers. Comparison of the results of these examples shows the decrease in polymerization rate that occurs if in the catalyst composition a phosphorus bidentate ligand containing three atoms in the bridge connecting the two phosphorus atoms to each other is replaced by a phosphorus bidentate ligand containing a tetramethylene group as the bridge. This applies both for a tetra-aryl- and a tetra-alkylbisphosphine. On replacing a tetra-alkylbisphosphine in which the alkyl groups attached to phosphorus are identical by a tetra-alkylbisphosphine in which the alkyl groups attached to phosphorus differ in carbon number, a further decrease in the polymerization rate takes place.Examples 6-10 relate to the preparation of carbon monoxide/ethene/propene terpolymers. Comparison of the results of examples 6-9 shows the decrease in polymerization rate that occurs if in the catalyst composition a tetra-arylbisphosphine containing three atoms in the bridge connecting the two phosphorus atoms is replaced by a tetra-arylbisphosphine containing a tetramethylene group as the bridge.Comparison of the results of examples 10 and 11 and of the results of examples 14 and 15 shows the increase in polymerization rate that occurs both in the preparation of carbon monoxide/ethene/propene terpolymers and in the preparation of carbon monoxide/propene copolymers if in the catalyst composition a tetra-alkylbisphosphine containing three atoms in the bridge connecting the two phosphorus atoms is replaced by a tetra-alkylbisphosphine containing a tetramethylene group as the bridge.Comparison of the results of examples 12 and 13 and of the results of examples 15 and 17 shows the increase in polymerization rate that occurs both in the preparation of carbon monoxide/ethene/propene terpolymers and in the preparation of carbon monoxide/propene copolymers if a tetra-alkylbisphosphine in which the alkyl groups attached to phosphorus are identical are replaced by a tetra-alkylbisphosphine in which the alkyl groups attached to phosphorus differ in carbon number.It was established by 13C-NMR analysis that the polymers prepared according to examples 1-20 were built up of linear chains in which the units from carbon monoxide on the one hand and the units from the olefin(s) used on the other hand were present in an alternating order. In the terpolymer chains the units from ethene and propene were present in a random distribution.	Process for the preparation of polymers in which a mixture of carbon monoxide with one or more α-olefins having at least three carbon atoms per molecule (C3+ α-olefins) and optionally also with ethene is contacted at elevated temperature and pressure with a catalyst composition which contains a Group VIII metal and a phosphorus bidentate ligand of the general formula (R2)(R4)P-R3-P(R2)(R4) in which R2 and R4 are identical or different optionally polar substituted monovalent aliphatic hydrocarbyl groups and in which R3 is a divalent organic bridging group characterized in that the bridging group R3 is a tetramethylene group. Process according to claim 1, characterized in that the catalyst composition additionally contains an anion of an acid with a pKa of less than 4 in a quantity of 1-100 mol per g.atom Group VIII metal.Process according to claim 1 or 2, characterized in that the catalyst composition contains the phosphorus bidentate ligand in a quantity of 0.5-2 mol per g.atom Group VIII metal.Process according to one or more of claims 1-3, characterized in that the catalyst composition contains a phosphorus bidentate ligand in which the R2 and R4 groups each contain no more than 10 carbon atoms.Process according to one or more of claims 1-4, characterized in that the catalyst composition contains a phosphorus bidentate ligand in which the R2 and R4 groups are identical alkyl groups.Process according to one or more of claims 1-4, characterized in that the catalyst composition contains a phosphorus bidentate ligand in which the R2 and R4 groups differ from each other in carbon number. Process according to claim 6, characterized in that the catalyst composition contains a phosphorus bidentate ligand in which the R2 and R4 groups are alkyl groups which differ in carbon number, one being a methyl group.Process according to one or more of claims 1-7, characterized in that it is carried out at a temperature of 25-150°C, a pressure of 2-150 bar and that per mol of olefin to be polymerized a quantity of catalyst composition is used which contains 10-7-10-3 g.atom Group VIII metal.	SHELL INT RESEARCH; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.	KLUSENER PETER ANTON AUGUST; SNEL JOHANNES JACOBUS MARIA; KLUSENER, PETER ANTON AUGUST; SNEL, JOHANNES JACOBUS MARIA
EP-0489474-B1	489,474	EP	B1	EN	19,950,719	1,992	20,100,220	new	G01P5	null	G01F1, G01P5	G01F 1/66A, G01P 5/26	Laser apparatus for measuring the velocity of a fluid	In a laser apparatus for measuring the velocity of a fluid, a measurement laser light beam (M) fed into the fluid and scattered by a particle within the fluid is made to interfere with a reference laser light beam (R) to generate an interference signal based on the velocity of the particle; the apparatus comprises a low-coherence laser source (10) and interferometric means (11, 12) which split the light beam of the laser source (10) into the stated reference light beam (R) and measurement light beam (M), and cause the reference light beam (R) derived from the laser source (10) to interfere with the backscattered component resulting from the scattering of the measurement light beam (M).	This invention relates to a laser apparatus for measuring the velocity of a fluid. Laser apparatus for measuring the velocity of a fluid in a pipe are known, based on measuring the frequency variation undergone by a laser beam when scattered by a particle within the fluid. The particle can be naturally present in the fluid or can be introduced artificially in order to effect the velocity measurement. The frequency variation is measured by an interferometric method, by which the laser beam which has undergone the frequency variation is made to interfere with another laser beam which has not undergone or has differently undergone the frequency variation. From WO-A-8 807 179 a dynamic light scattering apparatus is known utilizing homodyne interferometric measurement techniques in which an incident measurement laser beam is scattered by the moving particles of the fluid under study and then made to interfere with a reference beam derived from the same laser source using a beam-splitter. From the detected interference the velocity of the fluid under inspection is derived. Further EP-A- 0 374 027 and EP-A- 0 355 300 disclose laser doppler shift anemometers, in which coherent laser light is split into measurement and reference beams, the latter being modulated to provide a frequency shifted beam which then interferes with measurement light scattered by the moving fluid. In EP-A- 0 374 027 focussing is accomplished by focussing optics. The commonly used apparatus comprises a laser source which feeds the light beam to suitable optical elements which split it into two separate light beams; the two light beams, of which one is for reference and one for measurement, are concentrated by a lens onto an internal point of the pipe through which the fluid flows, by passing through a transparent window provided in the pipe wall; the light scattered along a determined axis by the particle passing through said internal point is collected external to the pipe by other optical elements, after passing either through said window or through another transparent window provided in the pipe wall, depending on the collection position. These other optical elements concentrate this scattered light onto a photodetector or onto a photomultiplier. The light scattered along said axis by the particles is the result of superimposing the light beam scattered by the effect of the reference light beam incident on the particle, onto the light beam scattered by the effect of the measurement light beam incident on the particle. Said axis can lie between the axes of the two incident light beams or can coincide with the axis of the incident reference light beam. Superimposing the two scattered light beams produces an interference light signal which is converted by the photodetector or photomultiplier into an electrical signal based on the velocity of the particle and hence of the fluid at that point of the pipe onto which the two incident light beams are concentrated. The two incident light beams enable the position within the pipe of the internal point onto which they are concentrated to be exactly determined. A processor unit connected to the output of the photodetector or photomultiplier provides data regarding the fluid velocity at that point. Measuring the fluid velocity within a pipe by such apparatus however has two considerable drawbacks. In this respect, such measurement requires the availability of one or more windows provided in the pipe wall and having an appropriate size and shape to enable the light beams to pass from the outside to the inside of the pipe and vice versa but to limit aberration effects. This however results in a measurement system wich is too demanding in that it requires considerable modifications to the pipe, which disturb its normal configuration. In addition, optical components of a certain size have to be positioned in proximity to the pipe. This apparatus cannot therefore be used if the pipe is not easily accessible. The object of the present invention is to provide a laser apparatus for measuring the velocity of a fluid within a pipe which obviates the drawbacks of the aforesaid apparatus. This object is attained by a laser apparatus for measuring the velocity of a fluid, according to claim 1 or 2. The characteristics and advantages of the present invention will be apparent from the description of some embodiments thereof given hereinafter by way of non-limiting example with reference to the accompanying drawings, in which: Figure 1 shows the basic scheme of an apparatus according to the invention; Figure 2 is a schematic illustration of a first apparatus of the invention; Figure 3 is a schematic illustration of a second apparatus of the invention; Figure 4 is a schematic illustration of a third apparatus of the invention; Figures 5 and 6 show variations in the position of a component of said apparatus. The scheme of Figure 1 shows a low-coherence laser source 10 which feeds a light beam to a beam splitter 11. The fed beam is split by the beam splitter 11 into a reflected light beam constituting a reference light beam R, and a transmitted light beam constituting a measurement light beam M. The reference light beam R encounters a mirror 12 and reverses in the direction of the beam splitter 11. The measurement light beam M is fed by way of example into a pipe 13 through which there flows a fluid, the velocity of which is to be measured. The measurement light beam M, directed perpendicular to the flow direction of the fluid in the pipe 13, penetrates into the pipe through a window provided in the pipe wall and consisting of a deflection prism 14 which deviates the light beam through an angle alpha. The measurement light beam M which has penetrated into the pipe 13 is scattered by the particles within the fluid which it encounters in its path. Specifically, the backscattered component resulting from the scattering of the measurement light beam incident on the particles, ie the component which has scattered rearwards along the same path as the incident measurement light beam, passes through the prism 14 to encounter the light beam reflected by the mirror 12 in the beam splitter 11. This backscattered component is known hereinafter as the backscattered measurement light beam. The two said light beams, ie the beam backscattered by the particles and the beam reflected by the mirror 12 are caused by the beam splitter 11 to interfere on a photodetector 15. With reference to the measurement light beam backscattered by a particle at the point in the pipe 13 indicated by x₁, because of the low-coherence characteristics of the laser source 10 interference occurs between the reference light beam reflected by the mirror 12 and the measurement light beam backscattered by the particle located at point x₁ only if the difference between the two optical arms of the described interferometer, ie the arm relative to the portion a and the arm relative to the portions b and c added together, is less than or equal to the coherence length of the laser source. If the difference between the optical arms is greater than the coherence length, there is no interference. As this coherence length is very small, of the order of tens of microns, it is apparent that when the optical arms of the interferometer respect said condition there is basically present at the point x₁ only the measurement light beam backscattered by the particle, to produce interference on the photodetector 15 with the reference light beam reflected by the mirror 12 in the position P₁ . The measurement light beam backscattered by the other particles lying along the path of the incident measurement light beam do not produce any interference as said condition is not respected. Said condition is inter alia a condition of balance between the optical arms of the interferometer. In this situation the measurement light beam backscattered by the particle at the point x₁ is shifted in frequency with respect to the light beam emitted by the laser source 10, and hence with respect to the reference light beam reflected by the mirror 12, by an amount directly proportional to the velocity of the particle and to the sine of the angle alpha, and inversely proportional to the average wavelength of the light beam emitted by the laser source 10. This frequency shift is detected by the interference produced on the photodetector 15, which emits an electrical signal corresponding to the optical interference signal, and hence a function of the velocity of the particle at the point x₁. By suitably processing this electrical signal using known methods, the value of the velocity of the particle at the point x₁ can be obtained. The prism 14 provides the correct deviation of the light beam within the pipe 13 to the line Y perpendicular to the pipe fluid flow direction required to produce the frequency shift of the backscattered measurement light beam. It should be noted that for optical communication between the outside and inside of the pipe 13, only one window (prism 14) is used, this being of small size as the incident measurement light beam and the backscattered light beam travel along the same optical path. As will be noted hereinafter, an apparatus based on this scheme does not require large-dimension optical components in proximity to the pipe, both because the reference light beam is obtained directly from the light beam emitted by the laser source and because the incident measurement light beam and the backscattered light beam travel along the same optical path. The initially stated drawbacks of known apparatus are therefore remedied. If the velocity of a particle at the point x₂ of the pipe 13 lying along the incident measurement light beam is to be measured, it is only necessary, from the aforegoing, to move the mirror 12 from its position P₁ to a position P₂ in which the difference between the two optical arms of the interferometer, ie the arm relative to the portion a′ and the arm relative to the portions b and c′ added together, is less than or equal to the coherence length of the laser source. From the aforegoing it is therefore possible to analyze the velocity of all the particles lying along the incident measurement light beam, and hence generally by suitably orientating the incident measurement light beam the velocity of the particles within the fluid, so that the velocity of the fluid can be analyzed along a chord or along a diameter of the pipe cross-section. This is extremely advantageous, as in practical applications the knowledge of the fluid velocity at one point of the pipe is often not sufficient to provide significant information on the fluid motion. Much more significant information for hydrodynamic purposes is that provided by measuring the distribution of the fluid velocity along a chord or along a diameter of the pipe cross-section. The known apparatus mentioned in the introduction involve a series of difficulties if investigating different points within the pipe. Firstly, it may be necessary to provide even larger windows of special shape to allow light beams to pass at variable inclinations as the point under measurement varies, and to limit the consequent aberration effects, with the result that the measurement system becomes even more demanding. The scanning of different points within the pipe requires the handling of a certain number of very large components comprising the apparatus, and this can prejudice their operation. Finally, the optical elements for projecting and collecting the light beams are optimized for a certain measurement depth within the pipe. Any significant variation in this depth varies the characteristics of the apparatus, to compromise measurement accuracy. These difficulties do not exist with the apparatus scheme of Figure 1. In this respect, as already stated, only a single small-dimension window is required. In addition the scanning of the various points within the pipe is effected by simply moving a single optical component, ie the mirror 12. Finally, the apparatus behaves equally in scanning every point within the pipe along the chord or diameter of the pipe cross-section, because the optical characteristics of the entire system remain constant as the mirror moves. This is because during this scanning, neither the path nor the inclination of the light beam changes within the pipe. The measurement accuracy therefore remains constant as the point of measurement varies. It should be added that the apparatus operating on the aforesaid principle to measure the fluid velocity at a point within the pipe does not require this measurement point to be geometrically defined by two light beams as in the known apparatus described in the introduction, but requires only the use of a single light beam as it is the condition of balance between the two optical arms of the interferometer which enables the point under measurement to be defined. In this respect the optical arm relative to the measurement light beam which defines the point under measurement is equal to the optical arm, of known value, relative to the reference light beam less the coherence length of the laser source. The measurement point is therefore definable with an accuracy which depends on the coherence length of the laser source, and is determined better than in the case of known apparatus. Figure 2 shows a first embodiment of an apparatus operating in accordance with the aforesaid principles. The apparatus comprises a superluminescent laser source 20, which as is well known known has low coherence characteristics. The light beam emitted by the source 20 is fed through an optical fibre 21 to a directional coupler 22 which splits it into a reference light beam and a measurement light beam. The reference light beam is fed through an optical fibre 23 to an optical collimation element 24 which directs the light beam onto a polarizing beam splitter 25. The light beam is then deviated by reflection by the beam splitter 25 onto a quarter-wave delay plate 26, passes through a modulator 27 and encounters a movable mirror 28 which reflects it. The light beam reflected by the mirror 28 again passes through the modulator 27 and the delay plate 26, then passes through the beam splitter 25 to be collected by an optical collection element 29. The light beam collected by the element 29 is fed through an optical fibre 30 to a directional coupler 31. The measurement light beam is fed through an optical fibre 32 to an optical collimation element 33 which directs the light beam onto a polarization beam splitter 34. The light beam passes through the beam splitter 34, and then through a quarter-wave delay plate 35, to encounter the deflection prism 14. As seen in the scheme of Figure 1, the light beam passes through the prism 14, penetrates into the pipe 13 at a suitable angle and is scattered by the particles within the fluid which it encounters during its path, for example at the points x₁, x₂....xn of the pipe 13. The measurement light beam backscattered along the path of the incident light beam passes through the prism 14 and the delay plate 35, and is reflected by the beam splitter 34 onto a deflection prism 36 which deviates the light beam onto an optical collection element 37. The backscattered measurement light beam collected by the element 37 is fed through an optical fibre 38 to the directional coupler 31. In the directional coupler 31 the reference light beam reflected by the mirror 28 is superimposed on the measurement light beam backscattered by the particles within the fluid at the points x₁, x₂.....xn. From two separate exits of the directional coupler 31 there are emitted two separate light signals, which are identical but 180° out of phase, each being the result of said superimposing of the reflected reference light beam on the backscattered measurement light beam. The two said light signals are fed via respective optical fibres 39 and 40 to two respective photodetectors 41 and 42. On each photodetector an optical interference signal is produced due to the superimposing of the reflected reference light beam on the backscattered measurement light beam. At the output of the two photodetectors 41 and 42 two identical electrical signals 180° out of phase are obtained corresponding to the two said interference signals. The outputs of the two photodetectors 41 and 42 are connected to an electronic processor unit 43. The unit 43 is also connected to a stepping motor 44 which moves a translator 45 to which the mirror 28 is fixed. The mirror 28 is moved parallel to itself by the translator 45, driven by the stepping motor 44. As in the scheme of Figure 1 and for the same reasons, in the apparatus of Figure 2 for each position of the mirror 28 there corresponds an interference signal based on the velocity of a particle passing through a specific point of the points x₁, x₂....xn. Hence by moving the mirror 28 by means of the motor 44 it is possible to measure the fluid velocity distribution at these points. In contrast to the scheme of Figure 1, dividing the light beam of the laser source into a reference light beam and a measurement light beam and combining the reference light beam reflected by the mirror with the measurement light beam backscattered by the particles is not done in the same optical element (which in the case of Figure 1 is the beam splitter 11) but is done in two different optical elements, ie in the two directional couplers 22 and 31. The use of optical fibres dispenses with the need for the obligatory alignments of the scheme of Figure 1. It should be noted that in the apparatus of Figure 2 the most bulky and voluminous part of the apparatus, ie the part for generating and dividing the laser beam and for forming, detecting and processing the interference, is totally separate from the part of minimum dimensions, indicated by S, which performs the function of an actual probe projecting and collecting the light beam, and comprising the optical collimation element 33, the beam splitter 34, the delay plate 35, the deflection prism 36 and the optical collection element 37. These two parts of the apparatus are in fact connected together by only two optical fibres 32 and 38, the length of which can be varied according to requirements, while respecting the necessary dimensions to provide the said balancing of the optical arms. This represents a great advantage in those cases in which there is difficulty in placing the entire apparatus close to the pipe 13, as the probe S can be positioned close to the pipe 13, with the rest of the apparatus positioned at the necessary distance. Splitting the interference signal into two identical signals out of phase by 180° allows differential measurement in which the difference is computed between the two signals, the resultant interference signal being advantageously double their intensity and free from noise. Operationally, the electronic processor unit 43 in driving the motor 44 moves the mirror 28 into the various measurement positions and computes the difference to provide the resultant interference signals. From the positions of the mirror 28 and the values of the interference signals, the unit 43 provides the data relative to the velocity of the fluid within the pipe 13 at the various points x₁. x₂.....xn. The modulator 27, which can be of electro-optical or acoustic-optical type, introduces a carrier signal to the reference light beam and improves the detection characteristics. The polarizing beam splitter 25 together with the quarter-wave delay plate 26, and the polarizing beam splitter 34 together with the quarter-wave delay plate 35, enable the polarization of the reference light signal and measurement light signal to be controlled such that interference between the two light signals is possible. Figure 3 shows an alternative apparatus to that of Figure 2. Again in this case, a superluminescent laser source 50 feeds a light beam through an optical fibre 51 to a directional coupler 52 which splits it into a reference light beam and a measurement light beam. However in this case the reference light beam is fed through an optical fibre 53 and an optical collimation element 54 to a movable right prism 55. The right prism 55 reflects the light beam onto an optical collection element 57. A modulator 56 is interposed between the prism 55 and the element 57. The light beam collected by the element 57 is fed through an optical fibre 58 to a directional coupler 59. In addition, in contrast to the apparatus of Figure 2, the measurement light beam is fed through an optical fibre 60 and an optical element 61 directly to the deflecting prism 14, the backscattered measurement light beam being collected by the same optical element 61 and fed through the same optical fibre 60 to the directional coupler 52 which has split the light beam of the laser source 50. The optical element 61 therefore acts jointly as a collimation element and a collection element, with the incident and backscattered measurement light beam travelling along the same optical fibre 60. From the directional coupler 52 the backscattered measurement light beam is fed through an optical fibre 62 to the directional coupler 59. In the same manner as the apparatus of Figure 2, the reference light beam reflected by the right prism 55 is superposed in the coupler 59 on the measurement light beam backscattered by the particles within the fluid at the points x₁, x₂.....xn of the pipe 13, two separate identical light signals out of phase by 180°, each resulting from said superimposing, being fed through two respective optical fibres 63 and 64 to two respective photodetectors 65 and 66. The outputs of the two photodetectors 65 and 66 are connected to an electronic processor unit 67. The unit 67 is also connected to a stepping motor 68 which moves a translator 69 to which the right prism 55 is fixed. The right prism 55 is moved parallel to itself by the translator 69, driven by the stepping motor 68. The operation of the apparatus of Figure 3 is analogous to that of the apparatus of Figure 2, taking account of the fact that the functions of the movable mirror 28 of Figure 2 are performed in Figure 3 by the right prism 55. The apparatus of Figure 3 is more simple than the apparatus of Figure 2, particularly because a single optical fibre 60 is provided, together with a single optical element 61, for projecting and collecting the measurement light beam. Because of the minimum dimensions of the probe of the apparatus of Figure 3, consisting only of the optical collimation and collection element 61, the most inaccessible pipes can be scanned. As in the case of the apparatus of Figure 2, the apparatus of Figure 4 comprises a superluminescent source 70 which feeds a light beam through an optical fibre 71 to a directional coupler 72 which splits it into a reference light beam and a measurement light beam. The reference light beam is fed through an optical fibre 73 and a modulator 74 to an optical collimation element 75 which produces at its exit a spatially wide optical field. The measurement light beam is fed through an optical fibre 76 to the same probe S as shown in Figure 2, which feeds the beam onto the deflection prism 14. The backscattered measurement light beam is fed through an optical fibre 77 to another optical collimation element 78 which produces at its exit a spatially wide optical field. The wide reference light beam produced by the element 75 is fed via a polarizing beam splitter 79 and a quarter-wave delay plate 80 to a multiple mirror 81. The multiple mirror 81 comprises a series of mirrors 82 arranged in an ordered manner within the optical field at a distance apart corresponding to the separation distance between the investigation points x₁, x₂....., xn within the pipe 13. The wide reference light beam reflected by the multiple mirror 81 is fed through the delay plate 80 and polarizing beam splitter 79 to a beam splitter 83. The wide measurement light beam produced by the element 78 is also fed to the beam splitter 83. The two said wide reference and measurement light beams are superimposed within the beam splitter 83, which feeds two separate identical wide light signals out of phase by 180°, each resulting from said superimposing, to two respective series of photodetectors indicated by two blocks 84 and 85. The outputs of the two series of photodetectors 84 and 85 are connected to an electronic processor unit 86. In this apparatus each mirror 82 allows the formation of an interference light signal relative to the measurement light beam backscattered by a particle within the fluid at a specific point of the points x₁, x₂.....xn. A respective pair of photodetectors, one pertaining to the photodetector series 84 and the other to the photodetector series 85, enables the unit 86 to compute the interference signal difference for the point under measurement and hence the fluid velocity at this point. The apparatus of Figure 4 therefore measures the fluid velocity at different points within the pipe at the same time without having to move the optical components within the apparatus, in contrast to the previously described apparatus in which the fluid velocity at one point is measured at a different time from that at another point, after moving an optical component (the mirror 28 or the right prism 55). Basically the apparatus of Figures 2 and 3 effect a serial reading of the fluid velocity at the various points of the pipe, whereas the apparatus of Figure 4 effects a parallel reading of this velocity. The apparatus of Figure 4 can be modified by replacing the optical fibres 76 and 77 with a single optical fibre and the probe S with an optical collimation and collection element, and feeding the backscattered measurement light beam from the directional coupler 72 to the optical collimation element 78, as in the case of the apparatus of Figure 3. The apparatus of Figures 2, 3 and 4 can use components which, either alone or in combination, perform functions equivalent to those illustrated. The movable mirror, the movable right prism and the multiple mirror can be replaced by one or more optical components, forming part of the interferometer, and able to vary the optical path of the reference light beam. The mirror and the prism can be replaced by any other reflecting element. The multiple mirror can be replaced by any optical component comprising a plurality of reflecting elements. Any other low-coherence laser source can be used in place of the superluminescent laser source. The photodetectors can be replaced by photoelectric transducers of any type, such as photomultipliers. A simple transparent element such as a glass plate can be used in place of the deflection prism 14, in which case the probe or the optical collimation and collection element must be inclined to the direction of fluid flow in the pipe, for the aforesaid reasons. The probe could also be inserted directly into the wall of the pipe 13, as shown in Figure 5, or into the pipe itself as shown in Figure 6, by obvious support and fixing means, so avoiding the use of a window. In Figures 5 and 6 the probe is shown by way of example as the optical collimation and collection element 61. In the apparatus of Figures 2, 3 and 4, instead of differential measurement, simple measurement of a single interference signal can be used as in the scheme of Figure 1, by employing a single photoelectric transducer in the apparatus of Figures 2 and 3, and a single series of photoelectric transducers in the apparatus of Figure 4. If it is desired to measure the fluid velocity at only one point of the pipe, a simplified version of the apparatus can be provided in which the optical path of the reference light beam is fixed, for example by using a fixed simple mirror or a fixed right prism. The fluid can be a liquid or an aeriform. With the described measurement system the velocity of a fluid moving within any delimited or non-delimited space can be measured by simply projecting the measurement light signal into the fluid and collecting that component thereof backscattered by the particles within the fluid.	A laser apparatus for measuring the velocity of a fluid, in which a measurement laser light beam (M) is fed into the fluid and scattered by particles within the fluid after which it is made to interfere with a reference laser light beam (R) to generate an interference signal indicative of the velocity of the particles, comprising a low-coherence laser source (10), interferometric means (22,52,72) for splitting the light beam of said laser source (10) into said reference light beam (R) and said measurement light beam (M), optical components arranged so as to cause the reference light beam (R) derived from the laser source (10) to interfere with the backscattered component resulting from the scattering of the measurement light beam (M), and photoelectric transducers (84,85) for detecting said interference signal, characterised in that said optical components include a plurality of reflecting elements (82) arranged such that each element defines a different optical path length for the part of the reference light beam (R) incident thereon. A laser apparatus for measuring the velocity of a fluid, in wich a measurement laser light beam (M) is fed into the fluid and scattered by particles within the fluid after which it is made to interfere with a reference laser light beam (R) to generate an interference signal indicative of the velocity of the particle, comprising a low-coherence laser source (10), interferometric means for splitting the light beam of said laser source (10) into said reference light beam (R) and said measurement light beam (M), optical components arranged so as to cause the reference light beam (R) derived from the laser source (10) to interfere with the backscattered component resulting from the scattering of the measurement light beam (M), photoelectric transducers (65, 66) for detecting said interference signal, characterised in that said optical components include a movable reflecting element (28, 55) for varying the optical path length of the reference light beam incident thereon, said reflecting element being connected to a translator (45, 69) movable by a motor (44, 68), an electronic processor unit (67) being provided connected to the motor (68) and transducers (65, 66), to determine from the interference signal and the position of the reflecting element (55) the velocity of each particle encountered within the fluid by the measurement light beam (M). A laser apparatus as claimed in claim 2, wherein the movable reflecting element (55) is a right prism (55) which deviates the reference light beam (R) from a first directional coupler (52) towards a second directional coupler (59). A laser apparatus as claimed in claim 3, wherein a modulator (56) is interposed between the right prism (55) and the second directional coupler (59). A laser apparatus as claimed in claim 1, wherein the interferometric means comprise a directional coupler (72) which splits the light beam emitted by the laser source (70) into said reference light beam (R) and said measurement light beam (M), the reference light beam (R) being fed to a first optical element (75) which produces at its exit a wide light beam directed to a first beam splitter (79) which feeds it to said plurality of reflecting elements (82), the measurement light beam (M) being fed to a probe (5) which projects it into the fluid and collects said backscattered component, feeding it to a second optical element (78) which produces at its exit a wide light beam and directs it to a second beam splitter (83), the first beam splitter (79) feeding the wide reference light beam (R) reflected by the reflecting elements (82) to the second beam splitter (83) to generate a plurality of interference signals. A laser apparatus as claimed in claim 5, wherein the probe (5) comprises a beam splitter (34) which feeds the measurement light beam (M) into the fluid and collects said backscattered component, feeding it to a deflection prism (36) which directs it to said second optical element (78). A laser apparatus as claimed in claim 5, wherein the probe (5) comprises a collimation and collection element (61) which feeds the measurement light beam (M) into the fluid and collects said backscattered component, feeding it to the directional coupler (52) which directs it to said second optical element (78), the connection between the directional coupler (52) and the collimation and collection element (61) being via a single optical fibre (60). A laser apparatus as claimed in claim 5, wherein said plurality of reflecting elements (82) form part of a multiple mirror (81). A laser apparatus as claimed in claim 1 or 2, for measuring the velocity of the fluid within a pipe (13), wherein the measurement laser beam (M) is fed into the pipe (13) via a window consisting of a deflection prism (14). A laser apparatus as claimed in claim 5, for measuring the velocity of the fluid within a pipe (13), wherein said probe (61) is inserted into the pipe wall. A laser apparatus as claimed in claim 5, for measuring the velocity of the fluid within a pipe (13), wherein said probe (61) is inserted into the pipe (13).	CISE SPA; CISE S.P.A.	GUSMEROLI VALERIA; MARTINELLI MARIO; GUSMEROLI, VALERIA; MARTINELLI, MARIO
EP-0489476-B1	489,476	EP	B1	EN	19,960,424	1,992	20,100,220	new	H01J61	null	H05B41, H01J61	H01J 61/54A	Rapid start fluorescent lamp having quick hot restarting	A rapid start fluorescent lamp (10) having an improved hot restarting time. The lamp (10) includes the standard envelope (12) and end cap (14) through which electrical connection is made by conductive feedthroughs (18,20) which extend through the lamp stem (16) to the interior of the lamp. One of the feedthroughs (20) is connected to the cathode (22), and the other is connected to the leads (28,30) of a fuse element (32) which is contained within an envelope to isolate the fusible element (32) from the lamp environment. A thermally activated bimetallic element (46) is disposed across the leads (28,30) of the fuse (24). The other lead (30) of the fusible element (32) is connected to the other end of the cathode (40). When the bimetal element (46) is cold, it will bridge the connection between the other feedthrough (18) to the other end of the cathode (22) to permit rapid starting. When the bimetal (46) heats up, the connection of both ends of the cathode (22) to the heating current is broken. The location of the bimetallic element (46) within the lamp (10) envelope (12) but not in the fuse (24) container permits it to open and close more rapidly. Additionally the fuse assembly (24) is utilized as part of the supporting structure for the filament (22) assembly.	BACKGROUND OF THE INVENTIONThe invention relates to fluorescent lamps of the so-called rapid start type. Such lamps are provided with thermal switches, responsive to cathode (filament) heat, for turning off the cathode heating current after starting and during lamp operation. Rapid start fluorescent lamps are provided with cathode heating current, for heating the cathodes to electron-emitting temperature so that the lamps start quickly without damaging the electron-emitting material of the cathodes. The cathode heating consumes about one and one-half to two watts of electrical power per cathode. While the lamps are operating, the cathodes can provide adequate electron emission without the need for the supply of heating current to the cathodes. Accordingly, turning off the cathode heating current when the lamps are operating can save about three or four watts of electrical energy per lamp, resulting in considerable energy and money savings in lighting systems. In this regard, see U.S. Patent No. 4,517,493. U.S. Pat. Nos. 4,097,779 and 4,114,968 disclose rapid start fluorescent lamps provided with a thermal cutout switch near each cathode, and in electrical series with the associated cathode, for turning off the cathode current after the lamps start and while they are operating. These patents disclose U-shaped bimetal switches sealed in glass envelopes which are mounted near each cathode. After each cathode is heated sufficiently by the heating current heat from the cathode causes the nearby bimetal switch member to bend and open the current circuit to the cathode. The manufacture of fluorescent lamps involves coating the tungsten cathode coils with an electron emission coating. After the lamps are assembled, the cathodes are activated by passing current through them to heat them. However, the cathode current cutout switches in the lamps will turn off the activation cathode heating current prior to complete activation of the cathodes. U.S. Pat. No. 4,114,968 solves this problem by connecting fuse wires across the thermal switch, for shorting the switch and permitting activation of the cathodes. The fuses are then blown (severed), by applying an electrical pulse through each of the series-connected fuses and cathodes. The fuses must be able to carry the cathode activation current and also be capable of being blown by a current pulse of insufficient strength to damage the cathode. Fuse timing is also important, since the fuse-blowing pulse must be applied while the thermal switch is in open condition so it will not short-circuit the pulse away from the fuse. Similar lamps are known from US-A-4 528 479 and US-A-4 709 187. The quick start designs currently being marketed share a common problem: hot restarting. When the lamps are turned off after the switches have opened, a cool-off period is required to allow the switches to close, thus permitting current to flow through the cathode and restart the lamp. A series of tests were performed on rapid start lamps from various manufacturers to determine the restart time in a worst case scenario. The test consisted of operating the lamps for 20 minutes at an ambient temperature of 198°C (110°F), which is the approximate temperature that the lamps experience in a standard four-lamp fixture. The lamps were then shut off for approximately two seconds and turned back on at 108 volts. The time that was required for the lamps to start was recorded. The times recorded for three major lamps manufacturers ranged from 52 to 68 seconds. All of these restart times are longer than would be considered acceptable by the consumer. The present invention is directed toward providing a rapid start lamp having a considerably shorter hot restart time. SUMMARY OF THE INVENTIONThis invention is directed to a rapid start fluorescent lamp according to claim 1 having an improved hot restarting time. The lamp includes the standard envelope and end cap through which electrical connection is made by conductive feedthroughs which extend through the lamp stem to the interior of the lamp. One of the feedthroughs is connected to the cathode (filament means), the other of is connected to the leads of a fusible element (fuse means) which is contained within an envelope to isolate the fusible element from the lamp environment. A thermally activated bimetallic element is disposed across the leads of the fuse. The other lead of the fusible element is connected to the other end of the cathode. When the bimetal element is cold, it will bridge the connection between the other feedthrough to the other end of the cathode to permit rapid starting by application of heating current. When the bimetal heats up, the connection of both ends of the cathode to the heating current is broken. In this design, the fusible element is enclosed within a container and is thus isolated from the lamp environment. However, the bimetallic element, since it is not located within the container may be is larger than that of previous lamps. According to the invention, the bimetallic element is positioned beneath the upper surface of the glass seal through which the feedthrough wires extend. By placing the bimetallic element in this location, the heat radiated by the arc glow and the heating of the filament prior to lamp starting does not cause premature opening of the switch which could prevent the lamp for starting. This positioning also permits rapid closing of the switch when the lamp is shut off thus permitting quicker hot restarting. Additionally, the cathode mount feedthroughs and fusible element are arranged in an economical manner which utilizes the leads of the fusible element as a supporting structure for the bimetallic switch, thus saving materials and expense, which are important considerations for mass produced lamps. The dependent claims describe particular embodiments of the invention. BRIEF DESCRIPTION OF THE DRAWINGSFor a better understanding of the invention, reference is made to the following drawings which are to be taken in connection with the detailed specification to follow: Fig. 1 is a front view of the cathode mount and bimetallic element constructed in accordance with the present invention; and Figs. 2 and 3 are a side view and a top view of the arrangement of Fig. 1. DESCRIPTION OF THE PREFERRED EMBODIMENTThe drawings illustrate a fluorescent lamp 10 which includes a glass envelope 12 and an end cap 14 of any standard design. Envelope 12 is generally constructed of glass and coated internally with a phosphor material and containing a gas fill as is known to those skilled in the art. Extending away from end cap 14 is a glass stem 16 through whose upper surface extend conductive feedthroughs 18, 20 which are connected to electrical connectors on end cap 14 and thereafter to the source of current. Feedthrough 20 provides electrical connection and mechanical support to one end of a cathode 22. The upper surface of stem 16 has been illustrated as flat, however a flat surface is not necessary as it may be of any configuration. Also mounted within envelope 12 is an enclosed fuse assembly 24, which includes a container 26 and a pair of lead wires 28, 30. Connected internally within container 24 between lead wires 28, 30 is a fusible (frangible) element 32. Fusible element 32 is mounted within container 24 so that it is isolated from the environment of envelope 12 which permits fusible element 32 to be blown after actuation of cathode 22 during lamp manufacture without contaminating the lamp environment. After fusible element 32 is severed it plays no part in the electrical connection of cathode 22. However fuse assembly 24 at all times serves as part of the mechanical support of the cathode and thermal switch. Lead 28 of fuse 24 is electrically and mechanically joined to feedthrough 18 by means of a connecting wire 34 which extends toward envelope 12. The lower end 36 of lead 28 of fuse 24 extends parallel to but beneath the upper surface 38 of lamp stem 16. Lead 30 of fuse 24 is connected to a wire 40 which leads upwardly and joins a support rod 42 which is connected to the other end of cathode 22. The lower portion 44 of lead 30 of fuse 24 also extends parallel and beneath the upper surface 38 of lamp stem 16. A bimetallic element 46 extends between portions 36 and 44 of fuse leads 28, 30 so as to provide electrical connection therebetween when it is unheated. One end of bimetallic element 46 is fixed to portion 36 of lead 28 and the other end of bimetallic element 46 contacts portion 44 of lead 30 when unheated. When bimetallic element 46 is heated, the free end will be biased away from contact with portion 44 of lead 30 to break the electrical connection between leads 28 and 30 and thus cut off the supply of heating current to cathode 22. In operation, upon cold starting, bimetallic element 46 will be in engagement of arm 34 of lead 30. Thus, an electrical connection will be made between feedthrough 18, connecting wire 34, fuse lead 28, bimetallic element 46, fuse lead 30, wire 40, support arm 42, cathode 22 and feedthrough 20. Accordingly, heating current will flow to cathode 22 for starting. After lamp 10 becomes lit, the heat of the lamp operation causes the free end of bimetallic element 46 to be biased away from arm 44 to break the electrical connection between feedthroughs 18 and 20 to cathode 22. Thus, only feedthrough 20 will be connected to cathode 22. The location of the bimetallic element 46 outside of fuse container 26 and its positioning according to the invention beneath the upper surface 38 of lamp stem 16 permits a larger than usual bimetallic element 46 to be utilized. Suitable dimensions are on the order of 14.45 x 3.25 x 0.15 millimetres. Suitable material for bimetallic element 46 is 40% nickel and 60% iron on the low expansion side and 75% nickel, 22% iron and 3% chrome on the high expansion side. Of course, the dimensions and composition may be varied depending on the application and desired operational parameters. In the location illustrated, the heat radiated by the arc glow of cathode 22 and its heating prior to starting will not cause premature opening of bimetallic element 46, which would prevent the lamp from starting. Tests indicate that the hot restarting time of a lamp constructed in accordance with the present invention is on the order of 30 seconds which is less than half the time of conventionally designed lamps. Clearly this delay is more acceptable to the consumer. Although the present invention has been described in conjunction with a preferred embodiment, it is to be understood that modifications and variations may be resorted to without departing from the scope of the claims as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended Claims.	A rapid start fluorescent lamp (10) comprising: a lamp envelope (12), an end cap (14) disposed on one end of said lamp envelope (12); a lamp stem (16) having an upper surface (38) disposed within said envelope (12); first and second conductive feedthroughs (18, 20) extending through the upper surface (38) of said lamp stem (16) to said end cap (14) for electrical connection thereto; filament means (22), said filament means (22) being electrically connected to one of said conductive feedthroughs (20); thermally activated switch means (46); the first and the second feedthrough (18, 20) being connected via the filament means (22) and the thermally activated switch means (46) when the switch means (46) are cold, the connection between the first and the second feedthrough (18, 20) via the filament means (22) and the switch means (46) and the switch means (46) being broken when the switch means (46) are heated, characterized in that said switch means (46) are positioned within said lamp envelope (12) at a level below that of the upper surface (38) of the lamp stem (16). The fluorescent lamp as claimed in Claim 1 wherein said switch means (46) are disposed so that the plane of the switch means is perpendicular to the longitudinal axis of the lamp envelope (12). The fluorescent lamp as claimed in Claim 1, the thermally activated switch means (46) being disposed across fuse means having a fusible element (32). The fluorescent lamp as claimed in Claim 3 wherein said fuse means includes a container (26) which seals said fusible element (32) therewithin so as to isolate the fusible element (32) from the environment of the lamp envelope (12). The fluorescent lamp as claimed in Claim 1 wherein said thermally activated switch means comprises a bimetallic element (46).	PHILIPS ELECTRONICS NV; PHILIPS ELECTRONICS N.V.	BOYCE WALTER; LEYH THOMAS; BOYCE, WALTER; LEYH, THOMAS
EP-0489479-B1	489,479	EP	B1	EN	19,941,214	1,992	20,100,220	new	F01C1	F01C21	F01C21, F04C18, F01C1	R04C230:60, F01C 21/00C, F01C 1/02B2, R05B230:60	Scroll type fluid machinery	The present invention relates to a scroll type fluid machinery provided with a slide type radius of revolution variable mechanism, and has an object of preventing unilateral working of a rotating bearing 23 due to tilted rotation of a drive bushing 21 and a balance weight 27 fixed thereto. The construction of the present invention is formed in such a manner that a bolt 41 for regulating tilted rotation is projected at an inner end of a rotary shaft 7, a shaft portion 41a thereof is made to penetrate through a vain hole 42 bored in the balance weight 27, and a bearing surface 41c of a head 41b thereof is brought into slidable contact with the inner end surface of the balance weight 27. When the radius of revolution is varied at the time of revolution in a solar motion of a revolving scroll 14, an eccentric driving pin 25 slides in a slide groove 24 and the shaft portion 41a of the bolt 41 slides in the vain hole 42 at the same time. In the interim, the bearing surface 41c of the head 41 comes into slidable contact with the inner end surface of the balance weight 27, thereby to suppress tilted rotation of the balance weight 27.	FIELD OF THE INVENTION AND RELATED ART STATEMENTThe present invention relates to a scroll type fluid machinery used as a compressor, an expansion machine and the like. Such a scroll type fluid machinery is known from US-A-3 986 799. Fig. 5 shows an example of another conventional scroll type compressor. In Fig. 5, a closed housing 1 consists of a cup-shaped body 2, a front end plate 4 fastened to the cup-shaped body 2 with a bolt 3, and a cylindrical member 6 fastened to the front end plate 4 with a bolt 5. A rotary shaft 7 which penetrates through the cylindrical member 6 is supported rotatably by the housing 1 through bearings 8 and 9. A stationary scroll 10 and a revolving scroll 14 are disposed in the housing 1. The stationary scroll 10 is provided with an end plate 11 and a spiral wrap 12 set up on the inner surface thereof, and the stationary scroll 10 is fixed in the housing 1 by fastening the end plate 11 to the cup-shaped body 2 with a bolt 13. The inside of the housing 1 is partitioned by having the outer circumferential surface of the end plate 11 and the inner circumferential surface of the cup-shaped body 2 come in close contact with each other, thus forming a discharge cavity 31 on the outside of the end plate 11 and delimiting a suction chamber 28 inside the end plate 11. Further, a discharge port 29 is bored at the center of the end plate 11, and the discharge port 29 is opened and closed by means of a discharge valve 30. The revolving scroll 14 is provided with an end plate 15 and a spiral wrap 16 which is set up on the inner surface thereof, and the spiral wrap 16 has substantially the same configuration as that of the spiral wrap 12 of the stationary scroll 10. The revolving scroll 14 and the stationary scroll 10 are eccentric with respect to each other by the radius of revolution in a solar motion, and are engaged with each other while shifting an angle by 180° as shown in the figure. Then, chip seals 17 buried in the tip surface of the spiral wrap 12 come into close contact with the inner surface of the end plate 15, chip seals 18 buried in the tip surface of the spiral wrap 16 come into close contact with the inner surface of the end plate 11, and side surface of the spiral wraps 12 and 16 come into linear contact with each other at a plurality of locations, thus forming a plurality of compression chambers 19a and 19b which form almost point symmetry with respect to the center of the spiral. A drive bushing 21 is fitted rotatably in a cylindrical boss 20 which is projected at a central part of the outer surface of the end plate 15 through a rotating bearing 23, and an eccentric driving pin 25 projected eccentrically at the inner end of the rotary shaft 7 is fitted slidably into a slide groove 24 which is bored in the drive bushing 21. Further, a balance weight 27 for balancing dynamic unbalance caused by revolution in a solar motion of the revolving scroll 14 is installed on the drive bushing 21. Besides, 36 denotes a thrust bearing which is interposed between a peripheral edge of the outer surface of the end plate 15 and the inner surface of the front end plate 4, 26 denotes a mechanism for checking rotation on its axis consisting of an Oldham's link which allows revolution in a solar motion of the revolving scroll but checks rotation on its axis thereof, and 37 denotes a balance weight fixed to the rotary shaft 7. Now, when the rotary shaft 7 is rotated, the revolving scroll 14 is driven through a revolution drive mechanism consisting of the eccentric driving pin 25, the drive bushing 21, the boss 20 and the like, and the revolving scroll 14 revolves in a solar motion on a circular orbit having the radius of revolution in a solar motion, viz., an eccentric quantity between the rotary shaft 7 and the eccentric driving pin 25 as the radius while being checked to rotate on its axis by means of the mechanism 26 for checking rotation on its axis. Then, the linear contact portion between the spiral wraps 12 and 16 moves gradually toward the center of the spiral. As a result, the compression chambers 19a and 19b move toward the center of the spiral while reducing the volume thereof. The gas which flows into a suction chamber 28 through a suction port not shown is taken into respective compression chambers 19a and 19b through outer end opening portions of the spiral wraps 12 and 16 in keeping with the above and reaches a chamber 22 at the center while being compressed. The gas passes further through a discharge port 29, pushes a discharge valve 30 open and is discharged into a discharge cavity 31, and flows out therefrom through a discharge port not shown. When the revolving scroll 14 is revolving in a solar motion, centrifugal force toward an eccentric direction of the revolving scroll 14 and gas force by the compressed gas in respective compression chambers 19a and 19b act on the revolving scroll 14, and the revolving scroll 14 is pushed in a direction of increasing the radius of revolution by resultant force of these forces. Thus, the side surface of the wrap 16 thereof comes in close contact with the side surface of the wrap 12 of the stationary scroll 10, thereby to prevent leakage of the gas in the compression chambers 19a and 19b. Then, when the side surface of the wrap 12 and the side surface of the wrap 16 slide while being in close contact with each other, the radius of revolution of the revolving scroll 14 varies automatically. In keeping with this, the eccentric driving pin 25 slides in the slide groove 24 in the longitudinal direction thereof, and outer end surfaces of the drive bushing 21 and the balance weight 27 slide on the inner end surface of the rotary shaft 7. In above-described scroll type fluid machinery, the center of gravity of the balance weight 27 is located to the left of the drive bushing 21 in the figure. Further, outer end surfaces of the drive bushing 21 and the balance weight 27 are slidable on the inner end surface of the rotary shaft 7, and the eccentric driving pin 25 is fitted into the slide groove 24 slidably. Therefore, when the revolving scroll 14 is revolving in a solar motion, the balance weight 27 and the drive bushing 21 formed in one body therewith rotate with tilting counterclockwise in the figure by means of centrifugal force acting on the center of gravity of the balance weight 27. As a result, there has been such a problem that unilateral working is produced on the rotating bearing 23 and the outer end surface of the drive bushing 21 works unilaterally on the inner end surface of the rotary shaft 7. OBJECT AND SUMMARY OF THE INVENTIONIt is an object of the present invention which has been made in view of such a point to provide a scroll type fluid machinery in which above-described problems are solved, unilateral working of a rotating bearing is prevented, and unilateral working between an outer end surface of a drive bushing and an inner end surface of a rotary shaft is also prevented. In order to achieve above-described object, according to the construction of the present invention, there is provided a scroll type fluid machinery in which a stationary scroll and a revolving scroll having spiral wraps set up on inner surfaces of end plates, respectively, are engaged with each other, a drive bushing is inserted rotatably into a boss which is projected at a central part of the outer surface of the end plate of the revolving scroll, an eccentric driving pin projected at an inner end of a rotary shaft is fitted slidably into a slide groove which is bored in the drive bushing, and a balance weight for balancing dynamic unbalance caused by revolution in a solar motion of the revolving scroll is provided on the drive bushing, characterized in that a tilted rotation regulating member is projected at the inner end of the rotary shafts the tilted rotation regulating member is made to penetrate through a hole which is bored in the drive bushing or the balance weight and has a size which allows sliding of the drive bushing, and a regulating surface which is in contact slidably with the inner end surface of the drive bushing or the balance weight is provided at a tip of the tilted rotation regulating member. It is also possible to construct above-mentioned tilted rotation regulating member with a bolt provided with a head which forms the regulating surface. It is also possible to have a skim interposed between the regulating surface and the inner end surface of the drive bushing or the balance weight. It is also possible to install a snap ring which constructs the regulating surface at a tip of a pin which forms the tilted rotation regulating member. The present invention being provided with above-described construction, the operation thereof is performed in such a manner that, when the radius of revolution of the revolving scroll is varied, the tilted rotation regulating member moves in the hole and the regulating surface comes in contact with the inner end surface of the drive bushing or the balance weight slidably so as to regulate tilted rotation of the drive bushing and the balance weight. As the effects of the present invention, tilted rotation of the drive bushing and the balance weight is regulated when the revolving scroll is revolving in a solar motion, thus making it possible to prevent flaking and wear between the drive bushing and the rotating bearing and between the outer end surface of the drive bushing or the balance weight and the inner end surface of the rotary shaft. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a partial sectional view taken along a line I-I in Fig. 2, showing a first embodiment of the present invention; Fig. 2 is a cross sectional view taken along a line II-II in Fig. 1; Fig. 3 is a partial longitudinal sectional view corresponding to Fig. 1 showing a second embodiment of the present invention; Fig. 4 is a partial longitudinal sectional view corresponding to Fig. 1 showing a third embodiment of the present invention; and Fig. 5 is a longitudinal sectional view of a conventional scroll type compressor. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTSPreferred embodiments of the present invention will be described in detail hereafter in an illustrative manner with reference to the drawings. Fig.1 and Fig. 2 show a first embodiment of the present invention, wherein Fig. 1 is a partial longitudinal sectional view taken along a line I-I in Fig. 2 and Fig. 2 is a cross sectional view taken along a line II-II in Fig. 1. As shown in Fig. 1 and Fig. 2, a collar 40 is provided at an inner end of a rotary shaft 7, and a tilted rotation regulating bolt 41 is installed fixedly on the collar 40. A shaft portion 41a of this bolt 41 penetrates through a hole 42 bored in a balance weight 27, and a bearing surface 41c of a head 41b thereof is in contact slidably with an inner end surface of the balance weight 27. Further, the hole 42 is formed in a size which allows sliding of a drive bushing 21. Other construction is similar to that of a conventional device shown in Fig. 5, and same reference numerals are affixed to corresponding members. Now, when the radius of revolution of a revolving scroll 14 is varied, an eccentric driving pin 25 slides in a slide groove 24 in accordance with the variation, and the shaft portion 41a of the tilted rotation regulating bolt 41 slides in the hole 42 at the same time. Further, the bearing surface 41c of the head 41b comes in slidable contact with the inner end surface of the balance weight 27 so as to regulate tilted rotation of the balance weight 27 and the drive bushing 21. It is possible to control tilted rotation quantity of the drive bushing 21 easily by adjusting the screwing quantity of the tilted rotation regulating bolt 41 into the collar 40. Further, since the bolt 41 is apart from the center of the drive bushing 21, tilted rotation of the drive bushing 21 can be regulated effectively. Fig. 3 shows a second embodiment of the present invention. This second embodiment is different from the first embodiment in a point that a skim 43 is interposed between the bearing surface of the head 41b and the inner end surface of the balance weight 27, but other construction remains the same, and same reference numerals are affixed to corresponding members. In the second embodiment, it is possible to prevent fretting between the bearing surface of the head 41b and the inner end surface of the balance weight 27 by means of the skim 43, and also to relieve working precision of respective components by selecting the wall thickness of the skim 43 appropriately. Fig. 4 shows a third embodiment of the present invention. In the third embodiment, a pin 44 is fixed to the collar 40, and a left end surface of a snap ring 45 locked to the head of the pin 44 is made to come into slidable contact with the inner end surface of the balance weight 27. Other construction is similar to that of the first embodiment, and same reference numbers are affixed to corresponding members. In above-mentioned respective embodiments, the bolt 41 or the pin 44 is fixed to the collar 40, but it is possible to install a tilted rotation regulating member having an optional configuration and structure projecting at the inner end of the rotary shaft 7, and it is also possible to directly regulate tilted rotation of the drive bushing 21 by the regulating surface provided on the tilted rotation regulating member. As it is apparent from the explanation described above, according to the present invention, a tilted rotation regulating member is projected at an inner end of a rotary shaft, the tilted rotation regulating member is made to penetrate through a hole which is bored in a drive bushing or a balance weight and has a size which allows sliding of the drive bushing, and a regulating surface which comes into slidable contact with the inner end surface of the drive bushing or the balance weight is provided at the tip thereof. Thus, tilted rotation of the drive bushing and the balance weight is regulated when the revolving scroll is revolving in a solar motion, thus making it possible to prevent flaking and wear between the drive bushing and the rotating bearing and between the outer end surface of the drive bushing or the balance weight and the inner end surface of the rotary shaft.	A scroll type fluid machinery in which a stationary scroll (10) and a revolving scroll (14) having spiral wraps (16) set up on inner surfaces of end plates (15), respectively, are engaged with each other, a drive bushing (21) is inserted rotatably into a boss (20) which is projected at a central part of the outer surface of the end plate (15) of said revolving scroll (14), an eccentric driving pin (25) projected at an inner end of a rotary shaft (7) is fitted slidably into a slide groove (24) which is bored in said drive bushing (21), and a balance weight (27) for balancing dynamic unbalance caused by revolution in a solar motion of said revolving scroll (14) is provided on said drive bushing (21), wherein a tilted rotation regulating member (41) is projected at the inner end of said rotary shaft, characterized in that said tilted rotation regulating member is made to penetrate through a hole (42) which is bored in said drive bushing (21) or said balance weight (27) and has a size which allows sliding of said drive bushing, and a regulating surface (41c) which is in slidable contact with the inner end surface of said drive bushing (21) or said balance weight (27) is provided at a tip of said tilted rotation regulating member. A scroll type fluid machinery according to Claim (1), characterized in that said tilted rotation regulating member is constructed of a bolt (41) provided with a head (41b) which forms said regulating surface (41c). A scroll type fluid machinery according to Claim (1), characterized in that a skim (43) is interposed between said regulating surface and the inner end surface of said drive bushing (21) or said balance weight (27). A scroll type fluid machinery according to Claim (1), characterized in that a snap ring (45) which forms said regulating surface is installed at a tip of a pin (44) forming said tilted rotation regulating member.	MITSUBISHI HEAVY IND LTD; MITSUBISHI JUKOGYO KABUSHIKI KAISHA	IIO TAKAYUKI C O MITSUBISHI JU; TANIGAKI RYUHEI C O MITSUBISHI; IIO, TAKAYUKI, C/O MITSUBISHI JUKOGYO K.K.; TANIGAKI, RYUHEI, C/O MITSUBISHI JUKOGYO K.K.
EP-0489486-B1	489,486	EP	B1	EN	19,941,026	1,992	20,100,220	new	B66F9	F16C33, F16C29, B66F9	B66F9	B66F 9/08B, B66F 9/14	Bearing mounting arrangement for a lift mast	A bearing mounting arrangement for a lift mast assembly has a retaining device (60) which maintains a bearing member (32) from movement relative to a first member (48) of a lift mast assembly and directs a flow of lubricant past a second surface of the bearing member and into a groove (44) opening at a first surface in the bearing member. The retaining device includes an elongate retaining member disposed in an aperture in the bearing member and the first member. The retaining device forcibly engages the bearing member and aligns the apertures in the bearing and first members. The bearing mounting arrangement is particularly useful for mounting a lift mast assembly on a material handling vehicle and a thrust bearing member on a side shift carriage.	This invention relates to a bearing mounting arrangement, for a lift mast assembly, according to the preamble of claim 1. A bearing mounting arrangement of this type is shown in FR-A-2 449 820. The invention also relates to a lift mast assembly comprising such a bearing mounting arrangement. Bearing mounting arrangements have been utilized for many years on lift mast assemblies in a variety of ways. In one application, the bearing mounting arrangement is utilized to attach the lift mast assembly pivotally to the material handling vehicle so that the lift mast assembly may pivot about a transverse vehicle axis. An example of such a bearing mounting arrangement is shown in US-A-3,556,247, which discloses a sleeve bearing and a two piece connecting flange mounted on an upright of the lift mast assembly. The two piece flange pivotally connects the lift mast assembly to the material handling vehicle. Frequently, the sleeve bearing is disposed between the two piece connecting flange and a cylindrical supporting flange. An example of a cylindrical supporting flange is a drive axle housing connected to the frame of the material handling vehicle. US-A-4,100,986 discloses such a mounting arrangement. In each of these disclosures the sleeve bearing slidably rotates on the cylindrical supporting flange during pivoting of the mast assembly. Owing to the absence or lack of adequate lubricant in the area of sliding movement of the sleeve bearing premature wearing of the sleeve bearing and of the cylindrical supporting flange occurs. This premature wear causes looseness in the connection and affects the operation of the lift mast assembly in a number of ways. For example, a sloppy connection will place excessive side loading on the tilt jacks and cause fluid leakage and tilt jack failure. The loose connection also reduces the vehicle operator's ability to position accurately the lift mast assembly and load engaging fork. Thus an increase in load cycle time and a reduction in throughput occurs. Bearing mounting arrangements are also used in a side shift carriage applications to provide relatively free sliding movement of a side shiftable frame relative to a carriage frame. The bearing mounting arrangement typically connects a plain bearing member to the side shiftable frame and maintains the plain bearing member from transverse movement relative to the side shiftable frame. Owing to the absence or lack of adequate lubricant to the proper surface of the plain bearing member the potential for premature wear of the plain bearing member and the carriage frame occurs. Premature wear of the plain bearing causes rubbing and binding of the side shiftable frame relative to the carriage frame. This results in a reduction in the ease of movement of the side shiftable frame and ultimately causes failure of the side shift carriage. In order to alleviate premature wear of either of the above discussed bearings it is necessary to direct lubricant to the surface of the bearing which bears against the relatively movable frame portion (the cylindrical supporting flange or the carriage frame). In an attempt to solve the problem a hole was provided in the sleeve bearing to pass lubricant from a passage in the connecting flange through the sleeve bearing and to the appropriate side of the sleeve bearing. During operation it was found that the majority of the lubricant would follow the path of least resistance and exit the bearing at the wrong side. It was discovered that over time, dirt and hardened lubricant would plug the hole and cause new fresh lubricant to be blocked from passing to the proper side of the bearing. From visual inspection it appeared that the lubricant was flowing to the proper location, however, premature wear and further inspection after tear down of the bearing mounting arrangement proved otherwise. In the aforementioned applications the bearings were retained from movement relative to the stationary members (carriage frame and connecting flange) by complicated fastening arrangements. These arrangements included closely toleranced dowel and pin fits, sophisticated bearing carriers and the like. Such retaining methods are expensive to manufacture and less than totally successful in retaining the bearing. According to the present invention, a bearing mounting arrangement, for a lift mast assembly, comprises a bearing member having first and second opposed surfaces, a groove disposed in the bearing member and opening at the first opposed surface, and an aperture disposed in the bearing member and opening into the groove; a first flange member having first and second surfaces and an aperture disposed therein and opening at the first and second surfaces; a second flange member having a bearing surface, which is engaged with the bearing member first surface and being slidably movable relative to the bearing member; and retaining means for maintaining the bearing member from sliding movement relative to the first flange member first surface and for directing lubricating fluid from the first flange member aperture, through the bearing member aperture, and into the groove, the retaining means including an elongate retaining member, having an aperture extending longitudinally therethrough, the elongate retaining member being disposed in the apertures of the bearing and first flange members and forcibly engaging the bearing member, which retains the elongate retaining member in the apertures of the bearing and first flange members. The invention also provides a lift mast assembly according to claims 13, 14 and 15. Because the retaining device maintains the bearing member from sliding movement relative to the first flange premature wear of the bearing member and associated componentry due to improper movement of the bearing member is eliminated. Since the retaining device positively prevents misalignment of the apertures in the bearing and the first flange members the potential for lubricant blockage due to misalignment between the apertures is eliminated. The retaining device also directs lubricant directly to the groove of the bearing member and reduces the potential for a significant amount of the lubricant to seep out from between the bearing member and the first flange. Thus, the potential for premature wear is reduced. Also, since the retaining device is preferably disposed in the aperture of the bearing member the potential for the lubricant in the aperture to become contaminated, to dry out and to plug the hole is reduced. Further, the optional addition of a pair of seals on opposite sides of the bearing member seals the bearing member from the environment and reduces the potential for dirt and the like from entering the sealed area and contaminating the lubricant. This not only reduces wear caused by contamination but also reduces the potential for the lubricant to harden and plug the aperture. In the accompanying drawings: Fig. 1 discloses a diagrammatic side elevational view of first and second embodiments of the present invention showing for the first embodiment a bearing mounting arrangement for connecting a lift mast assembly to a first flange of a material handling vehicle and showing for the second embodiment a bearing mounting arrangement for mounting a bearing member to the first flange of a side shiftable frame of a carriage assembly; Fig. 2 is a diagrammatic sectional view taken along lines 2-2 of Fig. 1 showing the bearing mounting arrangement for mounting the lift mast assembly on the material handling vehicle in greater detail; Fig. 3 is a diagrammatic enlarged detail of a portion of the bearing mounting arrangement of Fig. 2; Fig. 4 is a diagrammatic partial front elevational view of the lift mast assembly of Fig. 1 showing the alternate embodiment of the bearing mounting arrangement for a side shift carriage thrust bearing in greater detail; Fig. 5 is a diagrammatic enlarged side elevational view taken along lines 5-5 of Fig. 4 showing the second embodiment of the present invention in greater detail; and Fig. 6 is a diagrammatic enlarged cross-sectional view taken along lines 6-6 of Fig. 4 showing the second embodiment of the bearing mounting arrangement in even greater detail. With reference to the drawings, and particularly Fig. 1, a material handling vehicle 10 has a frame 12 and a drive axle assembly 14 connected to the frame 12 at a front end portion 16 of the frame 12. A lift mast assembly 18 is pivotally connected to the vehicle frame 12 for tipping movement in directions toward and away from the front end portion 16 of the vehicle. A pair of fluid operated tilt jacks 28 is connected to and between the vehicle frame 12 and a first pair of uprights 20, respectively, of the lift mast assembly. The fluid operated tilt jacks 28 tilt the lift mast assembly 18 about its pivotal connection so that the lift mast assembly 18 may be positioned to receive and deposit loads. The lift mast assembly 18 has a second pair of spaced apart uprights 22, a side shiftable carriage assembly 24 connected to the second pair of spaced apart uprights 22 and guided by the second pair of uprights 22 for elevational movement, and a pair of spaced apart load engaging forks 26 (only one shown) connected to the side shiftable carriage assembly 24. The side shiftable carriage assembly 24 is elevationally moved in a conventional manner by a fluid operated jack (not shown) so that the load engaging forks 26 may be elevationally aligned to deposit or retrieve loads in a well known manner. Referring to Figs. 1-6, a bearing mounting arrangement 30 is provided for connecting a bearing member 32 to the lift mast assembly 18. It is to be noted that the bearing mounting arrangement 30 is used in at least two different locations on the lift mast assembly. In a first embodiment (as best seen in Figs. 1-3), the bearing mounting arrangement 30 is used to pivotally connect the lift mast assembly 18 to the of the vehicle 10. In the second embodiment (as best seen in Figs. 4-6), the bearing mounting arrangement 30 is used in a thrust bearing application for the side shiftable carriage assembly 24. Due to similarities in the design of the bearing mounting arrangement 30 of the first and second embodiments all common elements of the second embodiment will have the same reference numeral as similar elements of the first embodiment, followed by a prime ('). A bearing member 32,32' has first and second opposed surfaces 36,36',38,38', first and second sides 40,40',42,42' and a groove 44,44' disposed in the bearing member 32,32' and opening at the first surface 36,36'. An aperture 46,46' is disposed in the bearing member 32,32', passes through the bearing member 32,32', and opens at the first and second sides 40,40',42,42'. In particular the aperture 46,46' opens into the groove 44,44' so that a lubricant may pass into the groove 44,44'. In each embodiment a first flange 48,48' has first and second surfaces 50,50',52,52' and an aperture 54,54' disposed therein. The aperture 54,54' extends through the first flange 48,48' and opens at the first and second surfaces 50,50',52,52'. The aperture 54,54' is positioned at a location on the first flange at which the bearing member 32,32' is to be mounted. The bearing member 32,32' is positioned on the first flange 48,48' with the bearing member second surface 38,38' being supported on the first flange member 48,48'. The aperture 46,46' of the bearing member 32,32' is aligned with the aperture 54,54' of the first flange 48,48'. A second flange member 56,56' has a bearing surface 58,58' and is slidably engaged with the first surface 36,36' of the bearing member 32,32'. The bearing surface 58,58' is relatively smooth so that the coefficient of friction is minimized and sliding movement between the bearing member 32,32' and the bearing surface 58,58' is achieved with a substantially reduced force. A retaining means 60,60' is provided for maintaining the bearing member 32,32' from sliding movement relative to the first flange 48,48' first surface 50,50' and for directing lubricating fluid through the aperture 54,54' in the first flange member 48,48', through the aperture 46,46' in the bearing member 32,32', and into the groove 44,44'. The retaining means 60,60' is disposed in the aperture of the bearing and first flange members 32,32',48,48' and substantially aligns the apertures 46,46',54,54' in the bearing and first flange members 32,32',48,48' so that lubricating fluid is directed through the apertures and into the groove 44,44' in the bearing member 32,32'. The retaining means 60,60' includes an elongate retaining member 62,62' having an aperture 64,64' longitudinally disposed therethrough. The elongate retaining member 62,62' is disposed in the apertures 46,46',54,54' of the first flange 48,48' and bearing members 32,32'. The aperture 64,64' in the elongate retaining member 62,62' is adapted to direct lubricant to the groove 44,44' in the bearing member 32,32' and reduce the possibility of lubricant from leaking at the juncture of second surface 38,38' of the bearing 32,32' and the first surface 50,50' of the first flange 48,48'. The elongate retaining member 62,62' forcibly engages the bearing member 32,32', which retains the elongate retaining member 62,62' in the apertures 46,46',54,54'. The elongate retaining member 62,62' also retains the bearing member 32,32' from movement in directions transverse the elongate retaining member 62,62'. The elongate retaining member 62,62' has first and second longitudinally spaced apart ends 66,66',68,68'. The first end 66,66' is disposed in the aperture 46,46' of the bearing member 32,32' and between the first and second surfaces 36,36'38,38' of the bearing member 32,32' so that the retaining member is spaced from the second flange 56,56' and free from engagement with the bearing surface 58,58' of the second flange 56,56'. The retaining means 60,60' includes securing means 70,70' for retaining the elongate retaining member 62,62' in the apertures 54,54',46,46' of the first flange and the bearing members 48,48'32,32'. In the first embodiment as shown in Figs. 2 and 3 the elongate retaining member 62 is a spring pin and the securing means 70 includes the force of the spring pin acting against the bearing member 32 and/or the first flange 48. In the second embodiment as shown in Figs. 4 and 6 the securing means 70', includes a head member 72 connected to the first end 66' of the elongate retaining member 62' and a nut member 74 screw threadably connected to a threaded end portion 76 of the elongate retaining member 62'. The head member 72 is forcibly engageable with the bearing member 32' and the nut member 74 is forcibly engageable with the first flange member 48'. The nut member 74 is adjustably connected to the threaded end portion 76, engageable with the first flange 48', and forcibly urges the bearing member 32' toward the first flange 48'. With reference to Figs. 1-3, the first embodiment of the present invention, the bearing mounting arrangement 30 is provided to connect the bearing member 32 to the drive axle assembly 14. The bearing member 32 is preferably a cylindrical split sleeve bearing of any suitable bearing material. The cylindrical bearing member 32 is disposed in a cylindrical bore defined by the first surface 50 of the first flange 48 and mounted on the bearing surface 58 of the second flange 56. The first flange 48 is split in two parts for mounting on the bearing surface 58 and also so that the bearing 32 may be assembled in the bore defined by surface 50. Screw threaded fasteners 59 connect the two parts together after assembly on the first surface 50. The first flange 48 is connected to one upright of the first pair of uprights 20 in any suitable manner, such as by welding, threaded fastener and the like. Although only a single bearing mounting arrangement 30 has been discussed with respect to the mounting of the lift mast assembly 18 on the drive axle assembly 14, It is to be noted that, a second bearing mounting arrangement (not shown) of identical construction is provided to mount the other upright of the first pair of uprights 20 on the drive axle assembly 14. A fitting 78,78' of the conventional type is provided to facilitate the connection of an external pressurized source of lubricant (not shown), such as a grease gun. Fittings of this type have an internal ball check to pass fluid in one direction and stop the passing of fluid in the opposite direction. In Figs. 2 and 3, the fitting 78 is screw threadably connected to the first flange 48 at the second surface 52 and in the aperture 54. The fitting 78 passes a lubricant from the source and into the aperture 54 so that the lubricant may be passed under pressure to the bearing member 32. The groove 44 in the bearing member 32 receives the lubricant directed under pressure by the elongate retaining member 62 and directs the lubricant to the appropriate locations on the first surface 36 of the bearing member. To distribute lubricant properly across the first surface 36, a plurality of branch grooves 80 intersecting groove 44 is provided. First and second spaced apart parallel seal retaining grooves 82,84 are radially disposed in the first flange 48. The first and second grooves 82,84 are radially open at the first surface 50. The bearing member 32 is disposed between the first and second grooves 82,84 and first and second lip type seals 86,88 are disposed in the first and second grooves 82,84 and engageable with the bearing surface 58 of the second flange. The seals 86,88 prevent dirt and contaminants from entering the area between the seals 86,88 and also reduce the potential for the drying out and hardening of the lubricant. With reference to the second embodiment of the present invention, as best shown in Fig, 6, the fitting 78' is connected to the second end 68' of the elongate retaining member 62, and delivers lubricating fluid directly from the source of pressurized lubricant flow to the aperture 64' in the elongate retaining member 62. The lubricant by virtue of the aperture 64' is directed to the groove 44'. It is to be noted that the head member 72 of the elongate retaining member 62, is disposed in a counter bore 90 in the bearing member 32'. The counter bore 90 is open to the first surface 36', to the groove 44' and axially aligned with the aperture 46'. The head member 72 is disposed between the first and second surfaces 36,38' and does not extend to the surface 36'. Thus, damage to the head member 72 and the second flange 56' due to rubbing is prevented. The groove 44' is preferably a plurality of grooves 44' extending radially outward from the counterbore 90 in the bearing member 32' and opening at the first surface 36'. A counter bore 92 is also disposed in the flange 48'. Counter bore 92 is axially aligned with aperture 54' and open to receive the nut member 74 therein. Counter bore 92 serves to shield and protect the fitting 78' from impact with external objects. The bearing mounting arrangement 30 includes a bearing carrier 94. The bearing carrier 94 has a first surface 96, a ridge 98 defining a recessed surface portion 100, and an aperture 102 disposed centrally in the recessed surface portion 100 of the bearing carrier 94 and opening at the first surface 96 and recessed surface 100. The bearing member 32', is disposed in the recessed surface portion 100 and retained by the ridge 98 from movement in directions along the recessed surface 100 and transverse the ridge 98. The elongate retaining member 62' is disposed in the aperture 102 and forcibly urges the bearing member 32' in a direction toward the recessed surface portion 100 and the bearing carrier 94 against the first surface 50' of the first flange 48'. It should be noted that the bearing carrier 94 may be eliminated in certain applications, such as light material handling applications. In such applications the bearing member 32' second surface 38' will bear directly against the first surface 50' of the first flange 48'. With reference to Figs. 4 and 5, the side shiftable carriage assembly 24 has a carriage frame 104. The carriage frame 104 has a pair of elevationally oriented spaced apart roller brackets 106 which are rollingly guidably connected to the second pair of uprights 22 for elevational movement. The carriage frame 104 has an elongate guide rail 108 connected to the pair of roller brackets 106 in any suitable manner. The second flange member 56' is also connected to the pair of roller brackets 106. The elongate guide rail 108 is elevationally spaced from the second flange member 56' and substantially parallel thereto. A side shiftable frame 110 having a hooklike end portion 112 is hung on the elongate guide rail 108 and movable along the guide rail 108 in directions transverse the uprights 20,22. The elongate guide rail 108 has a bearing member 114 connected thereto. The bearing member, of any suitable material, is disposed between the hooklike end portion 112 and the guide rail 108 and provides for friction free movement of the side shiftable frame 110. The first flange member 48' is connected to the side shiftable frame 110 at an elevational location spaced from the elongate guide rail 108 at which the first flange member 48' is aligned with the second flange member 56'. The bearing member 32', which is connected to the first flange member 48' is slidably engaged with the second flange member 56' and movable along the second flange member 56' in response to movement of the side shiftable frame 110 along the elongate guide rail 108. The load engaging forks 26 are hung on the side shiftable frame 110 in a conventional manner. A side shifting fluid operated jack 116 is connected to and between the side shiftable frame 110 and the carriage frame 104 and moves the side shiftable frame 110 along the elongate guide rail 108 so that the load engaging forks 26 may be aligned with a load to be lifted or a rack or the like at which a load is to be deposited without changing the position of the pair of forks 26 relative to each other. The bearing mounting arrangement 30 passes thrust loads from the side shiftable frame 110 to the carriage frame 104 and reduces the coefficient of friction between the side shiftable frame 110 and carriage frame 104 so that smooth, low force side shifting may be provided. The bearing carrier 94 has an extension portion 118 which extends elevationally past the second flange 56'. A finger 120 is attached to the extension portion 118 in any suitable manner, such as by screw threaded fasteners 122. The finger 120 and the hook like end portion 112 retains the side shiftable frame 110 on the carriage frame 104 and prevents inadvertent separation thereof. The finger 120 also limits the allowable amount of tipping movement of the side shiftable frame 110 in directions away from the carriage frame 104. Industrial ApplicabilityWith reference to the drawings, it is necessary to pivotally connect the lift mast assembly 18 to the vehicle frame 12 and more particularly to the second flange member 56 so that the lift mast assembly 18 may be pivoted for load pick up and deposit purposes. The bearing mounting arrangement 30 is provided for achieving this connection in an efficient and effective manner while maximizing the life of the bearing member 32 and the integrity of the connection. Since the retaining means 60 maintains the bearing member 32 in position and from sliding movement relative to the first surface 50 and ensures that the aperture 54 in the first flange 48 and the aperture 46 in the bearing member 32 remain aligned during assembly and operation, the potential for premature wear is reduced. This is primarily due to the fact that the retaining means 60 directs lubricant from the aperture 54, into the groove 46, and to the proper bearing area, between bearing surface 36 and 58, and restricts the leakage of lubricant at the juncture of the surface 38 and 50. Also, because the bearing member 32 is retained from slippage relative to the first flange 48, undesirable wear of the bearing second surface 38 is prevented. To lubricate the bearing member 32 one simply connects the source of pressurized lubrication to the fitting 78 and forces lubricant through apertures 54,64 and into groove 44. The seals 86,88 serve to retain the lubricant between the seals 86,88 and to prevent contamination of the area between the seals by dirt and the like and also reduces the possibility of the lubricant drying out and plugging the passageways. Since the first flange 48 is segmented in two parts removal of the lift mast assembly 18 is achieved by simply removing the screw threaded fasteners 59 and lifting the lift mast assembly 18 from being supported on the bearing surface 58. In the second embodiment, the side shiftable carriage assembly 24, the bearing mounting arrangement 30 provides for smooth and low effort movement of the side shift frame 110. Because the groove 44' in the bearing member 32' receives lubricant directly from the retaining means 60' the potential for leakage of lubricant to other areas of the bearing member 32' is substantially reduced. Since the lubricant is directed to the proper area of the bearing member 32' an adequate amount of lubrication is available to provide for low friction operation. Since the bearing member 32' is retained by the retaining means 60 from movement in directions parallel to first surface 50' of the first flange 48' the potential for undesirable wear and binding of the side shift frame 110 relative to the carriage frame 104 due to dislodging of the bearing member 32' is prevented.	A bearing mounting arrangement, for use in a lift mast assembly, the arrangement comprising a bearing member (32,32') having first and second opposed surfaces (36,36';38,38'), a groove (44,44') disposed in the bearing member and opening at the first opposed surface, and an aperture (46,46') disposed in the bearing member and opening into the groove; a first flange member (48,48') having first and second surfaces (50,50';52,52') and an aperture disposed therein and opening at the first and second surfaces; a second flange member (56,56') having a bearing surface (58,58'), which is engaged with the bearing member first surface (36,36') and being slidably movable relative to the bearing member (32,32'); and retaining means (60,60') for maintaining the bearing member (32,32') from sliding movement relative to the first flange member first surface (50,50') and for directing lubricating fluid from the first flange member aperture (54,54'), through the bearing member aperture (46,46'), and into the groove (44,44'), the retaining means including an elongate retaining member (62), having an aperture (64) extending longitudinally therethrough, the elongate retaining member being disposed in the apertures (46,54) of the bearing and first flange members, characterised in that the elongate retaining member (62) forcibly engages the bearing member (32), which retains the elongate retaining member in the apertures of the bearing and first flange members. An arrangement according to claim 1, wherein the retaining member is a spring pin (62). An arrangement according to claim 1 or claim 2, wherein the retaining member has first and second ends (66,66';68,68') of which the first end (66,66') is located in the aperture (46,46') of the bearing member between the first and second surfaces (36,36';38,38') of the bearing member. An arrangement according to any one of the preceding claims, including a lubrication receiving fitting (78) connected to the first flange (48) and arranged to be connected to a source of pressurized lubricant flow, to receive lubricant from the source, and to pass lubricant to the aperture (54) in the first flange member. An arrangement according to any one of the preceding claims, wherein the first surface (50) of the first flange member (48) is defined by a cylindrical bore disposed in the first flange member. An arrangement according to claim 5, wherein the cylindrical bore is oriented with its axis transverse to that of the aperture (54) in the first flange member. An arrangement according to claim 5 or claim 6, wherein the bearing member (32) is a cylindrical sleeve bearing disposed in the cylindrical bore of the first flange member (48). An arrangement according to claim 7, including first and second spaced apart parallel radially oriented seal grooves (82,84) disposed in the first flange member (48) and opening at the first surface of the first flange member; and first and second lip seals (86,88) disposed in respective one of the seal grooves and engaging the second flange member (56), the bearing member (32) being disposed axially between the lip seals. An arrangement according to claim 1, wherein the retaining member (62') has a screw threaded portion (76) at one end, and the securing means (70') includes a head member (72) connected to the second end of the retaining member; and a nut member (76) screw threadably connected to the threaded end portion (76) of the retaining member, the head end portion being engageable with the bearing member (32') and the nut member (74) being engageable with the first flange member (48'). An arrangement according to claim 1 or claim 9, including a lubrication receiving fitting (78') connected to the one end of the elongate retaining member and being arranged to be connected to a source of pressurized lubricant flow, to receive lubricant from the source, and to pass lubricant directly to the aperture (64') of the elongate retaining member. An arrangement according to claim 9 and claim 10, wherein the bearing member (32') includes a counter bore (92), in which the head member (72) is disposed between the first and second surfaces (36',38') of the bearing. An arrangement according to any one of claims 9 to 11 including a bearing carrier (94) having a first surface (96), a ridge (98) defining a recessed surface portion (109) in the bearing carrier and an aperture (102) disposed in the bearing carrier and opening at the first and recessed surfaces of the bearing carrier; the bearing member being disposed in recessed portion and retained by the ridge from movement in directions along the recessed surface portion; and the retaining member being disposed in the aperture (102) of the bearing carrier (94) and forcibly urging the bearing member in a direction towards the recessed surface portion and the bearing carrier against the first surface (50') of the first flange member. A lift mast assembly comprising a bearing mounting arrangement according to any one of the preceding claims. A lift mast assembly comprising a bearing mounting arrangement according to any one of claims 1 to 8, including an upright member (20), the first flange member (48) being connected to the upright and whereby the upright is pivotable about the bearing surface (58) of the second flange member (56). A lift mast assembly comprising a bearing mounting arrangement according to any one of claims 9 to 12, including a pair of spaced apart uprights (22); a carriage frame (104) having an elongate guide rail (108), the second flange member (56') being connected to the carriage frame at a location elevationally spaced from the guide rail, the carriage frame being movably connected to the pair of spaced apart uprights and elevationally movable along the pair of uprights, the guide rail being oriented transverse the pair of uprights; and a side shiftable frame (110) supported on the guide rail and moveable along the guide rail in directions transverse to the pair of uprights, the first flange member (48') being connected to the side shift frame at an elevation spaced from the guide rail, and the bearing member (32') being arranged to pass thrust loads from the side shaft frame to the carriage frame and permit slidable movements of the side shaft frame along the guide rail.	CATERPILLAR IND INC; CATERPILLAR INDUSTRIAL INC.	KEFFELER GARY L; MCVEEN MILFORD D; KEFFELER, GARY L.; MCVEEN, MILFORD D.
EP-0489490-B1	489,490	EP	B1	EN	19,961,211	1,992	20,100,220	new	F02D35	F02M25, F02D41	F02D41, F02M25	R02D41:00F4D, R02M25:08, F02M 25/08, F02D 41/14D5F4, F02D 41/00F4E, F02D 41/14D9B	Air/fuel ratio control with adaptive learning of purged fuel vapors	A control system for a vehicle having a fuel vapour recovery system coupled between an engine air/fuel intake and a fuel supply system (32), comprising: feedback control means (90) responsive to an exhaust gas oxygen sensor (80) for providing an air/fuel ratio indication of the engine operation; command means for providing a base fuel command in response to said air/fuel ratio indication; purging means (46,48,60) coupled to the fuel supply and the fuel vapour recovery system (32,44) for purging a vapour mixture of fuel vapour and air into the engine air/fuel intake; fuel vapour measurement means (100) for providing a measurement of fuel vapour content in said purged vapour mixture by subtracting a reference air/fuel ratio, related to engine operation without purging, from said air/fuel ratio indication to generate an air/fuel ratio error; and compensating means (118) for subtracting said fuel vapour content measurement from said base fuel command to operate the engine at a desired air/fuel ratio during fuel vapour purging.	The invention relates to air/fuel ratio control system and method for motor vehicles having a fuel vapour recovery system coupled between the fuel supply system and the air/fuel intake of an internal combustion engine, as defined by the preamble of claims 1 and 3. Modern engines are equipped with 3-way catalytic 10 converters (NOX, CO, and HC) to minimise emissions. Efficient operation requires that the engine's air/fuel ratio be maintained within an operating window of the catalytic converter. For a typical converter, the desired air/fuel ratio is referred to as stoichiometry which is typically 14.7 gms. (lbs) air/gm. (lb) fuel. During steady-state engine operation, the desired air/fuel ratio is approached by an air/fuel ratio feedback control system responsive to an exhaust gas oxygen sensor. More specifically, a fuel charge is first determined for open loop operation by dividing a measurement of inducted airflow by the desired air/fuel ratio (such as 14.7). This open loop charge is then trimmed by a feedback correction factor responsive to an exhaust gas oxygen sensor. Electronically actuated fuel injectors are actuated in response to the trimmed fuel charge determination. In this manner, steady-state engine operation is maintained near the desired air/fuel ratio. Air/fuel ratio control has been complicated, and in some cases made unachievable, by the addition of fuel vapour recovery systems. These systems store excess fuel vapors emitted from the fuel tank in a canister having activated charcoal or other hydrocarbon absorbing material to reduce emission of such vapors into the atmosphere. To replenish the canisters storage capacity, air is periodically purged through the canister, absorbing stored hydrocarbons, and the mixture of vapors and purged air inducted into the engine. Concurrently, vapors are inducted directly from the fuel tank into the engine. Induction of rich fuel vapors creates at least two types of problems for air/fuel ratio control systems. Since there is a time delay for an air/fuel charge to propagate through the engine to the exhaust sensor, any perturbation in inducted airflow, such as caused by the sudden change in throttle position, will result in an air/fuel transient until the feedback loop responsive to the exhaust gas oxygen sensor is able to correct for such perturbation. Further, conventional air/fuel ratio feedback control systems have a limited range of authority. Induction of rich fuel vapors may exceed the feedback system's range of authority resulting in an unacceptable increase in emissions. U.S. patent no. 4,715,340 has addressed some of the above problems. More specifically, a combined air/fuel ratio feedback control system and vapour purge system is disclosed. To reduce the air/fuel transient which may occur during rapid throttle changes, the purged rate of vapour flow is made proportional to the rate of inducted airflow. Allegedly, any change in inducted airflow will then be accompanied by a corresponding change in purged vapour flow such that the overall air/fuel ratio is not significantly perturbed during a change in throttle angle. The inventors herein have recognised numerous disadvantages with the prior approaches. For example, modern aerodynamic styling has resulted in less air cooling flow around the fuel system and, accordingly, an increase in fuel vapour generation. In addition, government regulations are restricting the amount of vapors which may be discharged into the atmosphere. This trend will continue on an ever more strident basis in the future. Accordingly fuel vapour recovery systems in which purge flow is proportional to airflow may no longer be satisfactory because the rate of purge flow may be less than required to adequately reduce fuel vapors at conditions other than full throttle. The inventors herein have therefore sought to provide a system which inducts PCT Publication No WO/8910472 discloses a system and a method for obtaining output values for actuating a tank venting valve connected to the intake pipe of an internal combustion engine, according to the preamble of Claims 1 and 3. The inventors have recognised numerous disadvantages with the prior approaches, For example, modern aerodynamic styling has resulted in less air cooling flow around the fuel system and, accordingly, an increase in fuel vapour generation. In addition, government regulations are restricting the amount of vapours which may be discharged into the atmosphere. This trend will continue on an ever more strident basis in the future. Accordingly fuel vapour recovery systems in which purge flow is proportional to air flow may no longer be satisfactory because the rate of purge flow may be less than required to adequately reduce fuel vapours at conditions other than full throttle. The inventors herein have therefore sought to provide a system which inducts fuel vapors at a maximum rate over all engine operating conditions including idle. A need exists for such a system which does not exceed the air/fuel feedback system's range of authority and which does not introduce air/fuel transients during sudden throttle changes. The present invention provides both a control system and method for controlling air/fuel operation of an engine wherein a fuel vapour recovery system is coupled between an air/fuel intake and a fuel supply system, according to claims 1 and 3. An advantage of the invention is that engine air/fuel ratio control is maintained without significant transients while fuel vapors are purged despite variations in induced airflow. Another advantage is that the purged vapour mixture is maintained at a substantially constant flow rate over a range of engine operating conditions such as variations in inducted airflow. Accordingly, maximum purge of vapors is achieved even at idle conditions. Another advantage of the above aspect of the invention is that the actual fuel vapour content of the purged vapour mixture is learned or measured. Accordingly, highly accurate air/fuel ratio control is obtainable when purging fuel vapors. An other advantage of the invention is that the purged vapour mixture is maintained at a substantially constant flow rate over a range of engine operating conditions such as variations in inducted airflow. Accordingly, maximum purge of vapors is achieved even at idle conditions. Another advantage of the above aspect of the invention, is that the actual fuel vapour content of the purged vapour mixture is measured. Accordingly, highly accurate air/fuel ratio control is obtainable when purging fuel vapors. An additional advantage is that the purged flow rate remains substantially constant regardless of variations in manifold pressure of the engine. The invention will now be described further, by way of example, with reference to the accompanying drawings, in which : Figure 1 is a block diagram of an embodiment wherein the invention is used to advantage; Figures 2A-2H illustrate various electrical waveforms associated with the block diagram shown in Figure 1; Figure 3 is a high level flowchart illustrating various decision making steps performed by a portion of the components illustrated in Figure 1; and Figures 4A-4D are a graphical representation in accordance with the illustration shown in Figure 3. Referring first to Figure 1, engine 14 is shown as a central fuel injected engine having throttle body 18 coupled to intake manifold 20. Throttle body 18 is shown having throttle plate 24 positioned therein for controlling the induction of ambient air into intake manifold 20. Fuel injector 26 injects a predetermined amount of fuel into throttle body 18 in response to fuel controller 30 as described in greater detail later herein. Fuel is delivered to fuel injector 26 by a conventional fuel system including fuel tank 32, fuel pump 36, and fuel rail 38 coupled to fuel injector 26. Fuel vapour recovery system 44 is shown coupled between fuel tank 32 and intake manifold 20 via purge line 46 and purge control valve 48. In this particular example, fuel vapour recovery system 44 includes vapour purge line 46 connected to fuel tank 32 and canister 56 which is connected in parallel to fuel tank 32 for absorbing fuel vapors therefrom by activated charcoal contained within the canister. As described in greater detail later herein, purge control valve 48 is controlled by purge rate controller 52 to maintain a substantially constant flow of vapors therethrough regardless of the rate of air inducted into throttle body 18 or the manifold pressure of intake manifold 20. In this particular example, valve 48 is a pulse width actuated solenoid valve having constant cross-sectional area. A valve having a variable orifice may also be used to advantage such as a control valve supplied by SIEMENS as part no. F3DE-9C915-AA. During fuel vapour purge, air is drawn through canister 56 via inlet vent 60 absorbing hydrocarbons from the activated charcoal. The mixture of air and absorbed vapors is then inducted into intake manifold 20 via purge control valve 48. Concurrently, fuel vapors from fuel tank 32 are drawn into intake manifold 20 via purge control valve 48. Accordingly, a mixture of purged air and fuel vapors from both fuel tank 32 and canister 56 are purged into engine 14 by fuel vapour recovery system 44 during purge operations. Conventional sensors are shown coupled to engine 14 for providing indications of engine operation. In this example, these sensors include mass airflow sensor 64 which provides a measurement of mass airflow (MAF) inducted into engine 14. Manifold pressure sensor 68 provides a measurement (MAP) of absolute manifold pressure in intake manifold 20. Temperature sensor 70 provides a measurement of engine operating temperature (T). Engine speed sensor 74 provides a measurement of engine speed (rpm) and crank angle (CA). Engine 14 also includes exhaust manifold 76 coupled to conventional 3-way (NOX, CO, HC) catalytic converter 78. Exhaust gas oxygen sensor 80, a conventional two-state oxygen sensor in this example, is shown coupled to exhaust manifold 76 for providing an indication of air/fuel ratio operation of engine 14. More specifically, exhaust gas oxygen sensor 80 provides a signal having a high state when air/fuel ratio operation is at the rich side of a predetermined air/fuel ratio commonly referred to as stoichiometry (14.7 gms. (lbs) air/gm (lb) fuel in this particular example). When engine air/fuel ratio operation is lean of stoichiometry, exhaust gas oxygen sensor 80 provides its output signal at a low state. LAMBSE controller 90, a proportional plus integral controller in this particular example, integrates the output signal from exhaust gas oxygen sensor 80. The output control signal (LAMBSE) provided by LAMBSE controller 90 is at an average value of unity when engine 14 is operating, on average, at stoichiometry and there are no steady-state air/fuel errors or offsets. For a typical example of operation, LAMBSE ranges from .75-1.25. Base fuel controller 94 provides desired fuel charge signal Fd by dividing MAF by both LAMBSE and a reference or desired air/fuel ratio (A/FD) such as stoichiometry as shown by the following equation. Fd = MAFLAMBSE * A/FD During open loop operation, such as when engine 14 is cool and corrections from exhaust gas oxygen sensor 80 are not desired, signal LAMBSE is forced to unity. Continuing with Figure 1, vapour correction controller 100 provides output signal PCOMP representing a measurement of the mass flow of fuel vapors into intake manifold 20 during purge operation. More specifically, reference signal LAMR, unity in this particular example, is subtracted from signal LAMBSE to generate error signal LAMe. Integrator 112 integrates signal LAMe and provides an output to multiplier 116 which is multiplied by a preselected scaling factor. Vapour correction controller 100 is therefore an air/fuel ratio controller responsive to fuel vapour purging and having a slower response time than the air/fuel feedback system. As described in greater detail later herein, multiplier 116 also multiplies the integrated value of signal LAMe by correction factor Kp from purge rate controller 52. The resulting signal PCOMP from multiplier 116 in vapour correction controller 100 is subtracted from desired fuel signal Fd in summer 118. This modified desired fuel charge signal (Fdm) represents a correction to the desired fuel charge (Fd) generated by base fuel controller 94 for maintaining a desired air/fuel ratio (A/FD) during purging operations. Fuel controller 30 converts signal Fdm into a pulse width signal (fpw) having a pulse width directly correlated with signal Fdm. Fuel injector 26 is actuated during the pulse width of signal fpw such that the desired amount of fuel is metered into engine 14 for maintaining the desired air/fuel ratio (A/FD). Those skilled in the art will recognise that the operations described for base fuel controller 94 and vapour correction controller 100 may be performed by a microcomputer in which case the functional blocks shown in Figure 1 are representative of program steps. These operations may also be performed by discrete IC's or analog circuitry. An example of operation of the embodiment shown in Figure 1, and fuel vapour correction controller 100 in particular, is described with reference to operating conditions illustrated in Figures 2A-2H. For ease of illustration, zero propagation delay is assumed for an air/fuel charge to propagate through engine 14 to exhaust gas oxygen sensor 80. Propagation delay of course is not zero, but may be as high as several seconds. Any propagation delay would further dramatise the advantages of the invention herein over prior approaches. Steady-state engine operation is shown before time t1 wherein inducted airflow, as represented by signal MAF, is at steady-state, signal LAMBSE is at an average value of unity, purge has not yet been initiated, and the actual engine air/fuel ratio is at an average value of stoichiometry (14.7 in this particular example). Referring first to Figure 2C, vapour purge is initiated at time t1. In accordance with U.S. patent no. 4,641,623, the specification of which is incorporated herein by reference, purge flow is gradually ramped on until it reaches the desired value at time t2. For this particular example, the desired rate of purge flow is a maximum wherein the duty cycle of signal ppw is 100%. .Since the inducted mixture of air, fuel, purged fuel vapour, and purged air becomes richer as the purge flow is turned on, signal LAMBSE will gradually increase as purged fuel vapors are being inducted as shown between times t1 and t2 in Figure 2D. In response to this increase in signal LAMBSE, base fuel controller 94 gradually decreases desired fuel charge signal Fd as shown in Figure 2B such that the overall actual air/fuel ratio of engine 14 remains, on average, at 14.7 (see Figure 2H). Stated another way, fuel delivered is decreased as fuel vapour is increased to maintain the desired air/fuel ratio. Referring to Figures 2D and 2E, fuel vapour controller 100 provides signal PCOMP at a gradually increasing value as signal LAMBSE deviates from its reference value of unity. More specifically, as previously discussed herein, signal PCOMP is an integral of the difference between signal LAMBSE and its reference value of unity. It is seen that as signal PCOMP increases, the liquid fuel delivered (Fdm) to engine 14 is decreased such that signal LAMBSE is forced downward until an average value of unity is achieved at time t3. Signal PCOMP then reaches the value corresponding to the amount of purged fuel vapors. Accordingly, fuel vapour controller 100 adaptively learns the concentration of purged fuel vapors during a purge and compensates the overall engine air/fuel ratio for such purged fuel vapors. The operating range of authority of air/fuel feedback system 28 is therefore not reduced during fuel va]or purging. Any perturbation caused in engine air/fuel ratio by factors other than purged fuel vapors, such as perturbations in inducted airflow, are corrected by signal LAMBSE. Referring to Figure 2B and continuing with Figures 2D and 2E, it is seen that desired fuel signal Fd provided by base fuel controller 94 increases in correlation with a decrease in signal LAMBSE until, at time t3, signal Fd reaches its value before introduction of purging. However, referring to Figure 2F, modified desired fuel signal (Fdm) reaches a steady-state value at time t2 by operation of signal PCOMP (i.e., Fdm = Fd - PCOMP) such that the total fuel delivered to the engine (injected fuel plus purged fuel vapors) remains substantially constant before and during purging operation as shown in Figure 2G. Accordingly, fuel vapour correction controller 100 will generate signal PCOMP which is essentially a measurement of the amount of fuel vapors during purging operations. And base fuel controller 94 will generate a desired fuel charge signal (Fd) representative of fuel required to maintain the desired engine air/fuel ratio independently of purging operations. The illustrative example continues under conditions where the engine throttle, and accordingly inducted airflow (MAF), are suddenly changed as shown at time t4 in Figure 2A. Since the rate of purge flow is maintained relatively constant by operation of purge rate controller 52, as described in greater detail later herein, signal PCOMP remains at a substantially constant value despite the sudden change in inducted airflow (see Figure 2E). Correction for the lean offset provided by the sudden increase in inducted airflow will then be provided by base fuel controller 94 (as described previously herein and as further illustrated in Figures 2B, 2F, and 2G, and 2H). On the other hand, without operation of fuel vapour controller 100, a transient in engine air/fuel ratio would result with any sudden increase in throttle angle. This, as previously discussed, is indicative of prior feedback approaches. To illustrate the above problem, dashed lines are presented in Figures 2B, 2D, 2F, 2G, and 2H which are illustrative of operation without fuel vapour correction controller 100 and its output signal PCOMP. It is seen that the sudden change in airflow at time t4 causes a lean perturbation in air/fuel ratio until signal LAMBSE provides a correction at time t5. This perturbation occurs because base fuel controller 94 initially offsets desired fuel charge Fd in response to signal MAF (i.e., Fd = MAF/14.7/LAMBSE). The overall air/fuel mixture is now leaner than before time t4 because purge vapour flow has not increased in proportion to the increase in inducted airflow. LAMBSE controller 90 will detect this lean offset during the time interval from t4 through t5 and base fuel controller 94 will appropriately adjust the fuel delivered by time t5. However, an air/fuel transient occurs between times t4 and t5 as shown in Figure 2H. The air/fuel transient described above, however, does not occur in the Preferred Embodiment because fuel vapour correction controller 100 provides an immediate correction for the purged fuel vapors regardless of changes in inducted airflow. Operation of purge rate controller 52 and purge valve 48 are now described in more detail with reference to Figure 3 and Figures 4A-4C. As previously discussed herein, control valve 48 is a solenoid actuated valve having constant cross-sectional valve area. Vapour flow therethrough is therefore related to the on time during which the solenoid is actuated. Stated another way, vapour flow is related to the pulse width and duty cycle of signal ppw from purge rate controller 52. For example, at 100% duty cycle, vapour flow is at the maximum enabled by the cross-sectional valve area. Whereas, at 50% duty cycle, vapour flow is one-half of maximum assuming that vapour flow is linear to duty cycle under all operating conditions. This assumption of linearity is accurate when absolute manifold pressure (MAP) of intake manifold 20 is sufficiently low, or manifold vacuum is sufficiently high, for the vapour flow through purge valve 48 to be sonic. Otherwise, flow through purge valve 48 is both a function of MAP and the duty cycle of signal ppw. In general, purge rate controller 52 increases the duty cycle of signal ppw to compensate for any subsonic flow conditions caused by an increase in MAP to maintain a linear relationship between the duty cycle of signal ppw and vapour flow through purge valve 48. Referring specifically to Figure 3, a high level flowchart of a series of steps performed by a microcomputer are illustrated for embodiments in which the operation of purge rate controller 52 is performed by a microcomputer or equivalent device. Those skilled in the art will recognise that the operation of purge rate controller 52 described herein may also be performed by other conventional components such as discrete IC's or analog circuitry. Referring to the process steps shown in Figure 3, a purge command is provided during step 124 in response to engine operating conditions such as engine temperature (T), and engine speed (rpm). In response, a desired purge flow (Pfd), and the corresponding duty cycle for signal ppw (ppwd), are selected during steps 126 and 128 assuming a linear relationship. During step 134, a determination of whether purge valve 48 is operating under sonic or subsonic conditions is made. In this particular example, absolute manifold pressure is normalised to ambient barometric pressure (MAP/BP) and this ratio compared to a critical value (Pc) associated with the transition from sonic to subsonic flow for the particular valve utilised. If the ratio MAP/BP is greater than critical value Pc, then the duty cycle of signal ppw is incremented by a predetermined amount during step 136 as determined by a look up table of ppw versus MAP/BP for desired purge flow Pfd (see Figure 4B). In effect, the on time of purge valve 48 is being increased to compensate for the nonlinear relationship between flow and duty cycle during subsonic operation of purge valve 48. When 100% duty cycle is achieved, compensation for subsonic flow by duty cycle increase is no longer possible. If not corrected for, such conditions would result in a perturbation in air/fuel operation of engine 14. This condition is corrected by generating multiplier factor Kp as a function of MAP/BP and Pfd during step 144 (see also Figure 4C). Multiplier factor Kp multiplies the output of integrator 112 (see Figure 1) such that signal PCOMP is appropriately reduced, thereby averting a transient in the engine's air/fuel ratio. Stated another way, the fuel correction factor (PCOMP) which corrects the engine air/fuel ratio for a constant vapour flow is appropriately reduced when the vapour flow rate falls below the desired flow rate (Pfd) as a result of subsonic flow conditions through purge valve 48. The operation of purge rate controller 52 may be better understood by viewing an example of operation presented in Figures 4A-4D. Figure 4A represents purge flow as a function of the MAP/BP ratio for constant duty cycle of signal ppw. It is seen that when the ratio MAP/BP is below critical value Pc, flow through valve 48 is sonic such that there is no variation in Pfd. As the ratio MAP/BP exceeds critical value Pc, the flow through purge valve 48 becomes subsonic and Pfd can no longer be held at a constant value by a constant duty cycle of signal ppw. To compensate for degradation in purge flow caused by subsonic flow conditions, signal ppw is increased in accordance with a look up table as represented by Figure 4B. Referring to both Figures 4B and 4C, compensation for subsonic flow conditions is shown for a particular desired purge flow (Pfd1) wherein solid line 150 represents rate of purge flow (Pf) and dashed line 152 represents signal ppw. When the MAP/BP ratio exceeds Pc, signal ppw is increased in accordance with the look up function shown in Figure 4B such that Pfd1 remains substantially constant as shown between point 154 and point 156 in Figure 4C. When the MAP/BP ratio exceeds that associated with point 156 (duty cycle of signal ppw is at 100%), then compensation for subsonic flow conditions proceeds by generating compensation factor Kp. Compensating factor Kp is generated by a look up table of the MAP/BP ratio versus desired purge flow as shown in Figure 4D and previously discussed herein.	A control system for a vehicle having a fuel vapour recovery system coupled between a fuel supply system (32) and an intake manifold of an internal combustion engine, comprising: feedback control means (28) responsive to an air/fuel ratio indication of an exhaust gas oxygen sensor (80) for controlling the air/fuel ratio to a desired value; command means for providing a base fuel command in response to both said air/fuel ratio indication and a measurement of ambient air inducted through a throttle body into the engine; purging means (46,48,60) coupled to the fuel supply and the fuel vapour recovery system for periodically purging a vapour mixture of fuel vapour and air into the engine air/fuel intake, said purging means including an electronically controllable valve; vapour indicating means (100) for providing an indication of vapour content in said purged fuel vapours by subtracting a reference air/fuel ratio, related to engine operation without purging, from said air/fuel ratio indication to generate an air/fuel ratio error indication and by integrating said air/fuel ratio error indication; compensation means (118) for subtracting a purged vapour compensation factor (PCOMP), related to said vapour content indication, from said base fuel command for operating said engine at a desired air/fuel ratio during fuel vapour purging, means (52) to select a desired purge flow rate and duty cycle of the said valve, characterised in that said compensation means further includes; means to determine whether a normalised value of the pressure drop across the intake manifold exceeds a critical value (Pc) associated with the transition from sonic to subsonic flow through the said valve, means to increment the duty cycle of the valve by a predetermined amount if the normalised value of the pressure drop across the intake manifold exceeds the critical value (Pc), means to determine if the duty cycle of the said valve has reached 100%, means to generate a further compensation factor (Kp) when the duty cycle of the said valve has reached 100%, and means (116) to reduce the vapour compensation factor (PCOMP) by the further compensation factor (Kp) to correct for subsonic flow through the said valve. A control system according to claim 1, wherein said means to generate the further compensation factor (Kp) comprises a look up table of normalised pressure in said intake manifold versus purge flow rate. A method for controlling operation of an engine wherein a fuel recovery system is coupled between an air/fuel intake manifold and a fuel supply system, comprising the steps of ; providing an air/fuel ratio indication of the engine operation in response to an exhaust gas oxygen sensor; feedback-controlling the air/fuel ratio to a desired value in response to said air/fuel ratio indication; generating a base fuel command in response to said air/fuel ratio indication and to a measurement of ambient air inducted through a throttle body into the engine; periodically purging a vapour mixture of fuel and air into the engine air/fuel intake through an electronically controllable valve operable at selectable flow rates; measuring fuel vapour content in said purged vapour mixture by subtracting a reference air/fuel ratio, related to engine operation without purging, from said air/fuel ratio indication to generate an air/fuel error indication and by integrating said air/fuel ratio indication; subtracting a purged vapour compensation factor (PCOMP), related to said vapour content indication, from said base fuel command for operating said engine at a desired air/fuel ratio during vapour purging; selecting a desired purge flow rate and duty cycle for the said valve, characterised in that the method further comprises the steps of; determining whether a normalised value of the pressure drop across the inlet manifold exceeds a critical value (Pc) associated with the transition from sonic to subsonic flow through the said valve, incrementing the duty cycle of the valve by a predetermined amount if the normalised value of the pressure drop across the intake manifold exceeds the critical value (Pc), determining if the duty cycle of the said valve has reached 100%, generating a further compensation factor (Kp) when the duty cycle of the said valve has reached 100%, and reducing the vapour compensation factor (PCOMP) by the further compensation factor (Kp) to correct for subsonic flow through the said valve. A method according to claim 3, wherein the further compensation factor (Kp) is generated from a look up table relating the normalised value of the pressure drop across the intake manifold versus the desired purge flow.	FORD FRANCE; FORD MOTOR CO; FORD WERKE AG; FORD FRANCE S. A.; FORD MOTOR COMPANY LIMITED; FORD-WERKE AKTIENGESELLSCHAFT	DAVENPORT MARTIN FREDERICK; HAMBURG DOUGLAS RAY; DAVENPORT, MARTIN FREDERICK; HAMBURG, DOUGLAS RAY
EP-0489491-B1	489,491	EP	B1	EN	19,970,611	1,992	20,100,220	new	G06F3	G06F1	G06F1, B41J5, G06F3, G06F15	B41J 5/10C, G06F 1/16P2K4, T01H223:050	Personal computer and dissociated keyboard	This invention relates to a personal computer with a folding keyboard and, more particularly, to a personal computer contained within a compact enclosure when stored in a non-use position. The personal computer has a clamshell enclosure having first and second housings joined for pivotal movement one relative to the other about an elongate housing axis and between a folded position and a use position. Computer operating components are mounted in the enclosure. A keyboard assembly is operatively associated with the enclosure and the computer operating components and has first and second keyboard portions each bearing manually engageable elements for entering characters and commands. The portions are coupled together for pivotal movement one relative to the other about a keyboard axis perperdicular to the housing axis and coupled with the enclosure for sliding movement relative between a folded, stored position interposed between the housings and an opened, use position partially displaced from and overlying a side edge of the enclosure The keyboard assembly has, when folded about the keyboard axis, dimensions received wholly within the outline configuration of the enclosure.	This invention relates to a personal computer keyboard and, to a personal computer contained within a compact enclosure when stored in a non-use position. Personal computer systems have attained widespread use for providing computer power to many segments of today's modern society. Personal computer systems have heretofore been defined as a desk top, floor standing, or portable microcomputer that consists of a system unit having a single system processor and associated volatile and non-volatile memory, a display monitor, a keyboard, one or more diskette drives, a fixed disk storage, and an optional printer. One of the distinguishing characteristics of these systems is the use of a motherboard or system planar to electrically connect these components together. These systems are designed primarily to give independent computing power to a single user and are inexpensively priced for purchase by individuals or small businesses. Examples of such personal computer systems are IBM's PERSONAL COMPUTER AT; compatible computers offered by competitors of IBM; and IBM's PERSONAL SYSTEM/2 Models 25, 30, 50, 60, 70 and 80. These systems can be classified into two general families. The first family, usually referred to as Family I Models, use a bus architecture exemplified by the IBM PERSONAL COMPUTER AT and other IBM compatible machines. The second family, referred to as Family II Models, use IBM's MICRO CHANNEL bus architecture exemplified by IBM's PERSONAL SYSTEM/2 Models 50 through 80 and other MICRO CHANNEL machines. The Family I models typically have used the popular INTEL 8088, 8086, or 80286 microprocessor as the system processor. The 8088 and 8076 processors have the ability to address one megabyte of memory. The Family II models typically use the high speed INTEL 80286, 80386, and 80486 microprocessors which can operate in a real mode to emulate the slower speed INTEL 8086 microprocessor or a protected mode which extends the addressing range from 1 megabyte to 4 Gigabytes for some models. In essence, the real mode feature of the 80286, 80386, and 80486 processors provide hardware compatibility with software written for the 8086 and 8088 microprocessors. Portable personal computers have recently advanced through developments which have been characterised as luggable , to laptop , and to notebook . A luggable personal computer is one which is particularly configured to be fairly readily moved from one place to another, and which has a bulk and weight nearly the same as a more conventional desktop machine. A laptop personal computer is one which, while weighing about one half as much as and occupying less cubic volume than a luggable, is about the size and weight of a conventional business briefcase loaded with papers. A notebook personal computer typically is about the size of a conventional loose leaf binder holding letter size paper, and typically weighs about half as much as a laptop computer. As development of portable personal computers has advanced, substantially the full function of a more conventional desktop machine has been retained, with the exception that portable machines typically include a visual display integrated with the machine and users typically provide a separate printer which will be connected only as required. A limitation on the reduction in the size of personal computers has been the desire of users for a keyboard at least approximating those known and used with desktop and floor standing machines. Such conventional keyboards typically have an elongated rectangular form with alphanumeric keys arrayed in rows and staggered columns and with special function keys appropriate to the personal computer arrayed around the alphanumeric keys in a standard array. Such keyboards may have varying numbers and arrangements of keys, and several such arrangements have become more or less conventional and known by the number of keys provided. As efforts have been expended toward reducing the physical size of portable personal computers, some designers have chosen to reduce the size of the keys and thus the keyboards, while others have conventional keyboards. such efforts have succeeded to the point that notebook portable personal computers have had some success in the marketplace, however, users of such computers often have complaints about key size and keyboard arrangement as compared with more conventional keyboards used with desktop machines. Restraints on key size and arrangement have effectively imposed, prior to the present invention, a lower size limitation on keyboard length and width of about the size of a sheet of correspondence stationery. In the article Machine Design , Vol.55, No.3, February 1983, page 36, a pocket size computer/terminal device is illustrated which includes a keyboard made from folding or detachable modules. When folded, the device has conventional calculator keys, but when unfolded, a computer qwerty-style keyboard is provided, the calculator keys being on the reverse side of one of the unfolded modules. According to the present invention there is provided a personal computer having a keyboard assembly comprising a plurality of keyboard portions for operating the computer, the computer being characterised by: an elongate housing having a predetermined outline configuration and defining a housing axis; computer operating components mounted in said housing; and the keyboard assembly comprising first and second keyboard portions each bearing key elements for entering characters and commands, said portions being coupled together for pivotal movement one relative to the other about a keyboard axis perpendicular to said housing axis and coupled with said housing for movement relative thereto between a non-use stored position and an opened use position, said keyboard assembly being pivotable about said keyboard axis and having, when moved to said stored position, dimensions received wholly within the outline configuration of said housing. In the drawings:- Figure 1 is a perspective view of the portable personal computer of this invention in a non-use, stored or folded position; Figure 2 is a plan view from above showing the personal computer of Figure 1 in the process of being opened into a use position; Figure 3 is a perspective view showing the personal computer of Figure 1 and 2 opened into a first use position; Figure 4 is a view similar to Figure 3 showing the personal computer of this invention opened into an alternate use position; and Figure 5 is a schematic representation of the computer operating components of the portable personal computer of this invention. While the present invention will be described more fully hereinafter with reference to the accompanying drawings, in which a preferred embodiment of the present invention is shown, it is to be understood at the outset of the description which follows that persons of skill in the appropriate arts may modify the invention here described while still achieving the favourable results of this invention. Accordingly, the description which follows is to be understood as being a broad, teaching disclosure directed to persons of skill in the appropriate arts, and not as limiting upon the present invention. Referring now more particularly to the accompanying drawings, the portable personal computer of this invention is there generally identified at 10, and has a clamshell enclosure 11 having first and second housings 12, 14 joined for pivotal movement thereof one relative to the other about an elongate housing axis and between a folded position (Figure 1) and a use position (Figure 3 and 4). The enclosure 11 has a predetermined outline configuration, with each of the housings 12, 14 preferably having a generally rectangular parallelepiped configuration with predetermined length, width and depth dimensions. As herein used, length refers to the greater side edge dimension of the parallelogram defined by the exposed surface of one of the housings 12, 14, while width refers to the lesser side edge dimension of that surface and depth refers to the side edge dimension of the parallelepiped which is perpendicular to the surface side edges. In the form shown, the housings 12, 14 are joined for pivotal movement thereof one relative to the other about a housing axis parallel to the lengthwise dimensions thereof and defined by a hinge. The hinge structure may be any suitable hinge appropriate to the usage expected of the computer 10, such as a piano hinge, a living hinge moulded of synthetic materials, or other hinges known to persons skilled in the applicable arts of mechanical and aesthetic design. For compactness, it is preferred that the housings 12, 14 have length dimensions which are equal and width dimensions which are less than the length dimension. The width dimensions of the housings preferably are equal, as are the depth dimensions. Thus the portable personal computer may have somewhat the appearance of a book when in the non-use, folded or stored position (Figure 1). Computer operating components for supplying the desired computer functions are mounted in the housings 12, 14. At least certain of these components are mounted on a multilayer planar or motherboard (not visible in the drawings) which is mounted in the housings and provides a means for electrically interconnecting components of the computer 10. Figure 5 shows a block diagram of a personal computer system and illustrates the various components of the computer 10, including components mounted on the planar 20 and other hardware of the personal computer system. Connected to the planar is the system processor 32 comprised of a microprocessor which is connected by a high speed CPU local bus 34 through a bus control timing unit 35 to a memory control unit 36 which is further connected to a volatile random access memory (RAM) 38. While any appropriate microprocessor can be used, one suitable microprocessor is the 80286 which is sold by INTEL. While the present invention is described hereinafter with particular reference to the system block diagram of Figure 5, it is to be understood at the outset of the description which follows that it is contemplated that the apparatus in accordance with the present invention may be used with other hardware configurations of the planar board. For example, the system processor could be an Intel 80386 or 80486 microprocessor. Returning now to Figure 5, the CPU local bus 34 (comprising data, address and control components) provides for the connection of the microprocessor 32, a math coprocessor 39, a cache controller 40, and a cache memory 41. Also coupled on the CPU local bus 34 is a buffer 42. The buffer 42 is itself connected to a slower speed (compared to the CPU local bus) system bus 44, also comprising address, data and control components. The system bus 44 extends between the buffer 42 and a further buffer 68. The system bus 44 is further connected to a bus control and timing unit 35 and a DMA unit 48. The DMA unit 48 is comprised of a central arbitration unit 49 and DMA controller 50. An arbitration control bus 55 couples the DMA controller 50 and central arbitration unit 49 to a diskette adapter 56. Also connected to the system bus 44 is a memory control unit 36 which is comprised of a memory controller 59, an address multiplexor 60, and a data buffer 61. The memory control unit 36 is further connected to a random access memory as represented by the RAM module 38. The memory controller 36 includes the logic for mapping addresses to and from the microprocessor 32 to particular areas of RAM 38. This logic is used to reclaim RAM previously occupied by BIOS. Further generated by memory controller 36 is a ROM select signal (ROMSEL), that is used to enable or disable ROM 64. While the microcomputer system 10 is shown with a basic 1 megabyte RAM module, it is understood that additional memory can be interconnected as represented in Figure 5 by the optional memory modules 65 through 67. For purposes of illustration only, the present invention is described with reference to the basic one megabyte memory module 38. A latch buffer 68 is coupled between the system bus 44 and a planar I/O bus 69. The planar I/O bus 69 includes address, data, and control components respectively. Coupled along the planar I/O bus 69 are a variety of I/O adapters and other components such as the display adapter 70 (which is used to drive a display 71 described more fully hereinafter), a CMOS clock 72, nonvolatile CMOS RAM 74 herein after referred to as NVRAM, a RS232 adapter 76, a parallel adapter 78, a plurality of timers 80, a diskette adapter 56, an interrupt controller 84, a keyboard/auxiliary device controller 51, and read only memory 64. The read only memory 64 includes the BIOS that is used to interface between the I/O devices and the operating system of the microprocessor 32. BIOS stored in ROM 64 can be copied into RAM 38 to decrease the execution time of BIOS. ROM 64 is further responsive (via ROMSEL signal) to memory controller 36. If ROM 64 is enabled by memory controller 36, BIOS is executed out of ROM. If ROM 64 is disabled by memory controller 36, ROM is not responsive to address enquiries from the microprocessor 32 (i.e. BIOS is executed out of RAM). The clock 72 is used for time of day calculations and the NVRAM is used to store system configuration data. That is, the NVRAM will contain values which describe the present configuration of the system. For example, NVRAM contains information describing the capacity of a fixed disk or diskette, the type of display, the amount of memory, time, date, etc. Of particular importance NVRAM will contain data (can be one bit) which is used by memory controller 36 to determine whether BIOS is run out of ROM or RAM and whether to reclaim RAM intended to be used by BIOS RAM. Furthermore, these data are stored in NVRAM whenever a special configuration program, such as SET Configuration, is executed. The purpose of the SET Configuration program is to store values characterizing the configuration of the system to NVRAM. The computer 10 is provided with a fixed or hard disk drive, also known as a hardfile (not visible in the illustrations) and with a floppy disk drive 81. The floppy disk drive 81 is mounted in one housing 14, in particular relationship to certain other computer operating components as described hereinafter (notably the display 71). In order to realize the objects of this invention by providing a keyboard of substantially conventional key size and arrangement, the computer 10 in accordance with this invention has a keyboard assembly 90 operatively associated with the enclosure 11 and the computer operating components described immediately hereinabove. The assembly is formed from first and second keyboard portions 91, 92 each of which bears keys or other manually engageable elements for entering characters and commands. The keyboard assembly portions 91, 92 are operatively coupled together for pivotal movement one relative to the other about a keyboard axis which is perpendicular to the housing axis defined by the hinge mentioned above. The keyboard assembly portions 91, 92 are also operatively coupled with the enclosure 10 for sliding movement relative thereto between a folded, stored position interposed between the housings and an opened, use position partially displaced from and overlying a side edge of the enclosure 11, with the keyboard assembly 90 being pivotable about the keyboard axis and having, when folded, dimensions such that it is received wholly within the outline configuration of the enclosure 11 (Figure 1). Preferably, the keyboard assembly 90 is coupled (as described more fully hereinafter) to one of the clamshell enclosure housings (the housing 14 in the illustrations) which is herein identified as the coupled housing. Each of the keyboard assembly portions 91, 92 preferably has a generally rectangular parallelepiped configuration with predetermined length, width and depth dimensions. The meanings of length , width , and depth as used with reference to the keyboard assembly portions are generally the same as stated above with reference to the clamshell enclosure housings 12, 14, although care must be used due to the varying orientation of the portions 91, 92 during movement between stored and use positions as will be brought out hereinafter. Lengthwise is the greatest dimension of the keyboard assembly when oriented for use. The keyboard axis mentioned above extends parallel to the depthwise dimensions of the portions 91, 92 and generally perpendicular to the housing axis defined by the hinge mentioned hereinabove. The dimensions of the keyboard portions 91, 92 bear particular relationships to the dimensions of the clamshell enclosure housings 12, 14, in that the length dimensions of the portions are approximately equal to the widthwise dimension of the coupled housing 14 and the widthwise dimensions of the portions are approximately equal to one half of the lengthwise dimension of the coupled housing 14. In accordance with important distinguishing characteristics of this invention, the keyboard portions 91, 92 are movable between a folded position in which lengthwise side edges of the first and second portions adjoin (Figure 1) and an opened use position in which widthwise side edges of the first and second portions adjoin (Figures 3 and 4). This movement occurs about a joint which operatively couples the keyboard portions one to the other for pivotal movement one relative to the other about the keyboard axis mentioned above and operatively couples the portions with one of the housings 12, 14 (the coupled housing 14 in the illustrations) for sliding movement relative thereto between a position superposed on the coupled housing (Figure 4) and a position partially displaced from the coupled housing and partially overlying a lengthwise side edge thereof (Figure 3). The joint is preferable provided by a pin defining the keyboard axis. The pin functions as a sliding connector coupling the keyboard assembly 90 and the coupled housing 14 and accommodating linear movement of the keyboard axis between locations adjacent the two lengthwise side edges of the coupled housing. The pin also functions to capture the keyboard assembly against ready separation from the coupled housing. One manner of achieving this result is to provide a slot in the coupled housing (Figures 2, 3) with the pin having a headed end within the coupled housing 14. It will be noted that the keys provided on the keyboard portions 91, 92 are arrayed in the normal arrangement of lengthwise rows and angled widthwise columns, with function or command keys placed about the alphanumeric keys. Due the to presence of angled columns and the desire for generally parallelepiped configurations for the portions 91, 92, the division along the widthwise side edges which are brought into adjoining relation for use of the keyboard is not along a straight line. Instead, the division results in an interdigitated joining together of castellated, stairstepped or interrupted side edges. The keys provided on the keyboard portions may use presently known keyboard technologies to achieve the necessary function. Preferably, the keyboard uses membranes bearing conductive strips and a rubber dome key activation system to enable establishing contacts representative of manual activation of selected keys. However, the keyboard may use buckling spring or leaf spring technology, with the spring elements being either plastic materials for weight reduction or metal materials. Signals indicative of key depression are delivered to the computer operating components described above through a pair of keyboard scanning devices, one mounted in each of said keyboard portions for scanning those manually engageable elements mounted in the corresponding portion. The scanning devices forward to the keyboard/auxiliary controller 51 (and thence to the central processor unit 32) signals indicative of the characters and commands keyed by a user. Signals forwarded by the scanning devices preferably pass through signal communicating conductors extending through the pin which joins together the keyboard portions 91, 92 and the coupled housing 14. In use, when the portable personal computer 10 of this invention is stored or not in use, the keyboard portions 91, 92 are disassociated, pivoted or folded with lengthwise side edges adjoining. In such a position, and with the clamshell enclosure 11 folded closed about the housing axis defined by the hinge joining them, the exterior appearance of the computer 10 resembles a book. The housings 12, 14 are movable between the folded position just described, in which the first and second housings are superposed and externally facing planar parallelogram surfaces thereof of are parallel, and a opened use position (Figures 2, 3 and 4) in which the first and second housings are angularly disposed and the externally facing parallelogram surfaces thereof define therebetween an obtuse angle. As so opened, a user will be able to view a display screen 71 mounted in one of the housings. Preferably, and as illustrated, the display screen 71 is mounted in the one of the housings (housing 12) other than the coupled housing 14. The display may be any suitable display, with a preference at the time of disclosure of this invention for the type known as an LCD (for Liquid Crystal Display) screen. As known to persons of skill in the appropriate arts, such a display screen is capable of presenting to a user a visual display of information processed by the personal computer 10. As the computer 10 is opened into use position, the keyboard assembly becomes exposed and the keyboard portions may be pivoted downwardly (Figure 2) into a position in which the widthwise side edges interdigitate and adjoin and the keys come into the alignment and array known for conventional keyboards. As so positioned, use of the computer in known ways may begin. It will be noted that the keyboard may be positioned in at least two particular ways. First, should a user desire to use the portable computer at a conventional desk or the like, the keyboard assembly 90 may be moved to a position partially displaced from the coupled housing 14 and partially overlying a lengthwise side edge thereof. Preferably, when so positioned, the keyboard assumes an acute included angle to the horizontal of about twelve degrees, the same as the angle of a conventional desktop keyboard. Alternatively, should the user be required to use the computer in more restricted space (such as on the tray table of an airliner), the keyboard assembly 90 may be moved to a position superposed on the coupled housing 14 (Figure 4) while retaining the advantages of a substantially full sized keyboard. It is the joint connection described hereinabove which makes such usage possible. The knowledgeable reader will understand that the keyboard assembly of this invention, while disclosed with particular reference to a portable personal computer, will have utility apart from the specific embodiment illustrated and described in detail. More particularly, the keyboard apart from the portable computer may be used with more conventional desktop or upright personal computers, and may be housed only within a decorative housing, or simply unhoused. As will be understood, in the latter instances, the other elements described as being present in the preferred embodiment may be missing in such adapted embodiments.	A personal computer having a keyboard assembly comprising a plurality of keyboard portions for operating the computer, the computer being characterised by: an elongate housing having a predetermined outline configuration and defining a housing axis; computer operating components mounted in said housing; and the keyboard assembly comprising first (91) and second (92) keyboard portions each bearing key elements for entering characters and commands, said portions (91, 92) being coupled together for pivotal movement one relative to the other about a keyboard axis perpendicular to said housing axis and coupled with said housing for movement relative thereto between a non-use stored position and an opened use position, said keyboard assembly (90) being pivotable about said keyboard axis and having, when moved to said stored position, dimensions received wholly within the outline configuration of said housing. A personal computer according to Claim 1 wherein the housing constitutes one of first (12) and second (14) housings of a clamshell enclosure (11), the first and second housings being joined for pivotal movement thereof one relative to the other about an elongate housing axis and between a folded position and a use position, said enclosure having a predetermined outline configuration; the keyboard assembly (90) being coupled with said enclosure (11) for sliding movement relative thereto between a folded, stored position interposed between said housings (12, 14) and an opened, use position partial displaced from and overlying a side edge of said enclosure. A personal computer according to Claim 2 wherein the first (12) and second (14) housings each have a generally rectangular parallelepiped configuration of predetermined length, width and depth dimensions, said housings being joined for pivotal movement thereof one relative to the other about the housing axis parallel to the lengthwise dimensions. A personal computer according to Claim 3 wherein the length dimensions of said housings (12, 14) are equal and the width dimensions of said housings are less than said length dimension. A personal computer according to Claim 4 wherein said width dimensions of said housings (12, 14) are equal. A personal computer according to Claim 4 or 5 wherein said depth dimensions of said housings (12, 14) are equal. A personal computer according to Claim 3, 4, 5 or 6 wherein said housings are movable between a folded positions in which said first (12) and second (14) housings are superposed and externally facing planar parallelogram surfaces thereof are parallel and a opened use position in which said first (12) and second (14) housings are angularly disposed and the externally facing parallelogram surfaces thereof define therebetween an obtuse angle. A personal computer according to Claim 3, 4, 5, 6 or 7 wherein said computer operating components comprise: a display (71) for presenting to a user a visual display of information processed by the personal computer; a central processor unit (32) for manipulating information and operatively connected with said display (71); random access memory (38) for exchanging with said processor unit (32) information manipulated by said processor unit and for storing information exchanged; a direct memory access controller (50) operatively associated with said central processor unit (32) and said random access memory (38) for controlling access to said random access memory; a direct access storage device for exchanging information with said processor unit (32) and said random access memory (38) and operatively associated with said direct memory access controller (50); and a power supply for supplying energy for the operation of said computer operating components. A personal computer according to Claim 8 wherein said direct access storage device is mounted in one of said housings (12, 14) and said display (71) is mounted in the other of said housings (12, 14). A personal computer according to Claim 9 wherein said direct access storage device is mounted in the housing (14) to which the keyboard assembly (90) is coupled. A personal computer according to Claim 3 wherein said keyboard portions (91, 92) each have a generally rectangular parallelepiped configuration with predetermined length, width and depth dimensions, and further wherein said keyboard axis extends parallel to the depthwise dimensions of said portions. A personal computer according to Claim 11 wherein said keyboard portions (91, 92) are movable between a folded position in which lengthwise side edges of said first (91) and second (92) portions adjoin and an opened use position in which widthwise said edges of said first (91) and second (92) portions adjoin. A personal computer according to Claim 11 or 12 wherein said length dimensions of said keyboard portions (91, 92) are approximately equal to said widthwise dimension of said coupled housing and said widthwise dimensions of said keyboard portions (91, 92) are approximately equal to one half of said lengthwise dimension of said coupled housing, said keyboard assembly (90) being pivotable about said keyboard axis to length and width dimensions no greater than those of said housings. A personal computer according to any one of Claims 3 to 13 having a joint comprising a sliding connector coupling said keyboard assembly (90) and one of the housings (12, 14) and accommodating linear movement of said keyboard axis between locations adjacent each of the two lengthwise edges of said coupled housing. A personal computer according to Claim 14 wherein said joint captures said keyboard assembly (90) against (90) against ready separation from said coupled housing (12, 14). A personal computer as claimed in any preceding claim, wherein a pin operatively couples said keyboard portions (91, 92) one to the other for pivotal movement one relative to the other about the keyboard axis and operatively couples said keyboard portions (91, 92) with one of said housings for sliding movement relative thereto between a position superposed on said coupled housing and a position displaced from said coupled housing and partially overlying a lengthwise side edge thereof. A personal computer as claimed in Claim 16, further comprising: a pair of keyboard scanning devices, one mounted in each of said keyboard portions (91, 92) for scanning those key elements mounted in the corresponding portion, said scanning devices forwarding to a central processor unit (32) signals indicative of the characters and commands keyed by a user; and signal communicating conductors extending through said pin for operatively connecting said scanning devices and said central processor unit (32). A personal computer according to any preceding claim in the said keyboard assembly of which widthwise side edges of said first and second keyboard portions are castellated.	IBM; INTERNATIONAL BUSINESS MACHINES CORPORATION	POLLITT RICHARD FRANCIS; POLLITT, RICHARD FRANCIS
EP-0489492-B1	489,492	EP	B1	EN	19,940,622	1,992	20,100,220	new	C01B6	C01B6	B01J2, C01B6	B01J 2/30, C01B 6/21	Improved sodium borohydride compositions and improved method of producing compacted sodium borohydride	Sodium borohydride powder compositions include a silica-based anticaking agent to improve flowability without turbidity. In a method of making such a composition wherein a mixture of sodium borohydride and the anticaking agent are compacted under pressure, the use of the silica-based anticaking agent also improves processing, particularly the processing speed.	The present invention is directed to sodium borohydride compositions in powder form which provide improved free-flow and to sodium borohydride compositions which exhibit reduced turbidity when dissolved in aqueous media. The present invention is also directed to an improved method of producing compacted sodium borohydride. BACKGROUND OF THE INVENTION Sodium borohydride (NaBH₄) is a potent reducing agent useful in a variety of applications, including production of dithionite for pulp bleaching and recovery of heavy metals from waste streams. Dry sodium borohydride (referred to as SBH ) is typically produced as a powder having particle sizes of between about 30 and 100 µm and is used in many applications as a powder. To promote free-flow of SBH powder, it is known to admix SBH powder with an anticaking agent (referred to as ACA ). The most widely used anticaking agent has been magnesium carbonate-based products (referred to as mag carb ). When making SBH aqueous or nonaqueous solutions with magnesium carbonate-containing formulations, there is often a problem with turbidity, presumably because of inability of the magnesium carbonate to dissolve. There exists a need for powdered sodium borohydride compositions which exhibit turbidity when dissolved in aqueous media. The present invention provides a composition comprising sodium borohydride and a silica-based anticaking agent in an amount of 0.05 to 2 weight percent relative to the sodium borohydride. The silica-based anticaking agent provides improved free-flow of powdered sodium borohydride relative to magnesium cabonate-based anticaking agent. When dissolved in an aqueous medium, sodium borohydride that has been formulated with a silica based anti-caking agent exhibits substantially reduced turbidity. In accordance with another aspect of the present invention there is provided a method of producing compacted sodium borohydride by admixing powdered sodium borohydride with powdered anticaking agent and compacting said mixture under pressure, characterised in that said anticaking agent comprises at least 90 % by weight of silica. Significantly improved production rates are achieved when a silica-based anticaking agent is used. Powdered borohydride generally has particle sizes in the range of between 30 and 100 micrometers. By silica-based anticaking agent is meant powders of particle size between 1 and 20 nanometers and containing at least 90 weight percent, preferably 95 weight percent, silicon dioxide. The anticaking agent may be fine silica powder obtained by any one of several processes (e.g., fumed silica or precipitated silica). Alternatively, silica powders coated with a hydrophobic substance, such as a silane, a silicon oil, a hydrocarbon oil, chlorinated hydrocarbon oil, or mixtures thereof may be used. Such coated silicas are sold, for example, by Cabot Corp. and by Degussa Corp. The silica-based anticaking agent is used at a level of between 0.05 and 2 wt percent relative to the sodium borohydride, preferably in the range of 0.1 to 1 wt percent. To produce a free-flowing composition, SBH and the silica-based anticaking agent are thoroughly blended, e.g., using a ribbon blender. Another form in which SBH is often marketed is compacted bodies which may take the form of pellets, caplets or granules. In the terminology of compacted SBH products, pellets are those produced by compaction in individual dies on a rotating plate feed and tend to be relatively large, e.g., cylinders 25 mm in diameter, 6 mm height. Briquette forms (termed caplets ) are produced by compaction between continuous roller presses that provide appropriate indentations for formation of the compacted product. The roller press approach produces compacted products more efficiently than the rotating die method. Caplets are generally considerably smaller than pellets, one typical caplet is 17 mm long X 11 mm wide with a thickness of 5 mm. Granules are fragmented pellets or caplets, more generally fragmented caplets, and are typically size-sorted with screens according to use requirements. Compaction pressures for forming either pellets or caplets are typically in the range of between 350 and 700 kg/cm². Compacted SBH's have the advantage over powdered SBH of reducing dust. Larger compacted products are inherently easier to handle than powder. Importantly, in processes wherein solvent is passed through a bed of SBH, compacted products lend themselves to bed formation much more readily than do powders. (It may become nearly impossible to pass solvent through powder which becomes compacted, whereas a bed of pellets, caplets or granules provides openings through which solvent may pass.) Compacted SBH was initially made from pure SBH powder. It has been found, however, that the use of an anticaking agent is advantageous in producing compacted SBH, particularly in the continuous feed processes, such as those utilized in producing caplets, as free flow of the SBH enhances production rates. In accordance with the invention, it is now found that SBH with silica-based anticaking agent can be compacted at a much higher production rate than SBH with a magnesium carbonate-based anticaking agent. The invention will now be described in greater detail with reference to specific examples. Example 1COMPARISON OF FLOW AND TURBIDITY OF SODIUM BOROHYDRIDE WITH MAGNESIUM CARBONATE-BASED ANTICAKING AGENT AND SILICA-BASED ANTICAKING AGENTSodium borohydride was formulated with a magnesium carbonate based anticaking agent (Merck's Magcarb® L and silica based anticaking agent (Cabot's Cab-O-Sil® EH-5). The compositions, turbidity characteristics and flow characteristics, are shown below. (Total composition as listed is less than 100%; the balance is minor impurities, such as sodium borate, which sodium borohydride typically contains.) It can be seen that lower levels of the silica-based anticaking agent result in a better flow than greater amounts of magnesium carbonate-based anticaking agent. Also, the turbidity of a sodium borohydride solution in sodium hydroxide is almost eliminated. Example 2COMPARISON OF PRODUCTION RATES VIA THE BOLLER PRESS METHOD OF SODIUM BOROHYDRIDE CONTAINING 0.5% ANTICAKING AGENTEquipment: Commercial Roller Press Compactor Example 3Compositions were prepared containing 99.5% by weight SBH and 0.5% by weight anticaking agent. Flowability was tested initially and weekly. The results are as shown below.Sample Size: Approximately 50 g stored in constant temperature and humidity room (20°C/64% relative humidity). T-Tapping required (initially and 2-3 times during test) for complete flow. Example 4Compositions were formulated containing 99.5% by weight SBH and 0.5% by weight anticaking agent. Aqueous solutions (preadjusted to pH 12 with sodium hydroxide) of 0.1% SBH and 1.0% SBH were prepared, and turbidity was measured. The results are as follows: Some preliminary results indicate that sodium borohydride with silica-based anticaking agent also produces good turbidity results in a number of organic solvents, such as 1-hexanol; as good or even better than using magnesium carbonate-based anticaking agent.	A Composition comprising sodium borohydride and a silica-based anticaking agent in an amount of 0.05 to 2 weight percent relative to the sodium borohydride. A Composition according to claim 1 wherein said silica is a fumed silica. A Composition according to claim 1 wherein said silica is a precipitated silica. A composition according to any preceding claim wherein said anticaking agent is used in an amount of 0.1 to 1 weight percent relative to the sodium borohydride. A composition according to any preceding claim wherein said sodium borohydride has particle sizes from 30 to 100 µm. A Composition according to any preceding claim wherein said silica-based anticaking agent has particle sizes from 1 to 20 nm. A composition according to any preceding claim wherein said anticaking agent comprises at least 90 percent by weight silica the balance being a Coating of hydrophobic material. A composition according to claim 7 wherein said hydrophobic material is selected from silane, silicon oil, hydrocarbon oil, chlorinated hydrocarbon oil and mixtures thereof. A Composition according to any preceding claim which is compacted. A method of producing compacted sodium borohydride by admixing powdered sodium borohydride with powdered anticaking agent and compacting said mixture under pressure, characterised in that said anticaking agent comprises at least 90 % by weight of silica. A method according to claim 10 wherein said silica is coated with a hydrophobic coating. A method according to claim 10 or claim 11 wherein said mixture is compacted between patterned rollers. A method according to claim 10 or claim 11 wherein said mixture is compacted in dies.	MORTON INT INC; MORTON INTERNATIONAL, INC.	PATTON RICHARD A; RICHARDSON WALTER A; PATTON, RICHARD A.; RICHARDSON, WALTER A.
EP-0489495-B1	489,495	EP	B1	EN	19,960,306	1,992	20,100,220	new	C09J151	C08F8, C08F255	C08F8, C08F255, C09J151	C08F 8/34+10/00, C09J 151/06, C08F 255/02B+222/04, C08F 8/14+10/00	Modified halogenated polyolefin adhesives	An adhesive composition useful for bonding thermoplastic elastomers to substrates such as metal that contains a halogenated polyolefin that has been chemically modified to contain a polyhydroxylic aromatic compound and/or a sulfur-containing compound. The modified polyolefin is preferably prepared by first reacting the polyolefin with an acid anhydride and then reacting the anhydride-modified polyolefin with the polyhydroxylic aromatic compound and/or the sulfur-containing compound.	The present invention is concerned with a novel, chemically modified polymeric material that can be used to provide excellent adhesion between injection molded polyolefinic thermoplastic elastomers and metal substrates onto which the thermoplastic elastomer is molded. More particularly, the invention relates to halogenated polyolefins, such as chlorinated polypropylene, which have been modified to contain certain polyhydroxylic aromatic compounds and/or certain sulfur-containing compounds. In general, polyolefinic thermoplastic elastomers, such as those where polypropylene is the matrix and cured rubber forms a discrete second phase (e.g., SANTOPRENE supplied by Monsanto), adhere poorly to metal, glass, and other substrates. When these types of elastomers are molded against a substrate, such as a metal insert in injection molding, an adhesive must first be applied to the substrate to ensure sufficient adhesion between the elastomer and the substrate. Chlorinated polyolefins and modified chlorinated polyolefins are well known to provide adhesion to polyolefinic materials, such as polyolefinic thermoplastic elastomers and polypropylene (Eastman Chemicals Publication No. GN-360-C, August, 1988; Eastman Chemicals Publication No. X-294, March, 1989). The influence of the amount of chlorine, the molecular weight of the polymer, its melting point, and other variables on the efficacy of adhesion between chlorinated polypropylene and polyolefinic substrates has been reported by Fujimoto (F. Fujimoto, Paint and Resin, February, 1986, p. 36.). Chlorinated polyolefins are, for example, the primary ingredient in primers used to bond to polyolefins (Renout, European Patent Application 0 187 171, July 1986). Chlorinated polyolefins do not, however, strongly adhere to other materials such as metal. Eckhardt (U. S. Patent No. 3,620,860) describes chlorinated polymers of ethylene that are claimed to be effective temporary bonding agents for metals, but the substrates bonded by those chlorinated polymers are readily separated from each other. In order to attain adhesion between compositions containing chlorinated polyolefins and other materials, the chlorinated polyolefins must typically be mixed with other ingredients. Van Meesche and Radar (A. Van Meesche and C. Radar, Elastomerics, September, 1987, p. 21) describe compositions that are mixtures of modified polyolefins (chlorinated polyolefins) and polyurethane resins. These compositions are reported to provide adhesion to a wide variety of other substrates. These compositions have several drawbacks, including insufficient adhesion and environmental resistance. Modifications of polyolefins in order to promote adhesion to metal, glass, and other substrates are also well known in the art. Baum (U. S. Patent No. 3,211,804) describes the modification of polyolefins with polymethylolated phenolic material containing one or more phenolic nuclei and having substituted on the phenolic nuclei at least two methylol groups (-CH₂OH). Baum further describes the adhesional benefits of carboxyl and hydroxyl groups attached to the polyolefin. Van Meesche and Radar (A. Van Meesche and C. Radar, Elastomerics, September, 1987, p. 21) report that carboxylated polypropylene is an effective adhesive for bonding polyolefinic thermoplastic elastomers to metal, but it has the major disadvantage of a high activation temperature of ∼200 °C. Van der Kooi and Goettler (J. P. Van der Kooi and L. A. Goettler, Rubber World, Vol. 192, No. 2, 1985, p. 38) describe several modified polyolefins used to bond polyolefinic thermoplastic elastomers to metal, including carboxylated polyolefins. These polymers also have the disadvantage of a high activation temperature. Nogues (U. S. Patent 4,822,688) describes the use of non-halogenated polypropylene that has been grafted with maleic anhydride in adhesive formulations. Nogues further describes the reaction of such materials with polyols and polyamines. Bratawidjaja et al (Bratawidjaja, A. S.; Gitopadmoyo, I.; Watanabe, Y.; Hatakeyama, T. Journal of Applied Polymer Science, Vol. 37, 1989, p. 1141) also describe the relationship between the extent of grafting of maleic anhydride onto polypropylene and its adhesive strength to aluminum. These compositions have disadvantages that include high activation temperatures and insolubility in most solvents, precluding use in a solvent borne adhesive system. Other methods of bonding polyolefins to substrates typically involve surface pretreatment of the polyolefin prior to bonding. These technologies involve such processes as plasma treatment, corona discharge, and chemical etching as with chromic acid. These technologies are widely known and practiced but have several disadvantages. The foremost of these disadvantages, with respect to bonding during molding of polyolefins such as polyolefinic thermoplastic elastomers, is that the polyolefin must have a solid surface to pretreat. When molding these materials onto a substrate, as in injection molding onto a metal insert, there is no polyolefin surface that is readily modified prior to adhesion. Thus the process of injection or compression molding effectively precludes surface pretreatment of the polyolefin to promote adhesion either to the substrate or to an adhesive already applied to the substrate. Adhesives, such as described above, currently used for bonding polyolefinic thermoplastic elastomers to metal substrates have many drawbacks that are eliminated by the present invention. These drawbacks include the requirement for a primer applied to the substrate prior to the adhesive, poor shelf stability, poor environmental resistance, poor strength, inconvenient processing requirements, and toxic and/or flammable solvents. The present invention relates to a chemical modification of a halogenated polyolefin that permits surprisingly effective adhesion to substrates such as metal without decreasing the adhesion to polyolefinic thermoplastic elastomers. The present invention involves applications where the modified halogenated polyolefin is used either by itself or in formulations with other adhesive ingredients, such as polymers and adhesion promoters, known to those skilled in the art. The present chemical modification involves the attachment of certain chemical species to the halogenated polyolefin (usually chlorinated and/or brominated polypropylene) in quantities sufficient to provide significant adhesion to a substrate of choice while not interfering with adhesion to polyolefinic thermoplastic elastomers. Specifically, the chemical modification involves first grafting an acid anhydride onto the halogenated polyolefin in a known manner using an appropriate catalyst. The acid anhydride-modified polymer is then reacted with certain polyhydroxylic aromatic compounds that greatly increase its adhesion to a substrate of choice such as metal. Sulfur-containing compounds can additionally be used for this purpose. Attachment of these moieties to the halogenated polyolefin through reaction with the acid anhydride results in a material that effectively adheres both polyolefinic thermoplastic elastomers and metal substrates. Neither halogenated polyolefins nor maleic anhydride-modified halogenated polyolefins provide the adhesive properties of the chemically modified halogenated polyolefins of this invention. The nature of the group reacted with the grafted acid anhydride is critical to the present invention. It has presently been discovered that certain polyhydroxylic aromatic compounds either alone or in combination with certain sulfur-containing compounds are effective in generating significant adhesion between polyolefinic thermoplastic elastomers and metal substrates. The present invention comprises a halogenated polyolefin to which has been attached certain adhesion promoting agents. The adhesion promoting agents comprise certain polyhydroxylic aromatic compounds alone or in combination with certain sulfur-containing compounds and are chemically attached to the halogenated polyolefin by first reacting the polyolefin with the appropriate one or more adhesion promoting agents. Simple admixture of these agents is not sufficient to promote adhesion; they must be chemically reacted to achieve optimum results. The halogenated polyolefin can be any natural or synthetic halogenated polyolefin elastomer. Halogenated polyolefins and their preparation are well known to those skilled in the art. The halogens employed in the halogenated polyolefinic elastomer are typically chlorine or bromine, although fluorine can also be used. Mixtures of halogens can also be employed in which case the halogen-containing polyolefinic elastomer will have more than one type of halogen substituted thereon. The halogenated polyolefin typically has a halogen content ranging from about 10 to 70, preferably from about 20 to 45, percent by weight. Polyolefins which can be halogenated for use in the invention include, but are not limited to, polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-acrylic acid copolymers, ethylene-propylene-acrylic acid terpolymers, ethylene-propylene-diene terpolymers, ethylenevinyl acetate copolymer, polybutene, and polystyrene. Representative halogenated polyolefins include chlorinated natural rubber, chlorine- and bromine-containing synthetic rubbers including polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene, hexachloropentadiene, chlorinated butadiene styrene copolymers, chlorinated ethylene propylene copolymers and ethylene/propylene/nonconjugated diene terpolymers, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, brominated poly(2,3-dichloro-1,3-butadiene), copolymers of a-chloroacrylonitrile and 2,3-dichloro-1,3-butadiene, chlorinated poly(vinyl-chloride), and the like, including mixtures of such halogen-containing elastomers. Thus substantially any of the known halogen-containing derivatives of natural and synthetic elastomers can be employed in the practice of this invention, including mixtures of such elastomers. At the present time, chlorinated isotactic polypropylene (26% chlorine by weight) which results in a viscosity of 50-500 cps when dissolved in toluene (10% by weight), chlorinated polyethylene (25% chlorine by weight), and brominated chlorinated polyolefins, constitute preferred halogenated polyolefins for use in the present invention. The halogenated polyolefin is normally utilized in an amount from about 10 to about 99 percent by weight, preferably from about 30 to about 70 percent by weight of the total amount of adhesive precursor ingredients. Total amount of adhesive precursor ingredients herein refers to the total amount of halogenated polyolefin, acid anhydride, catalyst (if utilized), polyhydroxy aromatic compound and sulfur-containing compound utilized to prepare the present adhesive compositions. The acid anhydride utilized to prepare the halogenated polyolefin for further reaction with the present adhesion promoters can be any compound bearing at least one double bond, which is active in radical polymerization, and at least one five-centred cyclic acid anhydride group. By way of illustration, the grafting anhydrides can be maleic, citraconic, 2-methylmaleic, 2-chloromaleic, 2-carbo-methoxymaleic, 2,3-dimethylmaleic, 2,3-dichloromaleic, 2,3-dicarbomethoxymaleic, bicyclo-[2.2.1]hept-5-3n3-2,3-dicarboxylic, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, or the like. The presently preferred acid anhydride is maleic anhydride. The acid anhydride is utilized in an amount ranging from about 0.1 to 50, preferably about 1 to 10 percent by weight of the total amount of adhesive precursor ingredients. The polyhydroxylic aromatic compounds of the invention which are useful for imparting exceptional adhesion ability to the acid anhydride-modified polyolefins can be any compound containing an aromatic moiety to which is attached at least two OH groups. The polyhydroxylic aromatic compound typically contains from 6 to 24, preferably 6 to 14, carbon atoms and can contain multiple aromatic moieties, including fused aromatic moieties. Typical polyhydroxylic aromatic compounds include quinalizarin; 2,6-bis(hydroxymethyl)-p-cresol; alizarin; alizarin red S; acid alizarin voilet N; quercetin; fisetin; pyrogallol; pyrocatechol voilet; aurintricarboxylic acid; apigenin; naringenin; purpurogallin; and 2,4,5-trihydroxypyrimidine; and combinations thereof; with quinalizarin being particularly preferred. The polyhydroxylic aromatic compounds are typically employed in an amount ranging from about 0.1 to 50, preferably from about 5 to 30, percent by weight of the total amount of adhesive precursor ingredients. The sulfur-containing compounds can be any compound which contains at least one sulfur atom and one active hydrogen-containing group (such as -OH, -SH, or -NH₂). Typical sulfur compounds include 3-aminorhodanine; 1,5-pentanedithiol; p-benzene-dithiol; 2-mercaptoethanol; tioxolone; 6-methyl-2-thiouracil; 2-mercaptobenzothiozole; 2-mercaptoimidizole; 2-mercaptothiazoline; 2-mercapto-pyridinol; 2-hydroxethylsulfide; 2-hydroxyethyl-disulfide; 2-aminoethanethiol; p-mercaptoaniline; 2-aminoethyl-disulfide; and combinations thereof with 3-aminorhodanine and 1,5-pentanedithiol being preferred. The sulfur-containing compounds are typically utilized in an amount ranging from about 0.1 to 50, preferably from about 5 to 30, percent by weight of the total amount of adhesive precursor ingredients. One or more polyhydroxylic aromatic compounds may also be utilized in combination with one or more sulfur-containing compounds to impart adhesive properties to the modified polyolefins of the present invention. The polyhydroxylic aromatic compounds and sulfur-containing compounds used in the invention are known compounds available to those skilled in the art. The chemical modification is a two-step process. The first step is attachment of the acid anhydride to the halogenated polyolefin using conventional techniques which may or may not employ a catalyst or an initiator. A preferred technique for attaching the acid anhydride to the halogenated polyolefin involves utilizing an organic peroxide or other free radical initiator such as 2,2'-azo-bis-isobutyronitrile, dimethyl 2,2'-azo-isobutyrate, phenyl-azo-triphenylmethane or t-butylperbenzate as an initiator. The organic peroxide or other initiator initiates a free radical site on the halogenated polyolefin for reaction with the acid anhydride as is known in the art. Organic peroxides are preferred initiators and typical organic peroxides include benzoyl peroxide, t-butyl-peroxide, dicumylperoxide, acetyl peroxide, hydrogen peroxide, and t-amyl peroxide, with benzoyl peroxide being preferred. The organic peroxide is typically utilized in an amount ranging from about 0.01 to 5, preferably from about 0.5 to 3, percent by weight of the total amount of adhesive precursor ingredients. The reaction of the halogenated polyolefin and the acid anhydride in the presence of an organic peroxide is preferably carried out in the presence of a solvent such as benzene or chlorobenzene, with chlorobenzene being the preferred solvent. The halogenated polyolefin, solvent, and acid anhydride are typically combined and brought to reflux, after which the organic peroxide is added and the mixture refluxed from about 40 minutes to 1.5 hours. The resulting material has acid anhydride moieties actually grafted onto the chlorinated polypropylene chain. If maleic anhydride units are simply mixed with the chlorinated polypropylene, but not chemically attached with an initiator, the results are poor. Active sites may also be generated on the polyolefin through the use of diazo-type initiators or with electromagnetic treatment. The polyolefin may be preactivated independently of the acid anhydride and thereafter reacted with the anhydride or anhydride modification may be carried out simultaneously as described in U.S. Pat. Nos. 2,970,129 and 3,414,551, which are incorporated herein by reference. The second step involves attachment of the present adhesion promoting moieties to the anhydride-modified halogenated polyolefin. These moieties are reacted with the anhydride groups on the halogenated polyolefin. It is not necessary that all, or even a majority of the maleic anhydride units be reacted. It is often sufficient that only a small proportion (1-20%) of the maleic anhydride units be reacted with the adhesion promoting moiety. The reaction between the anhydride-modified polyolefin and the adhesion promoter is typically carried out by simply mixing the polyolefin and adhesion promoter in a suitable solvent. Typical solvents include benzene, toluene, chlorobenzene, chloroform and methylene chloride, with chlorobenzene being preferred. The mixture is then typically brought to reflux for a period of time ranging from 40 minutes to 1.5 hours in order to ensure sufficient reaction. The reacted polymer can optionally be purified in any of the many ways known in the art. These include repeated precipitation, followed by dissolution, and extraction with a Soxhlet-type apparatus. The resulting material can be dissolved in an appropriate solvent, such as toluene, xylene, or chlorobenzene for application. Alternatively, it can be dispersed in water using appropriate surfactants known to those skilled in the art. The material can also be used in solid form as a powder coating or a hot applied adhesive, eliminating the need for solvent. The resulting polymeric material of the present invention can be used singly as an adhesive or in conjunction with other adhesive ingredients or primers known to those skilled in the art. Optional ingredients include, but are not limited to, fillers, adhesion promoters such as silanes and zircoaluminates, other polymers, plasticizers, and inhibitors. The modified polyolefins of the invention are preferably dissolved in a solvent and applied to a metal substrate by dipping, brushing, spraying, or the like, so as to create one or more coats of the formulation. The coated substrate should be allowed to dry for a period of time ranging from 1 hour to 24 hours. Prior to application of the thermoplastic elastomer by injection molding, the coated substrate may optionally be preheated to a temperature between about 100°C and 150°C for between about 15 seconds and 10 minutes. When bonding thermoplastic elastomers to various substrates, the thermoplastic elastomer is typically applied to the surface of the substrate from an injection molding device according to techniques well known in the art. A thermoplastic elastomer applied from such a molding device typically has an initial temperature of from about 148.9°C (300°F) to about 232.2°C (450°F) and the coated substrate and thermoplastic elastomer are brought together under a pressure of from 3.45 x 10⁶ (500) to about 6.89 x 10⁷ Pa (10,000 psi). After the thermoplastic elastomer and substrate are brought together, the elastomer-substrate assembly is allowed to cool for a period from about 1 hour to about 24 hours. The thermoplastic elastomer and the substrate may also be bonded according to other methods such as assembly bonding or extrusion. Although the adhesives of the present invention are preferred for bonding thermoplastic elastomers to metal, the present adhesive compositions may be applied as an adhesive, primer or coating to any surface or substrate capable of receiving the adhesive. The material, which may be bonded to a surface such as a metal surface in accordance with the present invention, is preferably a polymeric material, including any elastomeric material selected from any of the natural rubbers and olefinic synthetic rubbers including polychloroprene, polybutadiene, neoprene, Buna-S, Buna-N, butyl rubber, brominated butyl rubber, nitrile rubber, and the like. The material is most preferably a thermoplastic elastomer such as the thermoplastic elastomers sold under the tradenames SANTOPRENE and ALCRYN by Monsanto and DuPont, respectively. The surface to which the material is bonded can be any surface capable of receiving the adhesive and is preferably a metal selected from any of the common structural metals such as iron, steel (including stainless steel), lead, aluminium, copper, brass, bronze, Monel metal, nickel, zinc and the like. The following examples are provided for illustration purposes only and are not intended to limit the scope of the invention. Example 1Chlorinated polypropylene (10g; 26% Cl by weight) is dissolved in 50 mL of chlorobenzene. Maleic anhydride (0.5g) is added and the solution brought to reflux. Benzoyl peroxide (0.2g) is added and the solution refluxed for 1 hr. The solution is cooled to room temperature, 3 g of quinalizarin added, and the solution heated to reflux for 1 hr. The solution is cooled to room temperature, 200mL of chlorobenzene is added, excess solid is filtered off, and the liquid poured into an excess of methanol (∼2.5 L) to precipitate the desired product. This material is optionally purified by dissolving in chlorobenzene (100mL) and precipitation in methanol (2.5 L) repeated several times. The solid material (referred to as CPP/Quinalizarin) is permitted to air dry for a few hours and then tested as desired. The CPP/Quinalizarin is dissolved in toluene (∼20% by weight) and then applied directly to the substrate according to ASTM D429B 0.025m (1 ) x 0.059m (2.36 ) steel alloy 1010 coupon). The substrates are allowed to air dry for at least 1 hr. and are then injection molded to a polyolefinic thermoplastic elastomer (SANTOPRENE 101-55). The elastomer-metal joints are formed by placing the adhesive-coated steel substrate into a mold and injection molding the elastomer onto the steel. Samples are molded with the mold temperature at 79.5°C (175°F). The joints are cooled and then tested in a 45° peel geometry according to ASTM D429B. Peel strength kg/m (1b/in.) and percent rubber failure are calculated and the results shown below in Table 1. A high percentage of rubber failure indicates a strong adhesive bond since rubber failure indicates that the bond was stronger than the rubber itself. Data was also obtained for coupons that were immersed in water for one week, and the results of the water test are set forth in Table 2. Example 2The CPP/Quinalizarin produced in Example 1 is tested as in Example 1 using SANTOPRENE 101-64 as the polyolefinic thermoplastic elastomer and grit-blasted steel as the substrate according to ASTM D429B (the mold is at room temperature during molding and a 45° peel geometry is used). The results are shown in Table 3 for initial peel strengths and Table 4 for peel strengths after exposure to water for one week under stress. Example3The material of Example 1 is made using 3-amino-rhodanine instead of quinalizarin (CPP/AR). Joints made as in Example 1 (mold temperature = 79.5°C (175°F) ; no preheating of the substrate prior to molding) had initial peel strength of 630 kg/m (35 lb/in) and a failure mode of 25% rubber tearing. Example 4The material of Example 1 is made using 2,6-bis (hydroxymethyl)-p-cresol instead of quinalizarin (CPP/BHMC). Solid CPP/BHMC is obtained by eliminating the final step involving dissolution of the product in toluene, and the solid is used to make joints by applying powdered CPP/BHMC to the steel substrate and melting the powder into the steel (mold temperature = 79.5°C (175°F); substrate is preheated for 30 sec at 143.3°C (2890°F) prior to molding). These joints have initial peel strength of 630 kg/m (37 lb/in) and a failure mode of 45% rubber tear. Example 5Chlorinated polypropylene is reacted with maleic anhydride and 1,5-pentanedithiol as in Example 1 with the dithiol substituting for quinalizarin. The product, referred to as CPP/Pentanedithiol, is tested as in Example 1 with the substrate being preheated for 5 minutes at 130°C immediately prior to insertion in the mold. The resulting joint exhibits an initial peel strength of 630 kg/m (36 lb/in.) and a failure mode of 89% rubber tear. As can be seen from the data in the above examples, the modified halogenated polyolefins of the present invention provide for moderate to excellent adhesive bonds between thermoplastic elastomers and substrates such as metal. In light of the difficulty in bonding thermoplastic elastomers in general, even a 25% rubber failure is deemed to be a successful thermoplastic-metal bond.	An adhesive composition comprising a reaction product prepared by grafting a halogenated polyolefin with an acid anhydride and then reacting the anhydride-grafted polyolefin with a polyhydroxylic aromatic compound. An adhesive composition according to Claim 1, wherein the halogenated polyolefin is selected from the group consisting of chlorinated polypropylene, chlorinated polyethylene, and brominated chlorinated polyolefins. An adhesive composition according to Claim 2, wherein the halogenated polyolefin is chlorinated isotactic polypropylene. An adhesive composition according to any one of the preceding claims, wherein the polyhydroxylic aromatic compound is selected from the group consisting of quinalizarin, 2,6-bis(hydroxymethyl)-p-cresol, alizarin, and alizarin red S. An adhesive composition according to Claim 4, wherein the polyhydroxylic aromatic compound is quinalizarin. An adhesive composition according to any one of the of the preceding Claims wherein the anhydride-grafted polyolefin is reacted with a polyhydroxylic compound and a sulfur-containing compound. An adhesive composition according to Claim 6 wherein the sulfur-containing compound is selected from the group consisting of 3-aminorhodanine, 1,5-pentanedithiol, and p-benzenedithiol. An adhesive composition according to Claim 7, wherein the sulfur-containing compound is 1,5-pentanedithiol. An adhesive composition according to any one of the preceding claims, wherein the acid anhydride is selected from the group consisting of maleic anhydride, citraconic anhydride, and 2-methylmaleic anhydride. An adhesive composition according to Claim 9, wherein the acid anhydride is maleic anhydride. An adhesive composition as claimed in any one of the preceding claims, wherein the reaction product produced by reacting from about 10 to 99 percent by weight of a halogenated polyolefin and from about 0.1 to 50 percent by weight of an acid anhydride; and wherein the reaction product is reacted with from about 0.1 to 50 percent by weight of at least one compound selected from a polyhydroxylic aromatic compound or a mixture of polyhydroxylic aromatic compound and a sulfur-containing compound; said percents by weight being based on the total amount of adhesive precursor ingredients. An adhesive composition according to Claim 11, wherein the halogenated polyolefin is present in an amount from about 30 to 70 percent by weight; the acid anhydride is present in an amount from about 1 to 10 percent by weight; and the polyhydroxylic aromatic compound or a mixture of polyhydroxydic aromatic compound and the sulfur-containing compound is present in an amount from about 5 to 30 percent by weight; said percents by weight being based on the total amount of adhesive precursor ingredients. An adhesive composition comprising the reaction product of: A). the reaction produce of from about 30 to 70 percent by weight of chlorinated polypropylene and from about 1 to 10 percent by weight of maleic anhydride; and B). from about 5 to 30 percent by weight of quinalizarin.	LORD CORP; LORD CORPORATION	HOLMES-FARLEY STEPHEN RANDALL; HOLMES-FARLEY, STEPHEN RANDALL
EP-0489496-B1	489,496	EP	B1	EN	19,960,814	1,992	20,100,220	new	A61B17	null	A61B17, A61M1	A61B 17/3203R, K61B17:3203	Water jet atherectomy device	A technique for treatment of plaque deposits (120) on the arterial wall (110) of a patient. The technique employs a high pressure jet (126) of sterile saline solution directed at the plaque deposit. The high pressure jet is located at the distal end of a guide wire or catheter (12) which is advanced through the vascular system to the site of the plaque deposit. Optional removal of the debris is via an evacuation lumen within the catheter. This particular technique directs the high pressure jet of fluid distal to the distal tip of the guide wire or catheter. This permits treatment of arteries, which are totally occluded, because the device need not transit the lesion to be effective. Some applications will use the high pressure jet of fluid to open a sufficient passage within the occlusion to permit further dilatation using a balloon (58) integral to or passed over the device. An ultrasonic transducer array located adjacent the high pressure jet permits the attending physician to monitor the procedure. This may be particularly important for those embodiments for which the high pressure jet of fluid may be inadvertently directed toward the vessel wall at short range. The ultrasound device ensures that the jet of fluid is directed at plaque, rather than the native vessel.	The present invention relates to apparatus for treating unwanted deposits within vessels or cavities of patients. Methods and apparatus have previously been proposed for removing tissue and various deposits from the body of a patient. U.S. Patent No.4 790 813 issued to Kensey and U.S. Patent No. 4 842 579 issued to Shiber describe techniques for the removal of plaque deposited in arteries by mechanical ablation using rotating cutting surfaces. These relatively traumatic approaches are directed to the treatment and removal of very hard substances. Pressurized fluids have been proposed to flush undesirable substances from body cavities. U.S. Patent No. 1 902 418 describes such a system for flushing body cavities of domesticated animals. More modern proposals tend to use vacuum rather than gravity as the primary means for removal of the deposits or tissue and to use relatively low fluid pressures for ablation. Thus, U.S. Patent No. 3 930 505 issued to Wallach describes a surgical apparatus for the removal of tissue from the eye of a patient. As with similar systems, Wallach uses a relatively low pressure jet of water (i.e. 103.4 to 24132kPa [15 to 3500 psi]) to disintegrate the tissue, and a suction pump to perform the actual removal. A similar approach applied to the cardiovascular system is discussed in U.S. Patent No. 4 690 672 issued to Veltrup. Veltrup also provides a low pressure jet of water (i.e. less than 3103 kPa (450 psi)) to flush the deposits. As with Wallach, Veltrup uses a vacuum pump for evacuation of the fragments. It seems apparent that the above-mentioned prior art uses only relatively low pressure jets for safety reasons. Furthermore, devices of most of that prior art are not suitable to treat fully occluded vessels as they require a portion of the device to transit the lesion. EP-A- 0 232 678 and DE-A- 3 715 418 each discloses apparatus for treating a deposit within a vessel of a patient, the apparatus comprising a device having a proximal end and a distal end, supplying means coupled to the proximal end of the device for supplying a fluid under high pressure and directing means coupled to the distal end of the device for directing a stream of the fluid under high pressure distal to the distal end of the device. The present invention, on the other hand, provides apparatus for treating a deposit within a vessel or cavity, that is vessels or cavities of humans or animals, using fluid under high pressure. Accordingly, the present invention provides an apparatus for treating a deposit within a vessel or cavity of a patient, which comprises: (a) a device having a proximal end and a distal end; and (b) supplying means coupled to said proximal end of said device for supplying a fluid under high pressure; (c) directing means coupled to said distal end of said device for directing a stream of the fluid under high pressure distal to said distal end of said device; characterised in that the directing means comprises a plurality of high pressure jets and each of the jets has a separate supply of the fluid. Said device can be a catheter or a guide wire. If desired, the catheter or other device used in the apparatus or method of the present invention can be one disclosed in our European Application 0 470 781. The term high pressure as used herein with reference to the liquid or other fluid refers to pressures above 24132 kPa i.e. 3,500 pounds per square inch (p.s.i.), for example pressures in the range 34475 to 344750 kPa (5,000 to 50,000 p.s.i.), especially 172375 kPa (25000 p.s.i.), 206850 kPa (30,000 p.s.i.), 241325 kPa (35,000 p.s.i) or other value in the range 137900 to 275800 kPa (20,000 to 40,000 p.s.i.). The following terms are relevant to the present invention. a) Atherosclerosis refers to a lesion which consists of deposits on the vessel intima of yellowish plaques containing cholesterol, lipid and possibly calcified material. b) Atherectomy refers to the removal of atheromatous plaque from the intima of an artery. The removal of the plaque is not done surgically, however. In the case of the apparatus of the present invention, the removal of plaque is accomplished by entering the vessel percutaneously, thus obviating the need for a surgical cutdown to access the vessel or access the vessel lumen. c) Rheolytic refers to breakup of plaque or thombus. In preferred forms the present invention overcomes the disadvantages of the prior art by providing a guide wire or catheter for the treatment of hardened or other deposits from a vessel or cavity of a patient. The term vessel or cavity as used herein refers, for example, to the cardiovascular system, vascular grafts, ureters, fallopian tubes, and other tubular tissues or cavities within the body. The high pressure jets are located at the distal end of the device which is advanced through the vessel or cavity to the location of the deposit. The stream of high pressure sterile saline ablates or otherwise treats the deposit upon contact. The resulting fragments may be removed through an evacuation lumen, and the force of the jets on the evacuation lumen can serve as a pump to remove the fragments through the catheter at positive pressure; evacuation does not require a vacuum. A key aspect of the present invention is that the high pressure jets of fluid are directed distal to the distal tip of the device. For this reason, the device is suitable for treatment of vessels which are fully occluded or nearly fully occluded. To improve monitoring possibilities during the procedure, an ultrasonic transducer array may be appropriately positioned at the distal end of the catheter. The transducer array may be directed toward the deposit or toward a mirror which is in turn directed toward the deposit by way of reflection. Angioscopy, fluorescence spectroscopy, or other monitoring methods may also be used to detect plaque. The device may employ as said plurality of high pressure jets multiple high pressure jets. The jet(s) may, for example, be directed parallel to the longitudinal axis of the vessel or may be angled toward or away from the longitudinal axis. Angled jets may be conveniently used to channel particulate material away from the vessel wall and toward the evacuation lumen. The jet(s) may be pulsed or operated at steady state. A distal balloon may be used to hold the device at the appropriate position within the vessel for ablation of the deposit, which provides an atherectomy function. An additional balloon may also be placed on the device or otherwise to provide dilation of the vessel, thereby providing an angioplasty function. There are now described, by way of example and with reference to the accompanying drawings, preferred embodiments of the apparatus of the present invention. It is to be noted that at least one of the embodiments described below does not have multiple high-pressure jets having separate supplies of fluid for the jets. Such embodiment(s) does not form part of the present invention. In the drawings: FIG. 1A is a plan view of an atherectomy system employing the present invention; FIG. 1B is a plan view of an atherectomy system having ultrasonic monitoring; FIG. 2A is a close-up sectioned view of manifold; FIG. 2B is a functional view of the manifold having ultrasonic monitoring; FIG. 3A is a partially sectioned view of the operation of a guide wire; FIG. 3B is a partially sectioned view of the operation of a catheter having a guide wire lumen; FIG. 3C is a partially sectioned view of the operation of a device having multiple high pressure jets; FIG. 3D is a partially sectioned view showing the operation of a guide wire having positioning bulbs; FIG. 3E is a partially sectioned view of the operation of a device having multiple high pressure jets and an evacuation lumen; FIG. 4 is a sectioned view of the distal tip of a catheter having a guide wire lumen; FIG. 5 is a transverse sectioned view of the catheter of FIG. 4; FIG. 6 is a partially sectioned view of a guide wire in use with a standard dilatation balloon catheter; FIG. 7 is a longitudinal sectioned view of the distal tip of a guide wire having a single high pressure jet and no evacuation lumen; FIG. 8 is a view of the distal tip of a catheter having multiple high pressure jets and an inflatable balloon; FIG. 9 is a transverse sectioned view of the catheter of Fig. 8 taken across the inflatable balloon; FIG. 10 is a transverse sectioned view of the catheter of Fig. 8 taken distal of the inflatable balloon; FIG. 11 is a view of the catheter of FIG. 8 taken from the distal end; FIG. 12 is a view of the distal end of a catheter having multiple jets, an inflatable balloon, an evacuation lumen, and a guide wire lumen; FIG. 13 is a transverse sectioned view of the catheter of FIG. 12 taken across the inflatable balloon; FIG. 14 is a view of the catheter of FIG. 12 taken from the distal end; FIG. 15 is a view of the distal end of a guide wire/catheter having multiple jets directed toward the longitudinal axis and forwardly directed ultrasonic transducers located on the tip; FIG. 16 is an end view of the guide wire/catheter of FIG. 15; FIG. 17 is a partially sectioned view of the distal end of a catheter having multiple, independently controlled jets; FIG. 18 is an end view of the catheter of FIG. 17; FIG. 19 is a transverse sectioned view of the catheter of FIG. 17 taken proximal of the nozzle assembly; FIG. 20 is a sectioned view of a catheter/guide wire having multiple jets directed parallel to the longitudinal axis and forwardly directed ultrasonic transducers located on the tip; FIG. 21 is a transverse sectioned view of the catheter/guide wire of FIG. 20 taken proximal of the nozzle assemblies; FIG. 22 is a view of the catheter/guide wire of FIG. 20 from the distal end; FIG. 23 is a longitudinal sectioned view of the distal end of a catheter having multiple angled jets and a guide wire lumen; FIG. 24 is a transverse sectioned view of the catheter of FIG. 23 taken proximal to the nozzle assembly; FIG. 25 is a transverse sectioned view of the catheter of FIG. 23 taken distal to FIG. 24; FIG. 26 is a view of the catheter of FIG. 23 taken from the distal end; FIG. 27 is a sectioned view of a guide wire having a positioning bulb; FIG. 28 is a view in partial phantom showing operation of a guide wire having a positioning bulb; FIG. 29 is a view of the guide wire of FIG. 28 taken from the distal end; FIG. 30 is a sectioned view of guide wire having multiple positioning bulbs; FIG. 31 is a sectioned view of the distal end of a catheter having multiple jets directed toward the longitudinal axis; FIG. 32 is a transverse sectioned view of the catheter of FIG. 31; and FIG. 33 is a view of the catheter of FIG. 31 taken from the distal end. It is to be noted that the elongate articles disclosed in Figures 3A, 3D, 7 to 27 and 30 and referred to in the relevant accompanying description as guide wires function as catheters, being tubes for admitting a fluid. The elongate articles disclosed in Figures 1A, 1B, 2A, 2B 3B, 4 to 6, 12 to 14, 23 to 26 and 31 to 33 and referred to in the relevant accompanying description as guide wires are indeed articles whose function is to act as a guide. FIG. 1A is a plan view of a high pressure catheter system 10 employing the present invention. Employing the present invention as a guide wire results in a similar system. However, the catheter application is described by way of example and not be be deemed as limiting, as it tends to be the more complex. Device body 12 is introduced into an artery of the patient at a convenient location, usually the femoral artery. DIstal end 56 is advanced to the site of the deposit to be treated. Ordinarily, this site will have been previously identified using a suitable diagnostic procedure, such as angiography. After location at the site of the deposit, the apparatus at distal end 56 of device body 12 serves to ablate and remove the deposit as explained in more detail below. Manifold 13 sealingly couples to the proximal end of device body 12 and serves to provide separate access to the various lumens of device body 12. Main branch 36 of manifold 13 sealingly couples to guide wire 32 to assist in positioning device body 12 in the manner known in the art. Note that in systems employing the present invention as a guide wire, guide wire 32 would not be needed. Positioning knob 34 assists the medical attendant in this procedure. Secondary branch 38 of manifold 13 permits access to device body 12 to supply the sterile saline solution under high pressure. Hypo tubing 40 is drawn from stainless steel to have the strength to handle the pressures up to 344 750 kPa (50,000 psi), and yet remain flexible enough to be positioned transarterially. Typical pressure is 206 850 kPa (30,000 psi) within the range of 34 475 kPa (5,000 psi) to 344 750 kPa (50,000 psi). Hypo tubing 40 traverses the entire length of device body 12 from distal end 56 to secondary branch 38. Preferably, and not by way of limitation, sterile saline is supplied by disposable saline solution bag 48. Low pressure tubing 50 conveys the sterile saline solution to high pressure piston pump 42. After pressurization by high pressure piston pump 42 of typically about 206 850 kPa (30,000 psi), the sterile saline solution is transported in the direction of arrow 44 through hypo tubing 40 to distal end 56 of device body 12. Safety monitor 52 functions to shut off high pressure piston pump 42 if a failure occurs. Secondary branch 22 of manifold 13 is coupled to the evacuation lumen of device body 12. Fragments of the ablated deposit are channeled from secondary branch 22 through low pressure tubing 26 in the direction of arrow 46. Safety monitor 24 ensures that the volume of effluent and pressures within the system are maintained within allowable tolerances. Peristaltic pump 28 meters the rate at which effluent is evacuated to disposable bag 30. The environment in which the ablation procedure occurs is greater than one atmosphere due to the impingement of the jet on the evacuation lumen. Peristaltic pump 28 meters evacuation of the effluent without ever creating a vacuum. FIG. 1B is a plan view of an alternative embodiment of the present invention. This catheter system includes all of the features of high pressure catheter system 10 with an inflatable distal balloon and ultrasonic monitoring. Distal balloon 58 may be inelastic such as those used in balloon dilatation, but may also be elastic such as a latex or rubber balloon. The balloon serves to hold the catheter in position to prevent inadvertent impingement of the high pressure jet on the vessel wall. This, or an additional balloon (not shown) located on the distal end of the catheter may be used as a vessel dilatation balloon after removal of the deposited material. In the alternative embodiment, manifold 13 (see also FIG. 1A) is replaced with manifold 14 having additional secondary branch 20. The inflation lumen of device body 12, which is coupled to distal balloon 58, is sealingly coupled through secondary branch 20 and flexible tubing 54 to balloon inflation device 16. In this way, distal movement of thumb plunger 18 causes inflation of distal balloon 58. An additional feature of the alternative embodiment is ultrasonic monitor 60 which is coupled via cable 64 to an ultrasonic transducer array (not shown in this view) located at distal end 56. Medical personnel may view the ablation procedure on screen 62 of ultrasonic monitor 60. FIG. 2A is a longitudinal sectioned view of manifold 14. It is preferably molded from a rigid plastic as two halves which are bonded together and are adhesively coupled to the catheter body 12 and hypo tube 40 at points 70, 76, 80, 84, 98, and 100. Device body 12 is sealingly coupled to the distal end using known techniques. Lumen 82 of secondary branch 22 is sealingly coupled to evacuation lumen 74. In most embodiments, evacuation lumen 74 will be the largest lumen of device body 12. Evacuation lumen 74 may also be coupled to main branch 36. Compression nut 88 attaches via threads 86 to compress O-ring 90 to sealingly engage guide wire 32. During initial positioning of device body 12, guide wire 32 may be located within evacuation lumen 74. Lumen 72 contains hypo tubing 40, which enters secondary branch 38, bends obliquely at point 94 and extends the length of lumen 72 distal to point 94. Also sharing lumen 72 is the function of inflating distal balloon 58. To accomplish this, lumen 66 of secondary branch 20 is coupled to lumen 72 at point 68. Fluid used to inflate distal balloon 58 (see also FIG. 1B) is forced through lumen 72 in that space not occupied by hypo tubing 40. FIG. 2B is a conceptualized view of the operation of manifold 14 wherein all referenced elements are as previously described. In this view it can be seen that septum 108 serves to separate evacuation lumen 74 from lumen 72. Flexible seal 106 seals secondary branch 38 against the walls of hypo tubing 40. FIG. 3A is a partially sectioned view of the operation of a rheolytic guide wire 112. To be useful, guide wire 112 must have a minimum outside diameter and maximum flexibility. In the present example, coronary artery 110 is completely occluded by calcified deposit 120. The medical condition cannot be treated using normal percutaneous translumenal coronary angioplasty (i.e. PTCA) because prior art guide wires and catheters are unable to cross the lesion at calcified deposit 120. This may also be the case in only partially occluded vessels, as well, if the opening within calcified deposit 120 is too small for a conventional guide wire or catheter. Guide wire 112 has a main body 116, which is a suitably coated length of stainless steel hypo tubing. It is necessary that the interior lumen of main body 116 have sufficient strength to handle the fluid under pressures up to 344 750 kPa (50,000 psi), typically about 206 850 kPa (30,000 psi). To achieve the desired small outside diameter, the hypo tubing of main body 116 is not covered with a separate sheath. Distal tubing 118 couples main body 116 with nozzle assembly 124. Jet 122 has a diameter of from 0.0254 to 0.102 mm (from 0.001 to .004 inch), for example from 0.0762 m to 0.102 mm (0.003 to 0.004 inch). Distal coil 114 encircles distal tubing 118 and provides the desired distal handling characteristics. In operation, jet 122 is positioned about 0.0254 to 5.08 mm (.001 to .200 inch) from calcified deposit 120. The high pressure fluid is supplied (see also FIGS. 1A and 1B) to produce high pressure stream 126, which abrades calcified deposit 120. Particulate material 128a-128n, which is generally small in size, can be generated from the ablation of plaque. The size of the particulate material is smallest when using a small orifice diameter and is smallest for hard materials, such as calcified plaque. Guide wire 112 has no evacuation lumen such that particulate material 128a-128n must be disposed of by the normal biochemical processes of the patient or other means. Guide wire 112 is advanced during the process until the lesion has been crossed, permitting another dilatation balloon or atherectomy device to be employed. FIG. 3B shows the operation of an atherectomy catheter 130 which is similar to rheolytic guide wire 112, except that it has a guide wire lumen 138. Atherectomy catheter 130 has a much larger outside diameter than guide wire 112. Outer sheath 132 is extruded from a flexible polymer. Septum 134 separates the interior of outer sheath 132 into two lumens. The smaller lumen contains main body 116 of stainless steel hypo tubing as described above. Distal tubing 118 couples main body 116 to nozzle assembly 124 containing jet 122. High pressure stream 126 is produced in the manner described above. The second and larger lumen formed within outer sheath 132 by septum 134 is guide wire lumen 138. This lumen is coupled to the manifold evacuation as explained above (see also FIGS. 1A and 1B). It contains guide wire 32. Note that because high pressure stream 126 is directed distal of the most distal point of atherectomy catheter 130, coronary artery 110, which is fully occluded by calcified deposit 120 may be treated in this manner. However, because the outside diameter of guide wire 112 is much smaller (see also FIG. 3A), guide wire 112 can be used for smaller diameter vessels. This device may have a balloon attached for dilatation following the removal of plaque. FIG. 3C is a partially sectioned view of the operation of a much larger catheter 142 employing multiple high pressure jets. This embodiment is well suited to treat conditions wherein calcified deposit 120 does not fully occlude coronary or peripheral artery 110, but can also be used to open completely occluded vessels. Distal tip 143 is advanced into the narrow lumen within calcified deposit 120, thus positioning the multiple jets around the periphery of calcified deposit 120. This configuration works well if the narrow lumen of calcified deposit 120 is centrally located and/or the multiple jets are individually controlled as is discussed in greater detail below. To properly control the process, catheter 142 may contain an ultrasonic transducer array 146. The configuration shown requires a larger outside diameter of the outer sheath than the embodiments previously described. Only shown in this view are two of the multiple high pressure jets. High pressure stream 152 is produced by jet 150 of nozzle assembly 148. Fluid communication is provided by hypo tubing 156 coupled to nozzle assembly 148. Similarly, high pressure stream 158 is produced by jet 160 of nozzle assembly 162. Hypo tubing 166 is coupled directly to nozzle assembly 162. Overwrap 154 is used to provide uniform diameter to the nozzle assembly. FIG. 3D is a view of the operation of a bulbous guide wire device having a pair of positioning bulbs 168 and 170. These positioning bulbs are fitted over rheolytic guide wire 112, for example, to ensure that high pressure stream 126 is not inadvertently directed against the walls of coronary artery 110. As can be seen, this restricts high pressure stream 126 to operate upon only the small central portion of calcified deposit 120. This device can be advantageously used preparatory to the use of catheter 142 (see also FIG. 3C). The small lumen abraded through calcified deposit 120 can be used for insertion of distal tip 143. The combination of these two devices permits treatment of coronary artery 110 having a complete occlusion, yet provides safety features to protect the walls of coronary artery 110. FIG. 3E is a view of the operation of a catheter 180 having an inflatable distal balloon 190. This balloon can be used to properly position and maintain the distal tip of catheter 180 to prevent inadvertent impingement of a high pressure jet against the wall of coronary artery 110. Balloon 190, if made of inelastic materials, may also be used for vessel dilatation as in balloon angioplasty. Note that the inflated balloon 190 also tends to prevent proximal flow of particulate material. Two to ten forward shooting jets, shown as 192 and 194, ablate plaque distal to the catheter. A rearward shooting jet 199 is directed as per arrow 197 into the evacuation port 201, which is coupled to evacuation lumen 200. The rearward jet generates a stagnation pressure, which drives flow out of the evacuation lumen. This device can contain a separate channel which will allow passage of an ultrasonic device to the distal tip in order to detect plaque. FIG. 4 is a longitudinally sectioned view of atherectomy catheter 130 having a single jet 122 and guide wire lumen 138. Operation is as previously described (see also FIG. 3B). FIG. 5 is a transverse sectioned view of atherectomy catheter 130. All referenced elements are as previously described. FIG. 6 is a partially sectioned view of guide wire 112 having a dilatation balloon catheter 172 passed over it. Guide wire 112 assumes its position in large central lumen 174. Outer concentric lumen 181 is employed to inflate dilatation balloon 176 by filling space 178 with a sterile saline solution under low pressure (e.g. 2068 kPa (300 psi)) in known manner. FIG. 7 is a longitudinally sectioned view of the distal end of guide wire 112. All referenced elements are as previously discussed. Lumen 184 of main body 116 has a diameter of about 0.0762 to 0.229 mm (.003 to .009 inch) which is about three times the diameter of jet 122. Distal tubing 118 is welded or brazed to main body 116 at point 186. FIG. 8 is a view in partial phantom of the distal end of a catheter 180 employing the present invention. Catheter 180 has a balloon 190 for dilatation and/or positioning and a multiple jet nozzle assembly 193 containing at least jets 192 and 194. It can be seen that though jets 192 and 194 direct their respective streams in a generally distal direction, the streams are angled toward the central longitudinal axis of catheter 180 as shown by arrows 191 and 195. This may be done as a safety feature to protect the vessel walls. Jet 199 is directed rearward as per arrow 197 into the evacuation port 201 for removal through evacuation lumen 200. FIG. 9 is a transverse sectioned view of catheter 180. Lumen 196 is used to inflate balloon 190 through inflation port 198. Evacuation lumen 200 is extruded in an irregular shape as shown. Small lumen 206 accommodates hypo tubing 208 having interior lumen 210. Catheter body 204 also has a large lumen which provides space for ultrasound device 202. FIG. 10 is a transverse sectioned view of catheter 180 taken distal to FIG. 9. Evacuation port 214 provides side access to evacuation lumen 200. All other referenced elements are as previously described. FIG. 11 is a view of catheter 180 taken from the distal end. Multiple jet nozzle assembly 193 has individual jets 192, 216, 218, 220, 194, 222, 224, and 226 all supplied from a single source of high pressure fluid (i.e. interior lumen 210 of hypo tubing 208). This does not permit the jets to be individually controlled. The individual jets 192, 216, 218, 220, 194, 222, and 226 are directed distal to the catheter in a converging pattern. Jet 224 is directed proximally as per arrow 227 into the evacuation lumen 200. Particulate material is removed due to the flow generated by this jet. All other referenced elements are as previously discussed. FIG. 12 is a partially sectioned view of catheter 228. It is similar in function to catheter 180 except that it has a slightly different lumen configuration. The interior of outer sheath 236 is divided into two lumens by septum 234. The smaller lumen 238 is employed to inflate balloon 190 through inflation port 230. Smaller lumen 238 also contains hypo tubing 208, which becomes the sole use of smaller lumen 238 distal to point 232. The larger lumen 239 is used for a guide wire and evacuation of particulate material. When the larger lumen 239 is used for evacuation, a proximally directed jet 224 is directed as per arrow 227. Particulate material is removed through lumen 239. Jets 194 and 192 are directed distally in the direction of arrows 191 and 195, respectively. All other referenced elements are as previously described. FIG. 13 is a transverse sectioned view of catheter 228 taken across balloon 190. All referenced elements are as previously described. FIG. 14 is a view of catheter 228 taken from the distal end. As with catheter 180, multiple jet nozzle assembly 193 provides a number of separate jets supplied from a single source (i.e. hypo tube 208). One or more jet(s) may be directed proximally. All referenced elements are as previously described. FIG. 15 is a view of the distal end of atherectomy catheter 240. Outer sheath 244 is a flexible polymer which covers a number of separate hypo tubes, each of which feeding a separate jet of multiple nozzle assembly 242. Providing separate supply to each jet permits maximum control of the procedure, as it allows selection of which areas are to be ablated by the corresponding high pressure streams. Each of jets 248a-248n is fabricated similar to the jets previously discussed. To further control the procedure, a separate ultrasonic transducer may be associated with each of the separately controlled jets. The transducers are located between the jets and are labeled 249a-249n. This enables the attending medical personnel to separately monitor the action of each of the jets. Distal tip 246 is a smooth hemisphere to reduce trauma during insertion. FIG. 16 is a view of atherectomy catheter 240 taken from the distal end. All referenced elements are as previously described. FIG. 17 is a longitudinal view of catheter 240. The view is partially sectioned and partially in phantom to show coupling of individual hypo tubes 256a-256n to nozzles 252a-252n, respectively. Outer sheath 257 is sealed to end member 251 as shown. Smooth distal tip 254 reduces trauma. FIG. 18 is a view of catheter 250 taken from the distal end. All referenced elements are as previously described. FIG. 19 is a transverse sectioned view of catheter 250 showing the details of the main catheter body. Hypo tubes 256a-256n are arranged about the inner periphery of outer sheath 257. Interspersed with the hypo tubes are individual ultrasonic transducer cables 260a-260n each of which is coupled to the corresponding one of the multiple ultrasonic transducers at the distal tip. In this manner, the attending medical personnel may individually monitor each of the high pressure jets. The remainder of central lumen 258 may be used for evacuation of particulate material. FIG. 20 is a partially sectioned view of the distal end of catheter 142, which has multiple jets. As explained above, catheter 142 is best suited to enlarge a passage through a deposit wherein the initial passage is sufficiently large to accommodate distal tip 143. Lumen 262 of hypo tubing 156 is isolated from lumen 264 of hypo tubing 166, permitting separate control of jets 150 and 160. The transducer 146 is attached to shaft 266 which is part of the transducer device. FIG. 21 is a transverse sectioned view of catheter 142. Individual hypo tubes 263, 265, 268, 270, 272, 274, 276, 278, 280, and 282 each supply a different one of the high pressure jets providing maximum control as described above. The hypo tubes are located about the outer periphery of inner sheath 267. All other referenced elements are as previously described. FIG. 22 is a view of catheter 142 taken from the distal end. As explained above, jets 150, 160, 295, 296, 294, 292, 290, 288, 286, and 284 are separately controlled from separate hypo tubes (see also Figs. 20 and 21). FIG. 23 is a partially sectioned view of catheter 300. This embodiment has multiple jets on nozzle assembly 312 supplied from distal port 322 attached to single hypo tube 314. Outer catheter body 302 has a larger guide wire lumen 304 separated by septum 306 from smaller lumen 308 containing single hypo tube 314. Distal member 310 is molded to provide attachment of outer catheter body 302 and nozzle assembly 312. Distal member 310 is tapered at point 324 to permit the multiple jets to be angled toward the longitudinal axis as shown by arrows 316 and 318. FIG. 24 is a transverse sectioned view of catheter 300 taken through outer catheter body 302. All referenced elements are as previously described. FIG. 25 is a transverse sectioned view of catheter 300 taken through distal member 310. All referenced elements are as previously described. FIG. 26 is a view from the distal end of catheter 300. Nozzle assembly 312 contains jets 326a-326n. FIG. 27 is a partially sectioned view of a bulbous guide wire 330 having positioning bulbs. The bulb assembly comprising, bulb 168 and bulb 170, is slipped over main body 116 of a guide wire. In the present embodiment, main body 116 is attached under septum 338. This provides a larger lumen 336 for insertion of a guide wire or another device. As explained above, use of the structure comprising bulbs 168 and 170 protects the vessel wall from inadvertent abrasion by the high pressure stream produced by jet 122. All other referenced elements are as previously described. FIG. 28 is a top view in partial phantom of catheter/guide wire 330. All referenced elements are as previously described. FIG. 29 is a view of catheter/guide wire 330 taken from the distal end. All referenced elements are as previously described. FIG. 30 is a partially sectioned view of guide wire 340 having positioning bulbs 168 and 170. Jet 122 directs a high pressure stream distal from lumen 342. Unlike catheter/guide wire 330, guide wire 340 has no separate lumen for another device. All other referenced elements are as previously described. FIG. 31 is a partially sectioned view of catheter 344. Outer sheath 346 provides a single large lumen 348 which provides for passage of guide wire 360, hypo tubing 350, and evacuation of particulate material. Nozzle assembly 352 has a number of separate jets supplied by single hypo tubing 350. Some of the jets of nozzle assembly 352 may be directed proximally as shown by arrow 358 to encourage rapid evacuation of particulate material. Other jets, though directed distally, are angled toward the central longitudinal axis as shown by arrows 354 and 356. FIG. 32 is a transverse sectioned view of catheter 344 taken across outer sheath 346. All referenced elements are as previously described. FIG. 33 is a view of catheter 344 taken from the distal end. Nozzle assembly 352 has separate jets 362a-362n. Some of the separate jets may be directed toward the central longitudinal access as shown by arrow 364.	An apparatus for treating a deposit (120) within a vessel or cavity (110) of a patient, which comprises: (a) a device (142; 240) having a proximal end and a distal end; and (b) supplying means coupled to said proximal end of said device for supplying a fluid under high pressure; (c) directing means coupled to said distal end of said device for directing a stream of the fluid under high pressure distal to said distal end of said device; characterised in that the directing means comprises a plurality of high pressure jets (150, 160; 252a - 252n) and each of the jets has a separate supply (156, 166; 256a to 256n) of the fluid. An apparatus according to Claim l, wherein the fluid is a saline solution. An apparatus according to any of the preceding claims, which includes monitoring means (146; 260a - 260n) coupled to said device. An apparatus according to Claim 3, wherein the monitoring means comprises an ultrasonic transducer array, an angioscope or a fluoroscopic spectroscope. An apparatus according to Claims 3 or 4, wherein the monitoring means is directed toward the deposit. An apparatus according to Claim 3 or 4, wherein the monitoring means is directed toward a reflecting device. An apparatus according to any of the preceding claims, wherein the directing means directs the stream of fluid under high pressure parallel to the longitudinal axis of said device. An apparatus according to any of Claims 1 to 6, wherein the directing means directs the stream of fluid under high pressure nonparallel to the longitudinal axis of said device. An apparatus according to any of the preceding claims, which includes evacuating means coupled to said distal end of said device for evacuating particulate matter ablated from the deposit. An apparatus according to any of the preceding claims which includes a positioning means attached to said device near said distal end. An apparatus according to Claim 10, wherein the position-means comprises an inflatable balloon.	POSSIS MEDICAL INC; POSSIS MEDICAL, INC.	DRASLER WILLIAM J; DUTCHER ROBERT G; JENSON MARK L; PROTONOTARIOS EMMANUIL I; THIELEN JOSEPH M; DRASLER, WILLIAM J.; DUTCHER, ROBERT G.; JENSON, MARK L.; PROTONOTARIOS, EMMANUIL I.; THIELEN, JOSEPH M.
EP-0489498-B1	489,498	EP	B1	EN	19,940,511	1,992	20,100,220	new	E21B43	E21B41, C23F11	C09K8, C23F11	C09K 8/54, C23F 11/04, C09K 8/74	Acidizing subterranean formations	A subterranean formation is acidized employing an acidic solution comprising hydrochloric acid containing a corrosion inhibitor. The corrosion inhibitor comprises the product of the reaction (i) a compound having at least one reactive hydrogen atom and having no groups reactive under the conditions of reaction other than hydrogen, (ii) a carbonyl compound having at least one hydrogen atom on the carbon atom adjacent to the carbonyl group, (iii) an aldehyde, (iv) a fatty compound and an acid source which is admixed with a source of antimony ions.	The present invention relates to a method of acidizing a subterranean formation or well bore. Acidizing and fracturing treatments using aqueous acidic solutions commonly are carried out in hydrocarbon-containing subterranean formations penetrated by a wellbore to accomplish a number of purposes, one of which is to increase the permeability of the formation. The increase in formation permeability normally results in an increase in the recovery of hydrocarbons from the formation. In acidizing treatments, aqueous acidic solutions are introduced into the subterranean formation under pressure so that the acidic solution flows into the pore spaces of the formation. The acidic solution reacts with acid-soluble materials contained in the formation which results in an increase in the size of the pore spaces and an increase in the permeability of the formation. In fracture acidizing treatments, one or more fractures are produced in the formation and the acidic solution is introduced into the fracture to etch flow channels in the fracture face. The acid also enlarges the pore spaces in the fracture face and in the formation. The rate at which acidizing fluids react with reactive materials in the subterranean formation is a function of various factors including acid concentration, temperature, fluid velocity, the type of reactive material encountered and the like. Whatever the rate of reaction of the acidic solution, the solution can be introduced into the formation only a certain distance before it becomes spent. It is desirable to maintain the acidic solution in a reactive condition for as long a period of time as possible to maximize the permeability enhancement produced by the acidic solution. A problem associated with acidizing subterranean formations is the corrosion by the acidic solution of the tubular goods in the well bore and the other equipment used to carry out the treatment. The expense of repairing or replacing corrosion damaged equipment is extremely high. The corrosion problem is exacerbated by the elevated temperatures encountered in deeper formations. The increased corrosion rate of the ferrous and other metals comprising the tubular goods and other equipment results in quantities of the acidic solution being neutralized before it ever enters the subterranean formation. The partial neutralization of the acid results in the production of quantities of metal ions which are highly undesirable in the subterranean formation. Various methods have been proposed to decrease the corrosion problem related to acidizing treatments, however, the corrosion inhibitors employed generally are effective only at temperature levels below about 300°F (149°C). It would be desirable to provide a composition and method for acid treating a subterranean formation which overcomes at least some of the corrosion problem resulting from contact of the aqueous acidic treating solutions with ferrous and other metals. According to the present invention, there is provided a method of acidizing a subterranean formation penetrated by a well bore whereby the corrosive effect of an acidic solution on metal present in said well bore is minimized, said method comprising contacting said formation with an aqueous acidic solution comprising hydrochloric acid which contains a corrosion-reducing effective amount of a corrosion inhibitor, said corrosion inhibitor consisting essentially of a blend of a source of antimony ions and a reaction product, said reaction product being prepared by reacting at least four reaction constituents together in the presence of from 0.8 to 1.2 equivalents of an aqueous mineral acid catalyst at a temperature in the range of from 140°F (60°C) to 250°F (121°C) for a time of from 4 hours to 48 hours to thereby yield said reaction product; wherein at least one of said four reaction constituents is one equivalent of a group (i) compound, at least one of said four reaction constituents is from 0.6 to 10 equivalents of a group (ii) compound, at least one of said four reaction constituents is from 0.5 to 10 equivalents of a group (iii) compound and at least one of said four reaction constituents is from 0.10 to 10 equivalents of a group (iv) compound, and further wherein each of said reaction constituents are from different compounds; and wherein said group (i) compounds have at least one reactive hydrogen atom and have no groups reactive under the conditions of reaction other than hydrogen and include compounds selected from amines, amides, aldehydes, nitrogen heterocycles, ketones, phenols, acetylenic alcohols and substituted derivatives thereof; said group (ii) compounds include a carbonyl group and have at least one hydrogen atom on the carbon atom adjacent to the carbonyl group; said group (iii) compounds are aldehydes, and said group (iv) compounds are selected from fatty compounds having from 5 to 60 carbon atoms, alkyl nitrogen heterocycles having at least one alkyl group having from 1 to 18 carbon atoms, and 3 to 9 carbon atoms in the heterocyclic ring structure, and admixtures thereof. The invention also includes the aqueous acidic solution with corrosion inhibitor as defined above. The composition and method of the present invention substantially reduce the corrosive effect of the acid on ferrous metals and other alloys without reducing the effectiveness of the acidic solution in treating the subterranean formation. The acidizing solution is introduced into a subterranean formation through a well bore at a flow rate and pressure sufficient to permit the acid to dissolve formation materials or foreign material in the vicinity of the well bore. The acidic solution comprises hydrochloric acid, alone or mixed together with one or more acids. Acids that can be admixed with the hydrochloric acid include hydrofluoric acid, acetic acid, formic acid, sulfuric acid, phosphoric acid and mixtures thereof. The aqueous acidic solution should comprise hydrochloric acid in an amount of at least about 2% by weight of the acidizing solution. The corrosion inhibitor preferably comprises a composition comprising an admixture of a Mannich reaction product and an antimony compound. The Mannich reaction product is a reaction product of effective amounts of certain active hydrogen containing compounds with organic carbonyl compounds having a least one hydrogen atom on the carbon atom alpha to the carbonyl group, and a fatty acid or other fatty compound or alkyl nitrogen heterocycle, preferably 2 or 4 alkyl substituted, and an aldehyde, and particularly those aldehydes which may be selected from the group consisting of aliphatic aldehydes containing from 1 to 16 carbon and aromatic aldehydes having no functional groups which are reactive under the reaction conditions other than aldehydes, which are reacted in the presence of an acid catalyst of sufficient strength to form the product. The antimony compound is an antimony compound that is capable of activation by the Mannich reaction product to yield an inhibitor which will effectively prevent the attack on metal by aqueous hydrochloric acid solutions. As shown by the Examples below, the Mannich reaction product significantly reduces the corrosive effect of a hydrochloric acid solution on ferrous or other metals in contact with the acid solution. The antimony compound is activated by the Mannich reaction product to substantially enhance the reduction in corrosion achieved. The exact mechanism by which the Mannich reaction product activates the antimony compound is not known at this time. In certain applications it may be desirable, if not advantageous, to include at least one of the following classes of compounds in the inhibitor composition: a quantity of an acetylenic alcohol, a quaternary ammonium compound, a formic acid generating compound, a source of copper ions, a source of iodide, an aromatic hydrocarbon having high oil wetting characteristics, a surfactant to facilitate dispersion of the corrosion inhibitor in the acidic solution or mixtures of the same. These additives broaden the utility of the inventive inhibitor composition, enhance the effectiveness of the composition and/or facilitate use thereof. In preparing the Mannich reaction product employed in the inhibitor of the present invention the active hydrogen compound containing at least one active hydrogen atom is reacted with a carbonyl compound having at least one hydrogen atom attached to the carbon atom alpha to the carbonyl group, an aldehyde, a fatty acid or other fatty material or alkyl nitrogen heterocycles and an acid catalyst at a temperature of from about 60°C (140°F) to about 121°C (250°F) for from 4 to about 48 hours. It is to be understood that the duration of the reaction may significantly exceed 48 hours without any adverse effects; however such extensive periods are not required to yield usable products. The active hydrogen compounds which can be employed in accordance with the present invention are those organic ammonia derivatives having at least one hydrogen atom attached to nitrogen, as for example, primary and secondary amines, diamines, amides, ureas, thioureas, ammonia and ammonium salts, alicyclic amines, heterocyclic amines, aromatic amines and the like which contain no group reactive under the conditions of the reaction other than hydrogen attached to nitrogen or fully substituted amines in which at least one hydrogen atom adjacent to the amine is activated by the presence of the amine or aldehydes, or ketones, or phenols or acetylenic alcohols as hereinafter described. Some of such compounds which have been found effective are the normal alkylamines having from 1 to 20 or more carbon atoms in the alkyl substituent, as for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonaldecylamine, eicosylamine, and mixtures thereof. The isoalkyl and tertiaryalkylamines having up to 20 carbon atoms in the alkyl substituent such as for example, isopropylamine, isobutylamine, isoamylamine, and the like, tertiarybutylamine, tertiaryamylamine and the like; the dialkylamines having from 1 to 20 alkyl groups in the alkyl substituents such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, didecylamine, dioctadecylamine and the like, as well as the diiso and tertiaryalkylamines, and mixtures thereof. The diamines which are useful as the active hydrogen compound include those diamines having from 1 to 20 carbon atoms in the alkyl portions thereof such as methylenediamine, ethylenediamine, propylenediamine, butylenediamine, diaminopentane (see pentylenediamine), diaminohexane (hexylenediamine) and the like. In addition other nitrogen- containing compounds having an active hydrogen on the nitrogen atom such as ammonia, ureas, thioureas, amides, ammonium salts and alicyclic, heterocyclic and aromatic amines are operative as the active hydrogen compound in accordance with the present invention. Thus, one can employ ammonia, urea, thiourea, 1-acetyl-2-thiourea, 1,3-di-(Rosin Amine D) thiourea, 1,3-dibutylthiourea and the like, acetamide, N-1-napthylacetamide, oxamide, adipamide, propionamide, thioacetamide, malonamide, formamide, alpha-cyanoacetamide, succinimide, n-butyramide, dimethylacetamide, N-methyl-acetamide, n-butyloxamate, hexanamide, phthalimide, n-valer-amide, isobutyramide, Armid 12 (95 percent dodecanamide, 4 percent tetradecanamide, 1 percent decanamide), N,N'-dibenzyldithiooxamide, dithiooxamide, Armid C (amide of coco fatty acids), 1-napthaleneacetamide, Armid O (91 percent oleamide, 6 percent stearylamide, 3 percent linolamide), N,N'-dimethylthiooxamide, acetanilide, Armid HT (75 percent stearylamide, 22 percent palmitamide, 3 percent oleamide), nonanamide, N,N'dicyclohexyldithiooxamide, benzamide, B-isothioureidopropionic acid, N,N'bis(hydroxy-methyl)dithiooxamide, and the like, 2-methylpiperazine, morpholine, pyrrolidine, 2-aminoethylpiperazine, and the like, 2-naphthylamine, benzylamine, 2-aminopyridine, aniline and the like, 1,3-diphenyltriazene, and the like, ammonium chloride, monobasic ammonium phosphate, ammonium acetate, ammonium thiocyanate, ammonium oxalate, dibasic sodium ammonium phosphate and the like are effective sources of active hydrogen in accordance with the present invention. Fully substituted amines such as tetraethyl quaternary ammonium chloride and dimethyl dicoco quaternary ammonium chloride also may be utilized. The carbonyl compounds which are operative in accordance with the present invention are those having at least one hydrogen atom on the carbon atom alpha to the carbonyl group. Some of such carbonyls found to be effective are the aliphatic and aryl substituted aliphatic ketones and mixtures thereof, as for example, acetophenone, mesityl oxide, 1-acetonaphthone, 1 part acetophenone plus 1 part acetone, p-methoxyacetophenone, propiophenone, p-chloroacetophenone, isophorone, tetrolophenone, 2,4-pentanedione, Ketosol (75 percent phenethyl alcohol, 25 percent acetophenone), 2-acetylcyclohexanone, 2-acetonaphthone, 2-thienylketone, methyl isobutylketone, n-butyrophenone, acetone, 3,4-dihydro-1-(2H)-naphthalenone, 2-heptanone, diacetone alcohol, undecanone-2, and the like such as the aldehydes defined hereinafter. The class of fatty compounds found to be operative include the alkyl carboxylic acids, amines, amides and alcohols having from about 5 to about 60 carbon atoms, the olefinic carboxylic acids having from about 5 to about 60 carbon atoms and having from 1 or more unsaturated sites along the chain. In addition the various alkylene oxide adducts of the above fatty compounds have been found effective. Thus one can employ rendered animal fat, octanoic acid, myristic acid, pelargonic acid, abietic acid, acetic acid, lauric acid, formic acid, oleic acid, caprylic acid, tall oil acid, coco fatty acids + 15 moles ethylene oxide, oleic acid + 15 moles ethylene oxide, 70 percent rosin fatty acids + 15 moles ethylene oxide, tall oil + 4 moles propylene oxide + 8 moles ethylene oxide, tall oil + 6 moles propylene oxide + 12 moles ethylene oxide, tall oxide + 4 moles propylene oxide + 12 moles ethylene oxide, tall oil + 4 moles propylene oxide + 10 moles ethylene oxide, tall oil + 6 moles propylene oxide + 8 moles ethylene oxide, tall oil + 6 moles propylene oxide + 10 moles ethylene oxide, and the like. Further, alkyl aromatic nitrogen heterocycles are found to be operative. Thus, compounds such as 2-methyl pyridine, 4-methyl pyridine, 2-methyl quinoline, 4-methyl quinoline, alkyl pyridine and the like may be utilized. The term fatty as used herein refers to the length of the carbon chain, which should consist of at least about 5 carbon atoms. The degree of saturation or unsaturation of the fatty compound is unimportant so long as any substituents present do not cause unwanted side reactions. The class of aldehydes which are operative in accordance with the present invention include the aldehydes having from 1 to 16 or more carbon atoms. Thus one can employ formaldehyde, urotopine, benzaldehyde, heptanal, propanol, hexanal, octanal, decanal, hexadecanal, cinnamaldehyde and the like. The aldehydes also include any aldehyde generating materials under the conditions of the reaction such as paraformaldelyde, paraldehyde, acetals, hemiacetals, sulfite addition products and the like. The mineral acid catalyst which is employed in preparing the Mannich reaction product can be, for example, hydrochloric acid, sulfuric acid, methanesulfonic acid, phosphoric acid and the like. The acid catalyst can comprise substantially any acid which is a strong proton donor. The specific quantity of acid utilized can vary over wide ranges. Any quantity can be utilized that does not result in the occurrence of undesirable side reactions under the reaction conditions. Additional substituents which can be substituted for the various constituents of the reaction product are disclosed in U.S. Patents 3,630,933; 3,932,296; 3,077,454; 2,758,970; 2,489,668; 4,493,775; 3,634,270; and 3,094,490 and European Patent Application numbers 0 276 879 A1 and 0 212 752 A1. A preferred method of preparing the Mannich reaction product employed in the inhibitor composition of the present invention is to react about 1 equivalent of active hydrogen compound and from about 0.5 to about 10 equivalent of aldehyde and from about 0.6 to about 10 equivalents of carbonyl compound and from about 0.8 to about 1.2 equivalents of mineral acid catalyst with from about 0.15 to about 10 equivalents of fatty compound at a temperature of from about 60°C (140°F) to about 116°C (240°F) for from about 4 to 48 hours. Upon completion of the reaction, additional fatty material may be added with stirring to bring the ratio of fatty material to a level of from about 2 to about 20 equivalents. The term equivalent as used herein is defined as the number of moles of a compound that are present times the number of reactive sites on the compound under the conditions of the reaction. The antimony compound and any of the optional constituents are admixed with the Mannich reaction product or admixed in the acidic solution. The antimony compound which is employed in the corrosion inhibitor composition of the present invention can comprise any antimony compound which is activated by the Mannich reaction product of the corrosion inhibitor to cause the corrosion inhibitor to substantially reduce the corrosive effect of the acid in the aqueous acidic solution on ferrous or other metals in contact with the acid solution. As shown by Example III below, the antimony compound by itself does not significantly reduce the corrosive effect of the acid. As used herein and in the appended claims, an antimony compound that is activated or capable of activation by the Mannich reaction product is an antimony compound that is made active or more active by the Mannich reaction product in reducing the corrosive effect of the acid on ferrous or other metals in contact with the acid solution beyond the reduction in the corrosive effect achieved by the Mannich reaction product alone. The antimony compound is preferably soluble in the aqueous acidic solution, at least under the conditions in which the aqueous acidic solution is used. The antimony compound can comprise, for example, antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, potassium antimony tartrate and other alkali metal salts thereof, antimony tartrate, antimony trifluoride, antimony pentafluoride, antimony citrate, potassium pyroantimonate and other alkali metal salts thereof, antimony adducts of ethylene glycol, solutions containing (i) ethylene glycol, (ii) water and (iii) the oxidized product of hydrogen peroxide and antimony trioxide or any other trivalent antimony compound and the like. The acetylenic alcohols which may be employed in the present invention may suitably include substantially any of the acetylenic compounds having the general formula: wherein R₁, R₂ and R₃ are hydrogen, alkyl, phenyl, substituted phenyl or hydroxyalkyl radicals. Preferably, R₁ comprises hydrogen. Preferably, R₂ comprises hydrogen, methyl, ethyl or propyl radicals. Preferably, R₃ comprises an alkyl radical having the general formula CnH2n where n is an integer from 1 to 10. The acetylenic alcohols(s), in certain applications, further reduces the corrosive effect of the acid. Some examples of acetylenic alcohols which can be employed in accordance with the present invention are, for example, methyl butynol, methyl pentynol, hexynol, ethyl octynol, propargyl alcohol, benzylbutynol,ethynylcyclohexanol and the like. Preferred alcohols are hexynol, propargyl alcohol, methyl butynol and ethyl octynol. The quaternary aromatic ammonium compounds which may be employed in the present invention comprise aromatic nitrogen compounds which may be illustrated by alkyl pyridine-N-methyl chloride quaternary, alkyl pyridine-N-benzyl chloride quaternary, alkylquinoline-N-benzyl chloride quaternaries, alkylisoquinoline quaternaries, benzoquinoline quaternaries, chloromethylnaphthalene quaternaries of the above, admixtures of the compounds and the like. The alkyl group associated with the pyridine compounds can contain from 0 to 6 carbon atoms and with the quinoline compounds can contain from 0 to 8 carbon atoms. The quaternary ammonium compound(s) also function to reduce the corrosive effect of the acid in certain applications. The hydrocarbon compound which may be employed can comprise substantially any aromatic compound which exhibits high oil-wetting characteristics. The aromatic hydrocarbon compound can comprise, for example, xylenes, saturated biphenyl-xylenes admixtures, heavy aromatic naphtha, heavy aromatic solvent, tetralene, tetrahydroquinoline, tetrahydronaphthalene and the like. Additional additives which can be present in the corrosion inhibitor can comprise, for example, a solvent such as an alkanol to assist in maintaining the constituents of the corrosion inhibitor as a homogeneous admixture. Alkanols which can be employed in the present invention are, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl and the higher liquid members of these aliphatic alcohols. Preferably, the quantity of alkanol employed is that which merely is sufficient to maintain the constituents in homogeneous admixture as excess quantities have no demonstrable effect on the effectiveness of the corrosion inhibitor. Preferably, the alkanol comprises less than about fifteen percent by volume of the corrosion inhibitor composition to avoid unnecessary dilution of the inhibitor composition. The corrosion inhibitor also can include a surfactant which facilitates dispersion of the corrosion inhibitor in the aqueous acidic solution. Nonionic surfactants are preferred for use in the corrosion inhibitor. The nonionic surfactant can comprise an ethoxylated oleate, tall oils or ethoxylated fatty acids. The 8 to 20 moles of ethylene oxide adducts of octyl phenol, nonylphenol, tridecyl phenol and the like are preferred. Sufficient nonionic surfactant is admixed with the other constituents of the corrosion inhibitor to facilitate dispersion of the corrosion inhibitor in the aqueous acidic solution. Preferably, the surfactant comprises less than about 20 percent by volume of the corrosion inhibitor composition to avoid unnecessary dilution of the inhibitor composition. The Mannich reaction product comprises in the range of from about 3% to about 75% by weight of the corrosion inhibitor. More preferably, the Mannich reaction product comprises from about 35% to about 70% by weight of the corrosion inhibitor. The antimony compound may be present in the corrosion inhibitor in an amount sufficient to obtain a solution having a concentration of from about 0.0001 to about 0.1 molar in the aqueous acidic solution. Preferably, the antimony compound is present in an amount sufficient to provide a concentration in the aqueous acidic solution of from about 0.0007 to about 0.04 and most preferably of about 0.001 to about 0.04 molar. It is to be understood that larger quantities may be utilized but such use is generally unnecessary. Excessive amounts have no demonstrable effect except at highly elevated temperatures. The acetylenic alcohol, when present, can comprise from about 4 to about 80% by weight of the corrosion inhibitor. The quaternary aromatic ammonium compound, when present, can comprise from about 6 to about 80% by weight of the corrosion inhibitor. The aromatic hydrocarbon compound, when present, can comprise from about 0.5 to about 40% by weight of the corrosion inhibitor. The method of the present invention can be carried out by admixing the aqueous fluid with the acid to provide an acidic solution of a desired concentration. The corrosion inhibitor then is admixed with the solution in an amount sufficient to substantially reduce the corrosion rate of the acid on metal surfaces in contact or to be contacted with the acid. The amount of corrosion inhibitor utilized in the practice of the present invention can vary over a substantial range. Preferably, the inhibitor composition is present in an amount of from about 1 to about 20 volumes per 1000 volumes of aqueous acidic solution. The quantity of corrosion inhibitor will depend upon the concentration of the acid employed and the temperature at which the acidic solution will contact the metal surfaces. The aqueous acidic solution of the present invention can be prepared in any suitable tank equipped with suitable mixing means well known to individuals skilled in the art. The solution may be transferred either at a controlled rate directly into the well bore or into a convenient storage tank for injection down the well bore. The aqueous acidic solution is introduced into the subterranean formation whereby either foreign material in the well bore or in the formation or formation materials are dissolved to thereby increase the permeability of the formation. The increased permeability permits better flow of hydrocarbon fluids through the formation and into its well bore. The pumping rate and pressure utilized will depend upon the characteristics of the formation and whether or not fracturing of the formation is desired. After the aqueous acidic solution has been injected, the well may be shut in and allowed to stand for a period of several hours or more depending on the type of acid employed and the formation treated. If there is pressure on the well, pressure then can be released and the spent or at least partially spent aqueous acidic solution, containing salts formed by the reaction of the acid, is permitted to flow back into the well bore and is pumped or flowed to the surface for appropriate disposal. The well then can be placed on production or used for other purposes. In one preferred embodiment the Mannich reaction product is prepared by adding the following compounds to a reaction vessel on the basis of one mole of thiourea, 2 moles of acetophenone, 1.33 moles of oleic acid, 4.4 moles of formaldehyde and one mole of hydrochloric acid. The reactor contents are stirred to dissolve the thiourea and then heated under reflux conditions at a temperature of about 104°C (220°F) for about 16 hours. The reaction product is separated from the residue in the reactor vessel as a separated nonaqueous layer in the vessel, which forms upon cooling of the reaction mixture. The following examples are illustrative of the present invention. EXAMPLE IThe following composition was charged to a 250 ml. glass reaction flask equipped with a stirrer and reflux condenser. Thiourea0.15 moles Acetophenone0.3 moles 37% formaldehyde0.66 moles Concentrated HCl0.15 moles Oleic acid0.2 moles The materials may be added in any order to the reaction vessel. The charge is stirred and refluxed gently for about 16 hours while stirring. The product then is allowed to stand for about 0.5 hours during which time the temperature dropped from about 104°C (220°F) to about 49°C (120°F) and an aqueous layer separated in the flask. The crude reaction product, organic layer, was separated and stored. An inhibitor blend was prepared by adding 4 ml of the reaction mixture to 4 ml of methylnaphthylquinolinium chloride solution and 1.5 ml of nonylphenol ethoxylated with about 20 moles of ethylene oxide unless otherwise designated. A solution of 100 ml of 15% hydrochloric acid was prepared to which was added 1 ml of the foregoing blend and in some instances antimony was added to the solution to provide a concentration of about 0.018 moles/liter. The source of antimony was the reaction product of antimony trioxide and hydrogen peroxide in ethylene glycol and water. The corrosion loss determination in kg/m² (lb/ft²) then was made as follows: a coupon was cut from API N 80 steel oil field tubing and the surface area was determined. The coupon was weighed and placed in the acidic solution containing the inhibitor. The solution and coupon then was placed in an autoclave which was placed in a heating jacket preset to provide an autoclave temperature of about 149°C (300°F) and exposed for 2 hours. At the end of this time the coupon was removed, weighed and the corrosion loss calculated from the weight lost. To evaluate the scope of available substituents for use in the various method of the present invention, various compounds were substituted for the constituents in the inhibitor reaction mixture. The substitutions were made on a molar basis except as noted in the Tables. The foregoing data clearly illustrate the substantially improved corrosion reduction achieved through use of the composition of the present invention containing antimony. The data also illustrates the operability of the various described classes of substitutes for the various compounds in the composition. EXAMPLE IITo illustrate the utility of antimony in the various forms in which it is available, the following tests were performed. The corrosion loss determination was made in the same manner as Example I and the Mannich reaction product of Example I was utilized in formulating the inhibitor blend as described therein. A solution of 100 ml of 15% hydrochloric acid was prepared to which was added 1 ml. of the foregoing blend and 1.8 millimoles of antimony ion provided by an antimony compound as set forth hereinafter. The acid was heated to 149°C (300°F) and a coupon of API N 80 steel was exposed for 2 hours to the heated acid in the manner described in Example 1. The results are set forth in Table VI, below. A blank test was performed for comparison purposes in which no antimony compound was added to the reaction product of Example I admixed with the acid solution. The data clearly illustrates the enhanced corrosion protection achieved in the corrosion inhibitor blend upon incorporation of an antimony compound which is activated by the other constituents of the blend. EXAMPLE IIIAdditional tests were performed to show that antimony alone in a hydrochloric acid solution does not reduce the corrosive effects of the acid on metal surfaces. Corrosion losses experienced by metal coupons placed in hydrochloric acid solutions, with and without antimony present, were determined. The corrosion loss determinations were made in the manner described in Example I. In each test, a premeasured and preweighed coupon of API N 80 steel oil field tubing was placed in approximately 100 ml of a 15% hydrochloric acid solution. In the tests in which antimony was employed, a solution containing ethylene glycol, water and the oxidized product of hydrogen peroxide and antimony trioxide was added to the acid solution to provide a concentration of antimony in the solution of 0.018 moles/liter. The acid solution and coupon were then placed in an autoclave which was placed in a heating jacket preset to provide an autoclave temperature of about either 66°C (150°F), 93°C (200°F) or 149°C (300°F), and the acid solution and coupon were exposed to one of the above temperatures for two hours. At the end of the two hour period, the coupon was removed and weighed, and the corrosion loss was calculated from the weight lost. The results of these tests are set forth in Table VII below. The results shown in Table VII clearly demonstrate that the presence of antimony in the solution did not reduce the corrosive effects of the 15% hydrochloric acid on the metal coupons at any of the various temperatures. As shown by reference to the data in Table VII and Table I of Example I, a significant difference with respect to corrosion inhibition upon a metal surface is shown by a 15% hydrochloric solution containing antimony alone, the Mannich reaction product of the present invention without antimony, and the Mannich reaction product when combined with antimony, which difference is clearly not merely an additive effect. EXAMPLE IVFurther tests were carried out to illustrate the effectiveness of the inventive corrosion inhibitor when an acetylenic alcohol, quaternary ammonium compound and/or aromatic hydrocarbon having high oil wetting characteristics are employed therewith. In addition, tests were carried out to compare the effectiveness of the inventive corrosion inhibitor to the effectiveness of a prior art corrosion inhibitor that utilizes an admixture of an acetylenic alcohol, quaternary ammonium compound and aromatic hydrocarbon together with antimony. The prior art composition tested is described in U.S. Patent No. 4,498,997 to Walker. The Mannich reaction product described in Example I was utilized in forming the inventive corrosion inhibitor used in the tests. An inhibitor blend was prepared by adding the reaction product to a quantity of nonylphenol ethoxylated with about 20 moles of ethylene oxide (a dispersing agent). A solution of 100 ml of 15% hydrochloric acid was prepared to which was added 1.0 ml of the foregoing blend. The acetylenic alcohol employed in the tests was propargyl alcohol. The quaternary ammonium compound utilized was benzylquinolinium chloride. The aromatic hydrocarbon having high oil wetting characteristics was heavy aromatic naphtha. The prior art corrosion inhibitor tested was prepared by admixing propargyl alcohol, benzylquinolinium chloride, heavy aromatic naphtha and nonylphenol ethoxylated with about 20 moles of ethylene oxide (dispersing agent) to form an inhibitor blend. A solution of 100 ml of 15% hydrochloric acid was prepared to which was added 1.0 ml of the inhibitor blend. Tests were conducted with and without antimony. In the tests employing antimony, a solution containing ethylene glycol, water and the oxidized product of hydrogen peroxide and antimony trioxide was added to the acid solution in an amount sufficient to impart 1.8 millimoles of antimony thereto. Corrosion loss tests were carried out in the manner described in Example I. In each test, a premeasured and preweighed coupon of API N 80 steel oil field tubing was placed in the acid solution containing the inhibitor. The solution and coupon were then placed in an autoclave which was placed in a heating jacket preset to provide an autoclave temperature of about 149°C (300°F), and the solution and coupon were exposed at that temperature for 2 hours. At the end of the 2 hour period, the coupon was removed and weighed, and the corrosion loss was calculated from the weight lost. The results of these tests are shown by Table VIII below: The results of the above tests show that addition of an acetylenic alcohol, quaternary ammonium compound and/or aromatic hydrocarbon having high oil wetting characteristics does not substantially decrease and, in some cases, actually improves the protection against corrosion achieved by the inventive corrosion inhibiting composition. The results also show that the inventive corrosion inhibitor was just as effective as the prior art corrosion inhibitor in reducing corrosion by the acid. The Mannich reaction product employed in the inventive corrosion inhibitor is just as effective as the acetylenic alcohol/quaternary ammonium compound/aromatic hydrocarbon admixture in activating the antimony, Column B. Thus, the combination of the claimed reaction product with a source of antimony ions capable of activation by the reaction product very effectively reduces the corrosive effects of a hydrochloric acid solution in contact with metal surfaces, even at high temperatures. Example I clearly demonstrates the enhanced protection provided by the antimony and the broad classes of substitutes for the components forming the reaction product. Example II demonstrates the utility of antimony in the various forms in which it is available. Example III shows that antimony alone does not reduce the corrosive effect of the acid further supporting the synergistic relationship between the reaction product and the antimony. Example IV shows that an acetylenic alcohol, quaternary ammonium compound and aromatic hydrocarbon having high oil wetting characteristics can be used to broaden the utility of the inventive corrosion inhibitor without reducing the effectiveness thereof. Finally, Example IV also shows that the inventive corrosion inhibitor is just as effective as the prior art corrosion inhibitor disclosed in US-A-4,498,997 in reducing corrosion by the acid.	A method of acidizing a subterranean formation penetrated by a well bore whereby the corrosive effect of an acidic solution on metal present in said well bore is minimized, said method comprising contacting said formation with an aqueous acidic solution comprising hydrochloric acid which contains a corrosion-reducing effective amount of a corrosion inhibitor, said corrosion inhibitor consisting essentially of a blend of a source of antimony ions and a reaction product, said reaction product being prepared by reacting at least four reaction constituents together in the presence of from 0.8 to 1.2 equivalents of an aqueous mineral acid catalyst at a temperature in the range of from 140°F (60°C) to 250°F (121°C) for a time of from 4 hours to 48 hours to thereby yield said reaction product; wherein at least one of said four reaction constituents is one equivalent of a group (i) compound, at least one of said four reaction constituents is from 0.6 to 10 equivalents of a group (ii) compound, at least one of said four reaction constituents is from 0.5 to 10 equivalents of a group (iii) compound and at least one of said four reaction constituents is from 0.10 to 10 equivalents of a group (iv) compound, and further wherein each of said reaction constituents are from different compounds; and wherein said group (i) compounds have at least one reactive hydrogen atom and have no groups reactive under the conditions of reaction other than hydrogen and include compounds selected from amines, amides, aldehydes, nitrogen heterocycles, ketones, phenols, acetylenic alcohols and substituted derivatives thereof; said group (ii) compounds include a carbonyl group and have at least one hydrogen atom on the carbon atom adjacent to the carbonyl group; said group (iii) compounds are aldehydes, and said group (iv) compounds are selected from fatty compounds having from 5 to 60 carbon atoms, alkyl nitrogen heterocycles having at least one alkyl group having from 1 to 18 carbon atoms, and 3 to 9 carbon atoms in the heterocyclic ring structure, and admixtures thereof. A method according to claim 1, wherein said source of antimony ions comprises at least one of antimony trioxide, pentoxide, trichloride, pentachloride, trifluoride, pentafluoride, tartrate, citrate, alkali metal salts of antimony tartrate or citrate, alkali metal salts of pyroantimonate, antimony adducts of ethylene glycol and solutions containing (i) ethylene glycol, (ii) water and (iii) the product of hydrogen peroxide and a source of trivalent antimony ions. A method according to claim 1 or 2, wherein said antimony ion is present in said inhibitor in an amount of from 0.0001 to 0.1 molar with respect to said hydrochloric acid solution. A method according to claim 1,2 or 3, wherein said group (i) compounds have at least one reactive hydrogen atom attached to nitrogen and have no groups reactive under the conditions of reaction other than said hydrogen atom attached to nitrogen, and include compounds selected from the group consisting of amines, amides, nitrogen, heterocycles, and substituted derivatives thereof. A method according to claim 1,2,3 or 4, wherein said aqueous acidic solution also comprises a quaternary ammonium compound, an acetylenic alcohol, an aromatic hydrocarbon having high oil wetting characteristics, or a dispersing surfactant, or any mixture of two or more thereof. A method according to any preceding claim, wherein said group (i) compound is thiourea, said group (ii) compound is acetophenone, said group (iii) compound is formaldehyde, said group (iv) compound is oleic acid. A method according to any preceding claim, wherein said source of antimony ions is a solution containing ethylene glycol, water and the oxidized product of hydrogen peroxide and antimony trioxide. A method according to claim 5, wherein the aqueous acidic solution comprises a compound selected from methylnaphthylquinolinium chloride, nonylphenol ethoxylated with about 20 moles of ethylene oxide and mixtures of two or more thereof. A method according to any of claims 1 to 8, wherein said corrosion inhibitor is present in said solution in an amount in the range of 1 to 20 volumes inhibitor per 1000 volumes of aqueous acidic solution. A method according to claim 1, wherein said group (i) compound is selected from urea, guanidine carbonate, ammonium chloride, 2-picoline, quinaldine, morpholine, dibutylamine, butylamine, oleamide, tetraethylammonium chloride, 4-picoline, quinoline, cocoamine, dicocoamine and hexahydropyrimadine-2-thione; said group (ii) compound is acetophenone; said group (iii) compound is formaldehyde; and said group (iv) compound is oleic acid.	HALLIBURTON CO; HALLIBURTON COMPANY	WALKER MICHAEL L; WALKER, MICHAEL L.
EP-0489500-B1	489,500	EP	B1	EN	19,940,914	1,992	20,100,220	new	B60R9	null	B60R9	B60R 9/04	Slat assembly for vehicle article carriers	The present invention is a slat (24) for a vehicle article carrier adapted to be mounted in a longitudinally extending recess (32) in a generally horizontal extending exterior vehicle body surface (21). The slat (24) includes a channel member (40) adapted to be disposed in the recess (32). The channel member (40) has an upper surface (50,150,250) adapted to be disposed substantially flush with the vehicle body surface (31).	BACKGROUND OF THE INVENTION1. Field of the InventionThe present invention relates generally to an article carrier for vehicles, and more particularly, to a slat assembly for an article carrier on an automotive vehicle. 2. Description of the Related ArtVehicle article carriers frequently employ two separate subassemblies or portions: a rectangular framework which surrounds the load to be carried and a plurality of slats which rest on the roof or other vehicle body portion and carries the weight of the load. In such constructions, the framework and the slats are often secured to the vehicle body independently of one another. In still another vehicle article or luggage carrier, a crossbar replaces the framework as a means for confining the articles upon the slats. In prior U.S. Patent 4,182,471, an article carrier for vehicles was disclosed having slats extending above the vehicle body surface and crossbars which can be adjusted on the slats. The crossbars are easily removed, interchanged or adjusted in position on the slats in accordance with the needs of the user. This construction has achieved significant commercial success. Nevertheless, a need exists to provide a slat which is more aesthetically pleasing and easy to assemble. Therefore, it is believed that a need exists for a slat which does not extend above the vehicle body surface. More specifically, it is believed that a need exists for a slat which can be assembled and mounted substantially flush with the vehicle body surface. EP-A-0 325 876 discloses a slat assembly in accordance with the prior art portion of claim 1. With this prior arrangement, no means are provided for adjusting the vertical height of the upper surface of the channel relative to the upper surface of the vehicle and the only protection against ingress of material to the recess is provided by a member in the form of an embellishment strip, spanning the channel and the recess, and not permitting longitudinal adjustment of a supporting bracket lengthwise of the channel. The present invention includes the provision of means to adjust the vertical height of the upper surface of the channel relative to the adjacent surface portion of the vehicle such that the upper surface can be maintained substantially flush with the surface portion with the channel being available to provide immediate support for a vehicle article or carrier. With the arrangement of the present invention, as defined in claim 1, a slat is provided which, while being easy to assemble, is aesthetically pleasing and need not extend noticeably above the vehicle body surface in that it can be mounted at a desired height substantially flush with the vehicle body surface. A further advantage of the present invention is that the slat channel allows a crossbar to be locked or secured in place wherever required along the length of the slat. The latter advantage is not possible with the construction of EP-A-0 325 876 since the channel is designed to support a cross-bar supporting bracket at set locations only in respect of the channel whilst with the present invention, the bracket can be positioned as required lengthwise of the channel. The seal means provided in the present invention, because it fits around the channel frictionally to engage the side surfaces of the recess and the side walls of the channel leaves the top of the channel exposed for engagement by the bracket whilst sealing the space between the channel and the walls of the recess in the vehicle roof. Other objects, features and advantages of the present invention will be readily appreciated as the same becomes better understood when viewed in light of the following description and accompanying drawings. Brief Description of the DrawingsFigure 1 is a perspective view of a vehicle illustrating an article carrier mounted thereon which is constructed in accordance with the principles of the present invention. Figure 2 is an enlarged perspective view of a portion of the structure illustrated in circle 2 for the article carrier of Figure 1. Figure 3 is a sectional view of the structure illustrated in Figure 2 taken along line 3-3 thereof. FIG. 4 is a view of the structure similarly illustrated in FIG. 3. FIG. 5 is a view of the structure similarly illustrated in FIGS. 3 and 4. DESCRIPTION OF THE PREFERRED EMBODIMENT(S)FIG. 1 depicts a vehicle 20 such as an automobile having a generally horizontal roof 22 on which are mounted a pair of identical, parallel, transversely spaced side rails, slats or slat assemblies, generally indicated at 24. Although the slat assemblies 24 are shown mounted on the roof 22, the slat assemblies 24 of the present invention which form an article carrier may be mounted with equal utility on a truck lid or any other generally horizontal exterior body portion of the vehicle 20. Mounted on the roof 22 are a plurality of identical, parallel, transversely spaced support slats 26. The support slats 26 are disposed between the slat assemblies 24 such that the support slats 26 are transversely spaced between the slat assemblies 24. The slat assemblies 24 and support slats 26 may be secured on the roof 22 by means such as sheet metal screws (not shown), pop rivets, rivet nuts or the like. Mounted on the slat assemblies 24 are a pair of raised tubular restraining bars or crossbars 28 which are fitted at their opposite ends onto stanchions, bracket members or brackets 30. The brackets 30 include a locking structure (not shown) for locking the crossbars 28 into position along the slat assemblies 24. The locking structure may comprise a clamp lock with an adjustable wheel, a pin lock into apertures of the slat assemblies 24, or a clamp disposed within the slat assemblies 24. The locking structure allows the crossbars 28 to be positioned operably at any location or at predetermined locations along the length of the slat assemblies 24. Referring to FIGS. 2 and 3, only a portion of the slat assembly 24 and roof 22 are illustrated. The roof 22 has a vehicle body surface 31 including a plurality of transversely spaced and inwardly directed recesses 32. Preferably, the vehicle body surface 31 has a pair of recesses 32 with each recess 32 being disposed near the outermost side of the roof 22. Each recess 22 extends generally longitudinally along the vehicle body surface 31 and is defined by a bottom surface 34 being generally horizontal and a pair of side surfaces 36 and end surfaces 38 extending upwardly from edges of the bottom surface 34 at an angle or incline to the vehicle body surface 31. It should be appreciated that the surface 34,36 and 38 are integral and may form a weld ditch of the roof 22. The slat assembly 24 includes a channel member, generally indicated at 40, which extends generally longitudinally and is adapted to be received in each recess 32. The channel member 40 includes a generally horizontal bottom wall 42 and a pair of generally inclined upwardly and outwardly extending side walls 44. The bottom wall 42 has a transverse width less than a transverse width of the bottom surface 34 of the recess 32 to form a transverse space 45 between the side walls 44 and side surfaces 36 of the recess 32. The channel member 40 also includes generally horizontal side ledges 46 extending inwardly at the upper ends of the side walls 44. The side ledges 46 include an outer article supporting surface 48 and an inner upper surface 50 spaced generally vertically below the article supporting surface 48. The channel member 40 further includes a generally inclined end wall 52 extending upwardly and outwardly at an angle from a longitudinal end of the bottom wall 42 and a generally horizontal end ledge 54 extending longitudinally from the end wall 52. The end ledge 54 includes an outer article supporting surface 48 and an inner upper surface (not shown). The bottom wall 42 and side walls 44 and ledges 46 form an upwardly opening channel 56 which is wider at its bottom than at the top and closed at the longitudinal end by end wall 52 and ledge 54. It should be appreciated that the bottom wall 42, side walls 44 and ledges 46 are integral. It should also be appreciated that the article supporting surfaces 48 extend generally in the same plane. It should further be appreciated that the bottom wall 42 terminates before the end surface 38 to form a longitudinal space between the end wall 52 and end surface 38. The slat assembly 24 may include an elastomeric mounting pad 58 interposed between the bottom surface 34 of the recess 32 and a lower surface 59 of the bottom wall 42 of the channel member 40. The mounting pad 58 is generally planar and extends longitudinally. Preferably, the mounting pad 58 has a transverse width less than a transverse width of the bottom wall 42. The thickness or height of the mounting pad 58 may be varied such that the inner upper surface 50 is substantially flush with the vehicle body surface 31. As illustrated in FIG. 3, the inner upper surface 50 is disposed slightly below the vehicle body surface 31. It should be appreciated that the side walls 44 may have a vertical height less than, substantially flush or greater than a vertical height of the side surfaces 36. The slat assembly 24 includes a sealing strip, generally indicated at 60, disposed between the side surfaces 36 of the recess 32 and the side walls 44 of the channel member 40 and between the end surfaces 38 and end walls 52 thereof. As illustrated in FIG. 2, the sealing strip 60 includes side portions 62 extending longitudinally to close or seal the transverse space 45 and an end portion 64 extending transversely to close or seal a longitudinal space between the channel member 40 and recess 32. As illustrated in FIG. 3, the side portions 62 have a top surface 66, an outer surface 68 and an inner surface 70. The top surface 66 is adapted to be substantially flush with vehicle body surface 31 and the article supporting surface 48. The outer surface 68 is adapted to engage the intersection of the vehicle body surface 31 and side surface 36 of the recess 32 and the inner surface 70 is adapted to engage the upper end of the side walls 44 of the channel member 40. The inner surface 70 extends downwardly and partially along the side wall 44. Preferably, the sealing strip 60 is made of an elastomeric material and frictionally secured between the recess 32 and channel member 40. The sealing strip 60 is adapted to prevent foreign matter such as dirt, water or the like from entering the recess 32. The sealing strip 60 also provides an aesthetic appearance. Referring to FIG. 4, an alternate embodiment 124 of the slat assembly 24 according to the present invention is shown. Like parts of the slat assembly 24 have like numerals increased by one hundred (100). The channel member 140 includes a downwardly and generally vertical extending flange or lip 171 at the inner or free end of each side ledge 146. The flange 171 may include a plurality of notches (not shown) defined therein and spaced along the longitudinal length thereof. The slat assembly 124 may eliminate the separate mounting pad 58 by incorporating it as a bottom portion 172 of the sealing strip 160. The thickness or height of the bottom portion 172 may be varied such that the inner upper surface 150 is flush with the vehicle body surface 31. The bottom portion 172 extends transversely and longitudinally along the bottom wall 142. The sealing strip 160 includes generally inclined upwardly extending side portions 174 from the bottom portion 172 extending along the side walls 144 end cap portions 176 at the upper end of the side portions 174. The cap portions 176 include the top surface 166 which extends transversely such that the outer surface 168 overlaps the vehicle body surface 31 and the inner surface 170 overlaps the article supporting surface 48. It should be appreciated that the bottom portion 172, side portions 174 and cap portions 176 are integral and frictionally fit about the channel member 140. Referring to FIG. 5, an alternate embodiment 224 of the slat assembly 24 according to the present invention is shown. Like parts of the slat assembly 24 have like numerals increased by two hundred (200). The channel member 240 has a downwardly and generally vertical extending flanges or lip 280 at the inner or free end of each ledge 246. The flange 280 may include a plurality of notches (not shown) defined therein and spaced along the longitudinal length thereof. The sealing strip 260 includes the top surface 266 which is adapted to extend transversely substantially flush with the article supporting surface 248 at the inner surface 270 and to overlap the vehicle body surface 36 at the outer edge 268. The inner surface 270 is adapted to engage the upper end of the side wall 244 and extend downwardly partially therealong. The slat assembly 224 includes the mounting pad 258 having a thickness or height which may be varied such that the inner upper surface 250 is disposed slightly above the vehicle body surface 31.	A slat assembly (24) including a channel member (60) adapted to be mounted in a longitudinally extending recess (32) in a generally horizontally extending vehicle body surface (31) of a roof (22) of a vehicle for allowing slidable positioning and securing of a bracket (30) and a cross bar (28) along the length of said slat assembly (24), the channel member (40) comprising a bottom wall (42), a pair of side walls (44) extending upwardly from said bottom wall (42), and ledges (46) extending inwardly from said side walls which terminate to define a channel (56), said ledges (46) each including an upper surface (48), a member (60) engaging the channel member (40) and the edges of the recess (32), characterised in that means (58) are provided for adjusting a vertical height of said upper surface (46) relative to the vehicle body surface (31) such that said upper surface (48) is at a desired height relative to said vehicle body surface (31) of the vehicle, said means (58) for adjusting the vertical height being positioned within said recess (32) inbetween a bottom surface (34) of said recess (32) and said bottom wall (42) of said channel member (40); and in that said member (60) comprises sealing means (60) abuttingly engaging and frictionally secured between a side surface (36) of said recess (32) and one of said side walls (44) thereby to seal the space (45) therebetween. A slat assembly according to claim 1, wherein said ledges have an article supporting surface (48) as said upper surface spaced generally vertically from said surface (31) of said vehicle. A slat assembly according to claim 1 or 2, wherein said height adjusting means comprises a mounting pad (58) disposed between said bottom wall (42) of said channel member (40) and a bottom surface (34) of the recess (32). A slat assembly according to claim 3, wherein said mounting pad (58) has a transverse width less than a transverse width of said bottom wall (42). A slat assembly according to any preceding claim, wherein said upper surface (48) is flush with the surface (31) of the vehicle. A slat assembly according to any one of claims 1 to 4, wherein said upper surface (48) is disposed below the surface portion (31) of the vehicle. A slat assembly according to any one of claims 1 to 4, wherein said upper surface (48) is disposed above the surface portion (31) of the vehicle. A slat assembly according to any preceding claim, wherein said sealing means (60) comprises side portions (62) extending longitudinally and an end portion (64) extending transversely between said side portions at each end thereof. A slat assembly according to claim 8, wherein said side portions (62) have an outer surface (68), an inner surface (70) and a top surface (66) extending transversely between said outer surface (68) and said inner surface (62). A slat assembly according to claim 9, wherein said inner surface (70) so engages said side wall (44) as to extend downwardly and partially therealong. A slat assembly according to claim 9 or 10, wherein said top surface (66) of said sealing means (60) is substantially flush with the surface portion and said ledge. A slat assembly according to claim 9, 10 or 11, wherein said outer surface (68) overlaps the surface portion (31) of the vehicle. A slat assembly according to claim 9, 10, 11 or 12, wherein said sealing means comprises a bottom portion (172) extending along said bottom wall (142), side portions (174) extending along said side walls (144) and cap portions (176) at an upper end of said side walls (144), said cap portions including said upper surface (148), inner surface (130) and outer surface (168). A slat assembly according to claim 13, wherein said outer surface (168) overlaps the surface portion (31) and said inner surface (170) overlaps said ledge (146).	BOTT JOHN ANTHONY; BOTT, JOHN, A.	CUCHERAN JOHN STEPHEN; CUCHERAN, JOHN STEPHEN
EP-0489502-B1	489,502	EP	B1	EN	19,970,716	1,992	20,100,220	new	H02G1	null	H02G1	H02G 1/12B4B2B	Multiple blade set strip apparatus for cable and wire	The method of processing wire (10) to cut the wire into sections and to strip sheathing from the wire to expose wire ends at opposite ends of the sections, and by operation of wire feed means (21a) and cutter means, the steps that include operating the feed means and cutter means to displace the wire endwise along an axis to a first position; sever the wire thereby to form wire forward and rearward sections, the forward section having a rearward end portion; and, the rearward section having a forward end portion, and; stripping sheathing from the forward section rearward portion and from the rearward section forward portion thereby to expose wire ends at the portions; the cutter means including three blade pairs (13a,13b; 16a,16b; 17a,17b), each pair including two blades located at opposite sides of the axis (12), both blades (13a,13b) of one pair being displaced toward the wire to sever the wire, and both blades of the remaining two pairs being displaced toward the wire sections to strip sheathing from the rearward and forward portions during controlled endwise displacement of the sections.	This invention relates generally to wire or cable severing, as well as stripping sheathing from severed wire sections; and more particularly, it concerns unusual advantages, method and apparatus to effect severing of a wire or cable into two sections, and stripping of sheathing off ends of both sections, with minimal motions of severing and stripping elements and in minimum time. There is continual need for equipment capable of severing wire or cable into sections, and also capable of rapidly and efficiently stripping sheathing off ends of those sections. It is desirable that these functions be carried out as a wire or cable travels along generally the same axis, i.e. progresses forwardly, and that multiple wire and cable sections of selected length be produced, each having its opposite ends stripped of sheathing, to expose bare metal core wire at each end. Further, it is desirable that simple, radial and axial stripping adjustments be achieved upon multiple wire sections. SUMMARY OF THE INVENTIONIt is a major object of the invention to provide apparatus and method meeting the above need. The word wire will be used to include cable within its scope, and vice versa. The invention in both apparatus and method aspects is claimed in the claims which proceed from the disclosure in US-A-2934982. US-A-2934982 describes wire cutter and insulation stripping apparatus in which the wire feeding mechanism, which feeds wire into the cutting mechanism, is disconnected during cutting and stripping of the wire, the wire being severed and then the insulation being cut before the wire is moved axially. The invention refers to a method according to claim 1. Basically, the method involves processing the wire into sections as by displacing the wire endwise along an axis to a first position; severing the wire thereby to form wire forward and rearward sections, the forward section having a rearward end portion, and the rearward section having a forward end portion; the sections are then separated axially endwise; then the sheathing of both sections is cut; and then the sections are further separated axially relatively endwise to pull sheathing slugs off the wire end portions to expose wire cores. In this regard, the cutter means typically may include three blade pairs, each pair including two blades located at opposite sides of the axis, both blades of one pair being displaced toward the wire to sever the wire, and both blades of the remaining two pairs being displaced toward the wire sections to strip sheathing from the rearward and forward portions during controlled endwise displacement of the sections. Both blades of one pair are typically displaced into overlapping relation to sever the wire, and both blades of each of the remaining two pairs are displaced to cut only into opposite sides of the sheathing and to strip sheathing from the end portions of the sections as the sections are displaced endwise simultaneously. Another object is to displace the two sections endwise, thereby to displace wire incorporating one of the sections to the first position. In addition, the method may include the step of further separating the sections axially relatively endwise after the blades of the remaining two pairs have been displaced toward the wire sections to cut into the sheathing, thereby to pull sheathing slugs off the wire end portions to expose the wire end cores. Yet another object is to guide displacement of the wire endwise along the axis, at locations between blade pairs; and in this regard, both of the forward and rearward sections may be so guided. A further object is to carry out separation of the forward and rearward wire sections by advancing one section and retracting the other section, relative to the one blade pair; and the method typically involves carrying out further separation of the sections by further advancing the one section and further retracting the other section, relative to each one blade pair. The invention further refers to an apparatus according to claim 15. Forward and rearward pairs of endless conveyors are typically employed, each pair of conveyors defining a wire gripping zone, such zones maintained in alignment with the wire sections during separation of the latter. Means is further provided to maintain one conveyor of each pair laterally displaced relatively toward the other conveyor of the pair to clamp the wire sections between the conveyors of the pairs during the further separation of the wire sections, and operating the conveyor pairs in endless relation to effect the relative separation in a longitudinal direction. As will also be seen, the blades of the first cutter means typically have positions of relative overlap to sever the wire, in response to operation of the first drive means; and the blades of the second and third cutter means typically have positions of penetration only into the sheathing of the section end portions and to such depths as to enable stripping of the sheathing end portions in response to the controllable driving of the conveyor means. In addition, novel and unusually effective apparatus is provided to advance the three sets of blades simultaneously toward the wire to first sever, and subsequently strip wire sheathing, at multiple axial locations, wire sections being axially displaced while severing blades are closed, and prior to closure of sheath stripping blades toward the sections. These and other objects and advantages of the invention, as well as the details of an illustrative embodiment, will be more fully understood from the following specification and drawings, in which: DRAWING DESCRIPTIONFigs. 1a--1f are diagrammatic views showing steps in the method of wire or cable processing; Fig. 2 is a side view elevation showing wire displacing and processing apparatus; Fig. 3 is a top plan view showing the apparatus of Fig. 2; Fig. 4 is an end view, taken in elevation, showing wire belt displacing drive apparatus; Fig. 5 is an elevation showing spring urging of wire drive belts; Fig. 6 is an enlarged cross-section taken in elevation to show sheathing stripping actuator structure; Fig. 7 is a view like Fig. 6 but showing the blades in advanced positions; Fig. 8 is a plan view of the Fig. 6 and Fig. 7 mechanism; Fig. 9 is an end view showing wire severing blades in wire severing position, as in Fig. 1b; Fig. 10 is an end view like Fig. 9 showing the sheathing stripping blades, in sheathing stripping position, as per Fig. 1d; Fig. 10a is a view showing stripping blade edge penetration into wire sheathing; Fig. 11 is a view like Figs. 9 and 11, but showing all blades in retracted position, as in Figs. 1a and 1f; and Fig. 12 is an end view taken on lines 12-12 of Fig. 11. DETAILED DESCRIPTIONReferring first to Figs. 1a--1f, they show in diagrammatic form the positions of both wire severing and sheathing stripping blades, during various steps in the wire processing procedure or method. In this regard, the wire 10 (meant to also refer to cable) has a metal core 11a and a tubular sheathing 11b about the core. The wire is shown extending axially longitudinally in Figs. 1a--1f, the axis being located at 12. First cutter means is provided to include, or may be considered to include, multiple blades. See for example the two wire-cutting blades 13a and 13b of a first set, located or carried for movement laterally toward and away from the wire axis 12. A first drive for controllably simultaneously enabling or advancing the blades toward one another, laterally oppositely (see arrows 14a and 14b in Fig. 1b), is shown at 15. That drive is also operable to retract the blades 13a and 13b away from one another. Second and third cutter means are also provided, for sheathing stripping, and each may be considered to include multiple blades located for movement toward and away from the axis 12. See for example the second set of two blades 16a and 16b, and the third set of two blades 17a and 17b. Blades 16a and 16b are located or considered to be controllably simultaneously displaced, as by drive 18, laterally oppositely, toward one another (see arrows 19a and 19b in Fig. 1d), the drive also operable to retract the blades 16a and 16b away from one another. Similarly, the blades 17a and 17b are located or carried to be controllably displaced, simultaneously, laterally oppositely toward one another (see arrows 20a and 20b in Fig. 1d), and drive 18 may be used for this purpose. Thus, blades 16a and 16b may be displaced toward one another at the same time and to the same extent as blades 17a and 17b are displaced toward another, as is clear from Fig. 1d. The latter shows that the blades 16a and 16b, and 17a and 17b, do not sever the wire but may closely approach the wire while cutting into sheathing 11 for stripping purposes. Brief reference to Figs. 9-11 show the blades 16a and 16b to have V-shape, as do wire severing blades 13a and 13b, and blades 17a and 17b. Note edges 16a' and 16a and 16b' and 16b (of blades 16a and 16b) cutting into the sheathing in Fig. 10a to approach the wire core from four sides for efficient stripping, while leaving the core uncut. Similar functioning of blade edges 17a' and 17a , and 17b' and 17b also takes place, as in Fig. 1d. Fig. 1a shows displacement of the wire axially endwise and longitudinally, as by a conveyor means 21a to the first position as shown. Fig. 1b shows the step of severing the wire thereby to form wire forward and rearward sections 10a and 10b, the blades 13a and 13b being advanced laterally to accomplish complete severing at locus 22, as shown. Note that wire forward section 10a has a rearward end portion 10aa; and the wire rearward section 10b has a forward end portion 10bb. Fig. 1c shows the step of controllably separating the two sections 10a and 10b axially endwise oppositely, as to the positions shown, in which the end portions 10aa and 10bb are spaced from the closed-together blades 13a and 13b. Guides 24 and 25, provided between the blade sets, serve to accurately guide the wire and the sections 10a and 10b during the cutting and severing operation, as is clear from Figs. 1a--1f. Note the tapered entrances 24a and 25a to the guides to receive and center the forwardly advanced wire. Wire drives 21a and 21b are controllably operated to engage and separate the two sections 10a and 10b, as indicated in Figs. 1a and 1c. Fig. 1d shows a sub-step included within the step of stripping sheathing from the forward section rearward portion and from the rearward section forward portion thereby to expose wire ends at the portions. Note that blades 16a and 16b are simultaneously advanced laterally oppositely, as to blade edge positions described above as respects Fig. 10a, and as blades 17a and 17b are also simultaneously advanced laterally oppositely (as to the same extent if such stripping is to be equal for each wire section). Note that blades 13a and 13b now extend in laterally overlapping condition due to operation of drives 15 and 18 as one, i.e., equal rightward lateral displacement for blades 13a, 16a and 17a, and equal leftward lateral displacement for blades 13b, 16b and 17b; however, they may be separately driven so as not to extend in such relation, as shown. Blades 13a, 16a and 17a may be connected together to move rightwardly to equal extent; and blades 13b, 16b and 17b may also be connected together to move leftwardly as one, for extreme simplicity. Fig. 1e shows operation of the wire drives to further endwise separate the wire sections 10a and 10b so as to pull or strip two sheathing end portions 11b' and 11b from the wire sections 10a and 10b, thereby to expose the wire core end portions 11a' and 11a . The stripped sheathing end portions 11b' and 11b , or slugs, are allowed to drop out from between the pairs of guides 24 and 25 which may be split, as shown, to provide slug drop-out openings, and may be movable to facilitate such drop out. Fig. 1f shows all blades laterally retracted and the wire rearward section 10b fully advanced into position corresponding to Fig. 1a position for controlled length endwise positioning to be processed, as in Figs. 1b--1e to provide an exposed core end at its opposite end. Thus, controlled length wires (or cables), with exposed core lengths at each end of each wire, is efficiently and rapidly and controllably provided. See master control 35 to control all the driving, as described, and to be described. Referring now to Figs. 2-8, one form of apparatus to accomplish the above operations (Figs. 1a-1f) is shown in detail. A frame is provided, as at 40-44 and 44a, to mount two conveyors 45 and 46, which may be considered as included within the wire drives 30 and 31, as mentioned. Such conveyors may include two rearwardly positioned endless belts 47 and 48, and two forwardly positioned endless belts 49 and 50. The belts provide stretches, as at 47' and 48', which are adapted to sidewise flatly grip the wire 10 (and specifically the wire rearward section 10b) for endwise advancement and retraction, as during separation of the sections 10a and 10b in Fig. 1c; and stretches 49' and 50' are adapted to sidewise grip the wire 10 (and specifically the wire forward section 10a) for endwise advancement and retraction. The belts 47 and 48 are driven to advance or retract the wire section 10a as from a drive motor 52 (see Fig. 4). The output shaft 53 of the motor drives belt 54, as via a pulley 55, and belt 54 drives shafts 56 and 57. Shaft 56 drives another shaft 58, through gearing 59 and 60, to drive shaft 58 and upper conveyor belt 47 counter-clockwise; whereas lower shaft 57 and lower belt 48 are driven clockwise in Fig. 2. This drives the wire forwardly; whereas when motor 52 is reversed, the wire is driven rearwardly. Additional axles or shafts for the conveyor belts 47 and 48 appear at 58a and 57a. Fig. 2 shows conveyor rotors 60 and 61, and 62 and 63. These carry the belts 47 and 48. Axles 58a and 57a are driven by drive belts 64 and 65 extending between pulleys on the shafts 58 and 58a, and 57 and 57a, as shown. Accordingly, when the belt stretches 47' and 48' are closed against opposite sides of the wire 10, and the motor 52 is operating, the wire is displaced endwise. Means is provided to move the conveyor belt stretches 47' and 48' toward one another to clutch the wire, and away from one another to de-clutch the wire. See for example in Figs. 3-5 the motor or drive 66 carried by a frame part 67 to rotate a vertical screw shaft 68, as via motor output shaft 69, pulley 70, belt 71, and pulley 72 on the screw shaft 68. The screw shaft has screw thread engagement at 73 and 74 with frame members 75 and 76. Frame member 76 supports the ends of shafts 58 and 58a, via member extension 76a, as at 58' and 58a'; whereas frame member 75 supports the ends of shafts 57 and 57a, via member extension 75a, as at 57' and 57a'. Screw threading interfit at 74 is oppositely handed relative to threading interfit at 73, so that when shaft 68 is rotated in one direction about its axis, the frame members 75 and 76 are displaced toward one another, whereby conveyor stretches 47' and 48' may clamp the wire; and when the shaft 68 is rotated in the opposite direction about its axis, the members 75 and 76 are displaced away from each other, and the wire is de-clutched. The bearing supports at 80 and 81 for shafts 58 and 57 are made loose enough to accommodate such up/down movement of those shafts at the conveyor belt drive locations. Note also couplings at 110 and 111. Tension springs 90 and 91 are provided (see Fig. 5) between fixed frame structure 92 and shoulders 76a' on 76a to yieldably urge the structures 76 and 76a, and the belt stretch 47' downwardly; and similarly, tension springs 93 and 94 are provided between fixed frame structure 95 and shoulder 75a' on 75 to yieldably urge the structure 75 and 75a and the belt stretch 48' upwardly. This provides clearance take-up for better control of wire gripping or clamping. The forward conveyor unit 46 embodies conveyor belt drive and up/down movement the same as described in connection with unit 45 in Figs. 3-5. The drive motor 52a for driving the belt stretches 49' and 50' forwardly and reversely is seen in Fig. 3, as is the motor 66a to control belt clamping of the forward wire section. Mechanism between the motors 52a and 66a, and the respective forward conveyor belts 49 and 50, is the same as above described mechanism between motors 52 and 66 and the respective rearward conveyor belts 47 and 48; however, the motors 52 and 52a are typically operated simultaneously, either to drive the wire or wire sections forwardly, as in Figs. 1a and 1f, or to drive the wire sections endwise oppositely, as in Figs. 1c and 1e. A master control to control all drives, in a pre-programmed manner, is seen at 125. Referring to Fig. 11, the wire severing blades 13a and 13b are fully laterally retracted, as are the wire sheathing stripping blades 16a and 16b. Blades 17a and 17b are in axial alignment with blades 16a and 16b, and are not shovn. Note V-angled blade edges 13a' and 13a , and blade edges 13b' and 13b . The blades 13a, 16a and 17a at one side of the wire 10 are interconnected by axially extending carrier rod 80; and the blades 13b, 16b and 17b at the opposite sides of the wire are interconnected by axially extending carrier rod 81, laterally spaced from rod 80. Rods 80 and 81 are relatively movable laterally toward one another to effect wire severing, as by blades 13a and 13b (see Fig. 9 and also Fig. 1b). Rods 80 and 81 are further laterally movable toward one another to effect penetration of the blade edges 16a' and 16a , and 16b' and 16b into the sheathing (as in Figs. 10 and 10a), and as also seen in Fig. 1d. Thereafter, the wire forward and rearward sections 10a and 10b are separated as in Fig. 1e to endwise strip the slugs 10aa and 10bb, off the wire cores, as also seen in Fig. 11. Dropping of the slug is also seen in Fig. 11, as is lowering of a wire guide lower sector B of guide 11b , to release the slug. The upper guide sector is shown at A. A drive 130 is operable to lower and raise sector B. Means to effect the described lateral movement of the blade carrier rods 80 and 81 in shown in Figs. 3, and 6-8. As seen, a laterally extending lead screw 90 is rotatable by a drive motor 91, carried by frame part 92. See connecting shaft 93. As screw 90 rotates in one direction about its axis 90a, nuts 94 and 95 on the screw threads travel axially pppositely (see arrows 96 and 97) to move rod 80 to the right and rod 81 to the left, as in Figs. 9 and 10. See connectors 98 and 99 connecting nut 94 with rod 81, and connectors 100 and 101 connecting nut 95 with rod 80. A pair of parallel lead screws 90 may be utilized for these purposes, as see in Fig. 8, each driven by the motor 91, with one lead screw associated with blades 16a and 16b, and the other associated with blades 17a and 17b. Balanced force transmission to the two sets of blades is thereby effected. See also frame elements 110-116 supporting the structure, as indicated. Bearings appear at 117 and 118. An additional tubular wire guide is seen at 119.	A method of processing wire (10) to cut the wire into sections (10a,10b) and to strip sheathing (11b) from the wire to expose wire ends (11a ,11a') at opposite ends of the sections (10a,10b) including the steps of: a) displacing the wire (10) endwise along an axis (12) to a first position; b) severing the wire by a first blade means (13a,13b) thereby to form wire forward and rearward sections (10a,10b), the forward section having a rearward end portion (10aa), and the rearward section having a forward end portion (10bb), and c) penetrating the sheathing (11b) of the wire forward and rearward sections (10a,10b) by other blade means (16a,16b,17a,17b) spaced axially from said first blade means (13a,13b) to a predetermined depth; the method being characterised by: d) the other blade means having positions of penetration into said sheathing, only; e) the penetrating of the sheathing being effected by controllably displacing the other blade means to a selected depth by a drive means, the drive means being controlled by a master controller in a pre-programmed manner; f) separating said sections (10a,10b) axially relatively endwise prior to penetrating into the sheathing of both sections simultaneously, and, after penetrating the sheathing, g) further separating said forward and rearward sections (10a,10b) axially relatively endwise to pull sheathing (11b',11b ) from the forward section rearward portion (10aa) and from the rearward section forward portion (10bb) thereby to expose wire ends (11a ,11a') at said portions. A method of processing wire as claimed in claim 1 in which steps b) and c) are effected by a cutter means including three blade pairs, (13a,13b,16a,16b,17a,17b) each pair including two blades (13a,13b;16a,16b;17a,17b)located at opposite sides of said axis (12), both blades of one pair (13a,13b) being displaced toward the wire (10) to sever the wire, and both blades of the remaining two pairs (16a,16b,17a,17b) being displaced toward the wire sections (10a,10b) to penetrate said sheathing (11b). A method as claimed in claim 2 wherein both blades (16a,16b,17a,17b) of said remaining two pairs of blades are simultaneously displaced toward the wire sections (10a,10b) to cut into the sheathing (11b) of both sections (10a,10b) simultaneously. A method as claimed in any preceding claim including displacing the two sections (10a,10b) endwise, thereby to displace wire incorporating one of the sections (10a,10b) to said first position. A method as claimed in claim 2 or 3 wherein both blades (13a,13b) of said one pair of blades are displaced into overlapping relation to sever the wire (10), and both blades (16a,16b,17a,17b) of each of the remaining two pairs of blades are displaced to cut only into opposite sides of the sheathing (11b) to strip sheathing from said end portions (10aa,10bb) of said sections (10a,10b), as said sections are displaced endwise simultaneously. A method as claimed in any preceding claim, including separating both said forward and rearward sections (10a,10b) axially relatively endwise after said step b) severing of the wire (10) and prior to said step e) cutting. A method as claimed in claim 2 or any one of claims 3 to 6 as dependent on claim 2 including further separating said forward and rearward sections (10a,10b) axially relatively endwise after said blades (16a,16b,17a,17b) of the remaining two pairs of blades have been displaced toward the wire sections (10a,10b) to cut into the sheathing (11b), thereby to pull sheathing slugs (11b',11b ) off said wire end portions to expose said wire ends (11a',11a ). A method as claimed in claim 7 including allowing dropping of said stripped wire slugs (11b',11b ) downwardly. A method as claimed in any preceding claim, including guiding one or more of said displacements of the wire (10) or wire sections (10a,10b) endwise along said axis (12), at locations between said first blade means (13a,13b) and said other blade means (16a,16b or 17a,17b). A method as claimed in claim 2 or any one of claims 3 to 9 as dependent on claim 2 wherein said separating of the forward and rearward sections (10a,10b) is carried out by advancing one section (10a) and retracting the other section (10b), relative to said one blade pair (13a,13b). A method as claimed in claim 7 or 8 wherein said further separating of the forward and rearward sections (10a,10b) is carried out by further advancing one section (10a) and further retracting the other section (10b), relative to said one blade pair (13a,13b). A method as claimed in claim 11, including means (21b,21a) for advancing said one section (10a) and retracting said other section (10b), said means including forward and rearward pairs of endless conveyors (49,50,47,48), each pair of conveyors defining a wire gripping zone (49',50',47',48'), and including the step of maintaining said zones in alignment with said wire sections (10a,10b) during said further separating of the sections axially. A method as claimed in claim 12, including maintaining at least one conveyor of each pair (49,50;47,48) displaced relatively toward the other conveyor of said pair to clamp the wire sections (10a,10b) between said conveyors of said pairs during said further separation of the wire sections, and operating said conveyor pairs (49,50,47,48) in endless relation to effect said relative separation. A method as claimed in claim 2, or any one of claims 3 to 13 as dependent on claim 2, wherein the blades (13a,13b) of said one pair of blades have V-shaped edges (13a',13a ,13b',13b ) and the blades (16a,16b,17a,17b) of said remaining two pairs of blades have V-shaped edges (16a',16a ,16b',16b ,17a',17a ,17b',17b ) to cut into the sheathing (11b). Apparatus for carrying out the method of any of the preceding claims comprising processing longitudinally axially extending wire (10) that includes a core (11a) and protective structure (11b) extending about the core, the apparatus comprising: a) blade drive means (15,18) for driving a first blade means (13a,13b) for relative movement laterally to sever the wire (10) to form forward and rearward sections (10a,10b); and b) the blade drive means (15,18) being also for driving other blade means (16a,16b,17a,17b) spaced axially from said first blade means (13a,13b) for relative movement laterally to penetrate said protective structure (11b) to a predetermined depth; c) said first and other blade means being operatively interconnected to move laterally to first sever the wire (10) and to then penetrate said protective structure (11b) to said predetermined depth; and d) wire drive means (21a,21b) for displacing said wire (10) axially endwise to position the wire for severing by said first blade means (13a,13b); characterised by: e) said wire drive means (21a,21b) operating to displace said wire sections (10a,10b) axially oppositely relatively endwise after said severing by said first blade means (13a,13b) and prior to simultaneous penetration of said protective structure (11b) of both said wire sections (10a,10b) by said other blade means (16a,16b,17a,17b; f) said wire drive means being arranged to further displace said wire sections (10a,10b), after severing by said first blade means (13a,13b) and after simultaneous penetration of said protective structure (11b) of both said wire sections (10a,10b) by said other blade means (16a,16b,17a,17b), to effect stripping of protective structure (11b) from said wire sections (10a,10b), in the form of slugs (11b',11b ); g) the other blade means having positions of penetration into said protective structure, only; and h) a master controller arranged to control the blade drive means (15,18) in a pre-programmed manner to controllably displace the other blade means to penetrate the protective structure to a selected depth. Apparatus as claimed in claim 15, wherein said wire (10) has a longitudinal axis (12), said first blade means (13a,13b) having a first cutting edge (13a',13a ;13b',13b) and said other blade means (16a,16b,17a,17b) having another cutting edge (16a',16a ,17a',17a ;16b',16b ,17b',17b ), said cutting edges being differentially spaced from said axis (12) as said first and other blade means (13a,13b,16a,16b,17a,17b) are simultaneously moved toward said axis (12) prior to said severing of the wire (10). Apparatus as claimed in claim 15 or 16, wherein said first blade means includes a first set of blades (13a,13b), and said other blades means includes second and third sets of blades (16a,16b,17a,17b). Apparatus as claimed in claim 17, including wire guides (24,25) between said first and second blade means (13a,13b,16a,16b), and between said first and third blade means (13a,13b,17a,17b), said guides (24,25) including elements (A) that remain in guiding position, and other elements (B) movable out of guiding position to allow dropping of protective structure slugs (11b',11b ) stripped from wire ends (10aa,10bb). Apparatus as claimed in claim 18, including drive means (130) operatively connected with said other elements (A) to effect movement thereby into and out of wire guiding position. Apparatus as claimed in any one of claims 17 to 19 in which: a) said first, second and third blade means each includes multiple blades (13a,13b,16a,16b,17a,17b) located for movement toward said axis (12), the apparatus including: b) a first drive means (15;80,81,90,94,95) for controllably displacing said multiple blades (13a,13b) of said first blade means toward said axis (12) to sever the wire (10). c) and additional drive means (18;80,81,90,94,95) for controllably displacing said multiple blades of said second and third blade means (16a,16b,17a,17b) toward said axis (12) to cut into said protective structure (11b), said second and third blade means (16a,16b,17a,17b) respectively located at axially opposite sides of said first blade means (13a,13b) and axially spaced therefrom, d) the wire drive includes a conveyor drive means arranged to controllably drive a conveyor means so as to i) position the wire (10), to be severed by said first blade means, (13a,13b), thereby to produce forward and rearward wire sections, (10a,10b) ii) relatively displace said sections (10a,10b) axially, into positions to enable penetration of the blades of said second and third blade means (16a,16b,17a,17b) into said protective structure (11b), for subsequent stripping of said structure from a rearward portion of the forward section (10a) and from a forward portion of the rearward section (10b), as during controlled endwise displacement of said sections (10a,10b) by said conveyor means (47,48,49,50). Apparatus as claimed in claim 20, wherein said blades (13a,13b) of said first blade means have positions of relative overlap to sever the wire (10), in response to operation of said first drive means (15;80,81,90,94,95). Apparatus as claimed in claim 20 or claim 21, wherein said blades (16a,16b,17a,17b) of said second and third blade means have positions of penetration only into said protective structure (11b) of said section end portions (10aa,10bb) to enable stripping of said end portions in response to said controllable driving of said conveyor means (47,48,49,50). Apparatus as claimed in any of claims 20 to 22, wherein said conveyor means (47,48,49,50) includes forward and rearward pairs of endless conveyors (49,50,47,48) to respectively engage and displace the wire sections (10a,10b), while the blades (13a,13b) of the first blade means are closed in overlapping relation. Apparatus as claimed in claim 23, including actuator means (66,66a,68,69,70,71,72,75,76) to maintain at least one conveyor of each pair displaced relatively toward the other conveyor of said pair, to clamp the wire sections (10a,10b) between the conveyors during further separation of the sections (10a,10b) and during protective structure stripping. Apparatus as claimed in claim 23 or 24, wherein said conveyors comprise endless belts (47,48,49,50) and driven by the conveyor drive means (52;52a) to controllably advance and retract said belts endlessly. Apparatus as claimed in claim 24, wherein said actuator means includes a rotary screw (68), a drive (66;66a) to rotate the screw (68) and follower means (33,34,75,76) to convert rotary motion of the screw (68) into linear motion acting to displace the conveyor or conveyors (47,48,49,50). Apparatus as claimed in any of claims 15 to 26 wherein said blades (13a,13b) of the first blade means (13a,13b) have V-shaped edges (13a',13a ,13b',13b ). Apparatus as claimed in any of claims 15 to 27, wherein the blades of each of the other blade means (16a,16b,17a,17b) have V-shaped edges (16a',16a ,16b',16b ,17a',17a ,17b',17b ). Apparatus as claimed in claim 28, wherein said edges of the blades of the first blade means (13a,13b) are closer to said axis (12) than said edges of the other blade means (16a,16b,17a,17b), as said blades (13a,13b,16a,16b,17a,17b) approach said axis (12) for wire severing and protective structure stripping.	EUBANKS ENG CO; EUBANKS ENGINEERING COMPANY	HOFFA JACK L; HOFFA, JACK L.
EP-0489504-B1	489,504	EP	B1	EN	19,970,305	1,992	20,100,220	new	G06F5	G06F13	G06F13, G06F5	G06F 5/06P, G06F 13/28	Bidirectional FIFO buffer for interfacing between two buses	Data transfers between a workstation bus and a graphics adapter bus are handled by a plurality of first-in-first-out (FIFO) buffers, each of which is independently operable to transfer data in a selected direction between the two buses. The FIFOs are accessible either directly by the workstation processor or by means of a DMA operation. Each FIFO is assigned a unique range of addresses in the address space of the workstation processor to permit a workstation process to transfer a block of data to or from a selected FIFO using a single instruction. Workstation writes (reads) to a FIFO are suspended in response to a first status signal indicating that the high (low) threshold for that FIFO has been reached and are restarted in response to a second status signal indicating that the low (high) threshold has been reached. A buffer counter indicating the amount of data in each FIFO is initialized at zero for outbound transfers from the workstation to the adapter or at the maximum buffer count for inbound transfers from the adapter to the workstation. The buffer count is incremented in response to accesses from the workstation side and is decremented in response to accesses from the adapter side, regardless of the direction of transfer.	This invention relates to a FIFO buffer for interfacing between two system buses and. more particularly, to a buffer for interfacing between an I/O bus of a computer workstation and an internal bus of a graphics adapter. Data or information in computers is processed in a predominantly serial fashion. Many times there are sources and destinations of data that are connected by buses. Usually there is a mismatch in the rate at which data is produced and the rate at which it can be accepted. The data is therefore stored in a first-in-first-out (FIFO) buffer between the data source and data destination to accommodate any mismatches between the rate at which the data source can generate the data and the rate at which the data destination can process it. One such application for a FIFO buffer is for interfacing between the I/O system bus of a computer or workstation and the internal bus of a graphics adapter coupled to a display device. The buffering requirements are complicated by the fact that, typically, several processes are running concurrently on the workstation processor, each of which may have to access the graphics adapter. Also, in many systems, read access as well as write access to the graphics adapter is required. What is desired, therefore, is a FIFO buffer that can transfer data bidirectionally and can accommodate several processes running simultaneously on the workstation processor. Research Disclosure no.286 Feb 1988 p.64 discloses apparatus for controlling a FIFO to transfer data in a selected direction between a first line and a second line using a single buffer count for control of data transfers in both of the two access directions. The single value is interpreted differently depending on the direction of the data transfer. US Patent 4,285,038 discloses use of a FULL signal to stop a transmitting system from transmitting further data into a buffer when the buffer is full and an EMPTY signal to stop a receiving system from receiving further data from a buffer when the buffer is empty. According to the present invention there is provided an apparatus for controlling a FIFO buffer to transfer data in a selected direction between a first line and a second line, said buffer having a first transfer mode in which data is transferred from said first line to said second line and a second transfer mode in which data is transferred from said second line to said first line, comprising: means for storing a buffer count indicating the amount of data in said buffer; means for incrementing said count in either of said modes in response to the transfer of data between said first line and said buffer; means for decrementing said count in either of said modes in response to the transfer of data between said second line and said buffer; means for suspending the transfer of data between said first line and said buffer; and means for resuming said transfer of data between said first line and said buffer; characterised in that: said means for suspending the transfer of data is responsive to the determination of a predetermined relation between said count and a first threshold; and said means for resuming said transfer of data is responsive to the determination of a predetermined relation between said count and a second threshold. Further according to the present invention there is provided a method of controlling a FIFO buffer to transfer data in a selected direction between a first line and a second line, said buffer having a first transfer mode in which data is transferred from said first line to said second line and a second transfer mode in which data is transferred from said second line to said first line, comprising the steps of: storing a buffer count indicating the amount of data in said buffer; incrementing said count in either of said modes in response to the transfer of data between said first line and said buffer; decrementing said count in either of said modes in response to the transfer of data between said second line and said buffer; suspending the transfer of data between said first line and said buffer; and resuming said transfer between said first line and said buffer; characterised in that: said step of suspending the transfer of data is responsive to the determination of a predetermined relation between said count and a first threshold; and said step of resuming the transfer of data is responsive to the determination of a predetermined relation between said count and a second threshold. The FIFO interface may comprise a plurality of FIFO buffers coupled in parallel between two buses, with each FIFO being addressable over a range of addresses to facilitate block transfers. Each FIFO may be capable of data transfer in either direction from the buses, in accordance with a transfer direction bit which can be written to from the buses, and may be operable independently of the other FIFOs to permit data transfer by multiple applications running concurrently. Threshold crossings are used to pace (i.e. suspend and resume) processes accessing a buffer to minimize the software overhead required to avoid overrun or underrun. Thus, a process accessing a buffer is suspended in response to a buffer count (also referred to the the in-use count) crossing a first threshold (high threshold for a write and low threshold for a read) and is not resumed until the buffer count crosses a second threshold (low threshold for a write and high threshold for a read). DMA accesses are suspended and resumed in this manner by a DMA suspend signal sent to the DMA controller. Accesses by processes running on a workstation central processor are controlled by an interrupt handler responding to threshold interrupts. As one interrupt is generated the corresponding threshold is disabled and the other threshold enabled, so that a process accessing the FIFO is alternately suspended and resumed in response to high and low (or low and high if reading to the buffer) interrupts. These suspensions and resumptions are transparent to the process accessing the FIFO, which does not have to monitor the availability of buffer storage space but can simply assume that such space exists. Suspending the process while the buffer count progresses from the first threshold to the second threshold minimizes the thrashing that might occur when the buffer count continually crosses and then recrosses the same threshold. Preferably the threshold counts are stored in registers which, together with the buffer count register and interrupt enable registers, may be accessed from the buses to alter the register contents. This permits a first process to control a second process in a manner that is transparent to the controlled process simply by making suitable writes to the registers. Preferably, each buffer in-use counter is always incremented after accesses from the first bus and decremented after access from the second bus, regardless of the direction of data transfer, to minimize hardware complexity. The in-use counter thus indicates the number of filled buffer locations for one direction of data transfer (e.g. from the workstation to the graphics adapter) and the number of empty buffer locations for the other. To account for this varying significance of the buffer count, the threshold register contents and comparison operations are adjusted accordingly. In the drawings:Fig. 1 is a schematic diagram of a computer system incorporating a FIFO buffer constructed in accordance with our invention, Fig. 2 is a schematic diagram of the FIFO interface of our invention as it appears to the units to which it is attached, Fig. 3 is a schematic diagram of the internal structure of the FIFO interface shown in Fig. 2, Fig. 4 is a diagram illustrating how the FIFO pointers point to locations in the global memory of the FIFO interface shown in Fig. 3, Fig. 5 is a schematic diagram of the elements associated with one of the FIFOs of the interface shown in Fig. 3 and, Fig. 6 is a diagram illustrating the functioning of the in-use counter and threshold registers in the various modes of data transfer of the FIFO shown in Fig. 5. Referring first to Fig. 1, a system 100 incorporating our invention includes a central processing unit (CPU) or processor 102 coupled to main memory 104 directly and to an input/output (I/O) bus 108 through an I/O bus and direct memory access (DMA) controller 106. A bus interface 109 couples I/O bus 108 via line 111 to a graphics adapter 110, which is in turn coupled to a display monitor 112 of any suitable type known to the art. I/O bus 108 also couples controller 106 to one or more other peripherals, indicated generally by the rectangular box 114. These peripherals may include such standard devices as a keyboard, alternative input devices such as a mouse, a printer, secondary storage such as a magnetic or optical disk drive, or the like. Although the present invention is not limited to any particular system 100, an exemplary system would be a high-performance workstation such as the IBM RISC System/6000 computer, using a Micro Channel bus for I/O bus 108. For convenience in this specification, central processor 102, main memory 104 and I/O bus and DMA controller 106 will sometimes be collectively referred to as the workstation 116, as distinguished from such peripherals connected to the I/O bus 108 as the graphics adapter 110. Further, to distinguish processor 102, memory 104 and bus 108 from similar components of the graphics adapter 110, these workstation components will sometimes be referred to as the workstation processor 102, workstation memory 104 and workstation bus 108, respectively. Graphics adapter 110 runs asynchronously relative to workstation 116. Referring now to Fig. 2, graphics adapter 110 includes an internal adapter bus 202, which is connected to the bus interface 109 and hence to workstation bus 108 by way of a FIFO interface 200. As shown in Fig. 2, FIFO interface 200 may be conceptually regarded as consisting of four FIFOs, FIFOs 250, 252, 254 and 256, coupled in parallel between bus interface 109 and the adapter bus 202. As will be described below, FIFOs 250-256 may be used concurrently, to transfer data in a selected direction for each FIFO between workstation 116 and graphics adapter 110. Also coupled to adapter bus 202, as shown in Fig. 2, are one or more graphics processors indicated generally by the rectangle 204. Graphics adapter 110 additionally includes such standard components as a frame buffer (not shown) for storing a bit map of the image to be displayed on the monitor 112. These and similar components of the adapter 110 are not as such relevant to the present invention, however, and therefore have not been shown. Referring now to Fig. 3, line 111 from bus interface 109 alternately contains data and address information, which is multiplexed to minimize the number of parallel conductors. A transceiver 228 coupled to bus interface line 111 and FIFO interface data line 230 controls the transfer of data between the two lines. (For convenience herein, elements such as lines 111 and 230 will be referred to in the singular, even though they may in fact contain a number of conductors in parallel.) Data line 230 is coupled to various components of the FIFO interface 200, including a status register 232, an interrupt pending register 234 and a DMA destination address register 236. Status register 232 stores information indicating the status (e.g. high threshold reached, low threshold reached) of each of FIFOs 250-256, while interrupt pending register 234 stores information indicating whether an interrupt from a particular FIFO is currently pending. Status register 232 stores two bits for each FIFO, one for the high threshold and one for the low threshold. Each status bit is set to 1 whenever the corresponding threshold is crossed in one direction (from below for the high threshold and from above for the low threshold) and is reset to zero whenever the same threshold is recrossed in the opposite direction. Interrupt pending register 234 also stores two bits for each FIFO, one for each threshold. Each bit is set to 1 concurrently with the generation of an interrupt signal for the corresponding FIFO and threshold to indicate that an interrupt is pending and is reset to 0 when read by the workstation processor 102 (more particularly, by the interrupt handler running on the processor). DMA destination address register 236 stores a DMA address, which is used in an alternative mode of operation described below. A second transceiver 238 interconnects data line 230 with an adapter data line 240 originating from a bus controller (MBC in Fig. 3) 242 coupled to graphics adapter bus 202. Bus controller 242 also provides address information from adapter bus 202 on a separate adapter address line 244. A latch 246 responsive to line 111 from bus interface 109 supplies address information from line 111 (and thus ultimately from workstation 116) to one input of a multiplexer 248. DMA destination address register 236 provides the other input to multiplexer 248. Multiplexer 248 is suitably actuated to provide either the DMA address from register 236 or the workstation address signal from line 111 on an output line 268. The address signal selected by multiplexer 248 is supplied to one input of a multiplexer 270. Multiplexer 270 receives a second input from adapter address line 244 as well as a third address input from a FIFO address line 258, to be described below. Multiplexer 270 provides an output on line 272. Line 272 is also coupled to the output of an address decoder 274 that receives inputs from line 268 coupled to multiplexer 248 and from line 244 coupled to bus controller 242. FIFO interface 200 includes a global memory 206, which is preferably implemented by means of a video RAM (VRAM). Global memory 206 receives an address input from address line 272, has a parallel data port coupled to data line 230 and has a serial data port coupled to adapter data line 240. Depending on the mode of operation global memory 206 may receive, via multiplexer 270, a DMA destination address from register 236 through multiplexer 248, a workstation address from latch 246 through multiplexer 248, a FIFO address from line 258 or an adapter address from line 244. Alternatively, global memory 206 may receive an address from decoder 274 that is decoded from the adapter address on line 244 or the workstation or DMA address on line 268. Data may be written to or read from global memory 206 via either the parallel port coupled to data line 230 or the serial port coupled to adapter data line 240. This provision of dual ports allows data to be simultaneously written to and read from global memory 206. FIFOs 250-256 are implemented by means of four sets of FIFO registers 208-226, with one set of registers for each FIFO. These registers include, for each FIFO, a global pointer register 208, an index pointer register 210, an in-use count register 212, high and low threshold registers 214 and 216, high and low threshold enable registers 218 and 220, control register 222, and add and subtract registers 224 and 226. Global pointer register 208 stores the starting address of a 64K block in global memory reserved for the particular FIFO. Each FIFO can be located on any 64K byte boundary in global memory 206. The value stored in register 208 corresponds to the six most significant bits of the memory address (i.e. A21-A16). Typically, FIFOs 250-256 may be set up to occupy the top 256K of global memory 206. Index pointer register 210 contains the address offset within each FIFO for the next access from the workstation 116. The actual address in global memory 206, supplied on line 258, is the concatenation of the global pointer stored in register 208 and the index pointer stored in register 210, with the index pointer containing the 16 least significant address bits. Index pointer register 210 is updated by the FIFO control logic to be described in response to reads and writes to the FIFO. In general, accesses to a FIFO from either the workstation 116 or the adapter bus 202 are made by addressing global memory 206 via address decoder 274, since the desired access is to the next read or write buffer location rather than a particular memory location as such. Each of FIFOs 250-256 exists to workstation 116 and to graphics processors 204 as either a unique address or (as described below) a unique range of addresses in the address space of the addressing unit. Address decoder 274 decodes the address signal supplied to it from workstation 116 or from adapter bus 202 and selects the FIFO within whose range the address falls. The FIFO pointers direct accesses to the desired location within a FIFO. Accesses to portions of global memory other than the FIFO areas are made via multiplexer 270, which provides undecoded address signals to global memory address line 272. Fig. 4 shows how the various global pointers and index pointers are used to define FIFO areas in global memory 206. It will be assumed for the purpose of this figure that the global pointer registers 208 of the respective FIFOs 250-256 store global pointers GMP1-GMP4, while the index pointer registers 210 corresponding to the same FIFOs store respective index pointers IP1-IP4. As shown in the figure, each global pointer (e.g. GMP1) points to the starting address of the corresponding FIFO area. As noted above, this starting address must, in the particular implementation shown, be an integral multiple of 64K. The index pointer for each FIFO (e.g. IP1) indicates the address of the next access by workstation 116 relative to the starting address defined by the global pointer. In Fig. 4, four consecutive FIFO areas 260, 262, 264 and 266 are shown. In the embodiment shown, this is implemented by storing global pointers in registers 208 that differ by 1 from those of adjacent FIFOs to point to adjacent 64K blocks. Each FIFO in-use count register 212 holds a number representing the number of bytes of data in that FIFO. The required format of data in register 212 is changed by setting a transfer direction bit, to be described, in the corresponding control register 222. In the outbound (workstation-to-adapter) transfer mode the value stored is a number representing the number of bytes of data in that FIFO. In the inbound (adapter-to-workstation) transfer mode, the value stored is 64K (10000h in hexadecimal form) minus the number of bytes of data in the FIFO available to be read. For all operations, the FIFO in-use count register 212 is incremented every time the corresponding FIFO is accessed (written to or read) from the workstation side. Alteration of the content of the in-use count register 212 in response to accesses from the adapter side is effected by means of the add or subtract registers 224 and 226, in a manner to be described below. Each high threshold register 214 stores a threshold that is compared with the content of the in-use count register 212 for that FIFO. An interrupt will occur (if enabled) when the in-use count register 212 indicates that there is an amount of data in the FIFO at least equal to the high threshold. This interrupt is sent to the central processor 102 in the workstation 116 via the I/O bus 108. As is described in more detail below, the threshold value that is stored in register 214 depends on the setting of the transfer direction bit in the corresponding control register 222. When the transfer direction bit is a 0, indicating an outbound data transfer from the workstation 116 to the graphics adapter 110, the stored value corresponds to the desired threshold. On the other hand, when the transfer direction bit is 1, indicating an inbound transfer from the graphics adapter 110 to the workstation 116, the stored value is 64K (assuming this is the size of the corresponding FIFO area in global memory 206) minus the desired value. An interrupt occurs after a workstation access to the FIFO or when the in-use count register 212 is updated from the adapter side by a write to the add register 224 or subtract register 226. Each low threshold register 216 functions in a manner similar to that of the corresponding high threshold register 214. The value stored in register 216 defines a low threshold that is compared with the value stored in the in-use count register 212. An interrupt will occur (if enabled) when the in-use count register 212 indicates an amount of data in the FIFO equal to or less than the low threshold setting. This interrupt is sent to the workstation 116 in a manner similar to that of the high threshold interrupt. The value that is stored in register 216 depends on the setting of the transfer direction bit in the corresponding control register 222. When the transfer direction bit is 0, the value stored corresponds to the desired low threshold value. On the other hand, when the transfer direction bit is 1, the entered value is 64K minus the desired value, again assuming a FIFO area of this size in global memory 206. Like the high threshold interrupt, the low threshold interrupt occurs after a workstation access to the FIFO or when the in-use count register 212 is updated from the adapter side by a write to register 224 or 226. Each high threshold interrupt enable register 218 and low threshold interrupt enable register 220 stores one bit. When the high threshold interrupt enable bit is set to 1, an interrupt will be sent to the workstation 116 when the amount of data in the corresponding FIFO is equal to or greater than the high threshold setting for that FIFO as stored in high threshold register 214. This bit allows a workstation process to enable or disable the high threshold interrupt from the corresponding FIFO. When set to a 1, an interrupt will be generated when the in-use count register 212 crosses the high threshold in such a way as to cause a status bit for that FIFO, stored in status register 232 (Fig. 3), to toggle from 0 to 1. Once the interrupt is cleared via a read of the portion of interrupt pending register 234 (Fig. 3) corresponding to that FIFO, no more interrupts will be generated until the condition exists again where the corresponding bit in status register 234 toggles from 0 to 1. This enable bit is reset when the high threshold interrupt is generated. Each low threshold interrupt enable register 220 functions in a similar manner. When the low threshold interrupt enable register bit for a particular FIFO is set to a 1, an interrupt will be sent to the workstation 116 when the amount of data in the corresponding FIFO is less than or equal to the low threshold setting for that FIFO, as defined by the corresponding low threshold register 216. In a manner similar to that of the high threshold bit, this bit allows software to enable or disable the low threshold interrupt from the corresponding FIFO to the I/O bus 108. When set to a 1, an interrupt will be generated when the in-use count register 212 crosses the low threshold and then recrosses the same threshold. This is done to eliminate spurious low threshold interrupts before they are actually required. In other words, when a FIFO is being filled, it must be filled to above the low threshold, and then the interrupt will occur when enough data is removed to cross below the low threshold again. Once the interrupt is cleared via a read of the interrupt pending register 234, no more interrupts are generated until the condition exists again where the bit in status register 232 toggles from 0 to 1. This enable bit is reset when the low threshold interrupt is generated. Each control register 222 stores four bits: a reset index register bit, a reset in-use count bit, a transfer direction bit, and a DMA suspend enable bit. When set to a 1, the reset index register bit clears the index pointer register 210 for the corresponding FIFO. Similarly, the reset in-use count register bit, when set to a 1, clears the corresponding in-use count register 212. The transfer direction bit, as noted above, indicates the direction of transfer between the workstation 116 and the graphics adapter 110. When set to a 1, the transfer direction bit indicates that the direction of data flow is from the graphics adapter 110, more particularly the graphics adapter bus 202, to the workstation 116. If the transfer direction bit is set to 0, the data flow is from the workstation 116 to the bus 202 of the graphics adapter 110. This mode bit is used within the FIFO interface 200 to reverse the function of the high and low threshold registers 214 and 216 and status register 232 insofar as they regulate the suspension and resumption of workstation processes or DMA access. These changes are transparent to the programmer when this bit is used. The DMA suspend enable bit, when set to 1, suspends DMA to the corresponding FIFO when its in-use count register 212 reaches the high threshold value in the case of a data transfer from the workstation 116 (mode = 0), or low threshold value in the case of a data transfer to the workstation 116 from the graphics adapter 110 (mode = 1). DMA remains suspended until the in-use register 112 reaches the low threshold value in the case of a data transfer from the workstation 116 (mode = 0) or high threshold value in the case of a data transfer to the workstation 116 from the graphics adapter 110 (mode = 1). When this function is used, both the high and low threshold interrupt enable registers 218 and 220 for the particular FIFO are disabled by being set to 0. FIFO add and subtract registers 226 are accessible from the graphics adapter bus 202 and are used to update the in-use count register 212 for the particular FIFO. Each time a FIFO transfer from the graphics adapter bus 202 to the workstation 116 is started, add register 224 is set to 64K (10000h), indicating an empty FIFO. Subtract register 226 is used to indicate the number of bytes removed from the corresponding FIFO during a transfer from the workstation 116 to the graphics adapter bus 202 or the number of bytes transferred from the graphics adapter bus 202 into the corresponding FIFO during a data transfer in the other direction from the graphics adapter bus 202 to the workstation 116. These numbers are loaded into the subtract register 226 from the adapter bus 202 to decrement the in-use counter 212 by the number of bytes written to or read from the corresponding FIFO from the adapter bus side. Registers 208, 214, 216, 218 and 220 may be written to or read by the workstation 116, as appropriate. Registers 210 and 212 may be read from but not written to. In addition, control register 222 may be written to by the workstation 116, while add and subtract registers 224 and 226 may, as noted above, be written to from the adapter bus 202. Fig. 5 shows in further detail the connections between the various registers of FIFO 250. The remaining FIFOs 252-256 are identical to FIFO 250. In this figure is shown the particular portion 260 of global memory 206 allocated to FIFO 250, as determined by the content of the global pointer register 208 (labeled START ADD POINTER in Fig. 5). Those elements in the figure below global memory portion 260 are unique to FIFO 250, while the elements in the upper portion of the figure are common to the four FIFOs 250-256. As shown in Fig. 5, timing and control logic 276 (not shown in Fig. 3) is responsive to a decoded address signal supplied on line 272 from address decoder (labeled I/O Decode in Fig. 5) 274 and from DMA destination address register 236 as well as a read/write control signal on line 278 that originates ultimately from workstation 116. Timing and control logic 276 increments index pointer register 210 and in-use count register 212 as data is written to or read from global memory portion 260 by workstation 116. To update the in-use count register 212 as accesses are made from the graphics adapter bus 202, and to initialize the in-use count at 64K in the case of an inbound data transfer, an arithmetic logic unit (ALU) 280 is used. ALU 280 receives one input from in-use count register 212, an add input from add register 224 and a subtract input from subtract register 226. In response to an add/subtract signal from timing and control logic 276, ALU 280 either adds to the in-use count the value stored in add register 224 or subtracts from the count the value stored in subtract register 226 and stores the result in register 212, replacing its former contents. Also shown in Fig. 5 is a comparator 282 receiving inputs from the in-use count register 212, high threshold register 214 and low threshold register 216 for FIFO 250. In response to a compare signal received from timing and control logic 276, comparator 282 compares the in-use count with the threshold stored in registers 214 and 216 to provide an interrupt output on line 284 or a DMA suspend output on line 286 in the case of a successful comparison. Before FIFOs 250-256 are used, each of the global pointer registers 208 is programmed to point to a 64K block in global memory 206. The high and low threshold registers 214 and 216 are set to the selected values. The index pointer register 210 is initialized to zero at power up. The first FIFO access will be to the first location in the FIFO as pointed to by the global memory pointer stored in register 208 and the index pointer stored in register 210. For each access to the FIFO address range, the access will be to the memory location pointed to by the concatenation of these two pointers. A range of FIFO addresses are used for each FIFO to allow an application running on the workstation 116 to write to a selected FIFO using Store Multiple instructions. The Store Multiple instruction stores the contents of internal registers (not separately shown) in workstation processor 102 at successively increasing addresses. Conversely, the Load Multiple instruction reads a block of data from the selected FIFO, also at selectively increasing addresses. Preferably, a range of 128 words are provided for each FIFO. Thus, as shown in Fig. 5, address decoder 274 selects FIFO 250 on receiving an address signal from workstation 116 within the range of 0600h to 07FCh. In system 100, addresses are reckoned in bytes of 8 bits, with 4 bytes in each 32-bit word. This range has an extent (including the last but not first address) of 1FCh bytes, or 508 bytes in decimal notation, which corresponds in turn to an extent of 127 words, not counting the first address, or 128 words if the first address is included. As a multitasking system, workstation 116 can have multiple processes running simultaneously. Each of these processes can access the adapter 110 directly. To aid the operating system, running on workstation processor 102, in maintaining the state of the adapter 110 for each process, two sets of control registers (not separately shown) exist in different pages of workstation memory 104. This allows two processes to access adapter 110 simultaneously without any operating system overhead. It also allows an application to use the adapter 110 while another FIFO is being taken away from a process set up for another. FIFOs 250-256 can be accessed by workstation processor 102 directly by way of the four FIFO input address ranges, or by using the DMA controller 106 of workstation 116 for a DMA access. To perform a DMA access to a FIFO, DMA destination address register 236 (Figs. 2 and 3) is loaded with an address within the appropriate range to access the correct FIFO. Pacing of DMA accesses to the FIFO are controlled as described below. Whenever an access is made to one of the FIFO address ranges from workstation 116, timing and control logic 276 (Fig. 3) sends out a pulse to increment the corresponding index pointer register 210 and in-use count register 212. Timing and control logic 276 then sends out a pulse to perform a compare operation, which compares the in-use count stored in register 212 with the high and low threshold values stored in registers 214 and 216. Index pointer register 210 always points to the next location in global memory at the completion of any cycle. The in-use count stored in register 212 is also updated automatically during any adapter access to the FIFO. Data flows from workstation 116 directly to the appropriate memory location as pointed to by the concatenation of the global pointer stored in register 208 and index pointer stored in register 210. The index pointer is incremented appropriately for byte (8 bits), half-word (16 bits) and word accesses. When a FIFO is accessed from the adapter bus 202, the in-use count register is updated by graphics processor microcode by way of add and subtract registers 224 and 226. During DMA writes to a FIFO, all FIFO interrupts are suspended. Control or pacing of the data writes is done by an added control signal (line 286 in Fig. 5) to the bus interface 109. A high threshold status signal is gated into bus interface logic 109, which temporarily suspends DMA. Data is then removed from the FIFO by adapter 110 in the normal manner. DMA is restarted when enough data is removed from the FIFO that the state of low threshold status changes. Likewise, during DMA reads from a FIFO, all FIFO interrupts are again suspended. Control or pacing of the data reads is done by the same control signal to the bus interface 109. A low threshold status signal is gated into bus interface logic 109, which temporarily suspends DMA. Data is then added to the FIFO from the adapter bus 202 in the normal manner. DMA is restarted when enough data is added to the FIFO that the state of high threshold status changes. This pacing feature thus allows DMA accesses to the FIFO in either direction with no software intervention. For a transfer of data from the workstation 116 to the graphics adapter 110 (more particularly, to the graphics adapter bus 202), the FIFO to be used for that transfer is initialized by writing to the corresponding FIFO control register 222, setting the transfer direction bit to 0, indicating an outbound data transfer, and clearing the index pointer register 210 and in-use count register 212. As noted above, the index pointer stored in register 210 concatenated with the global memory pointer stored in register 208 indicates the location in global memory 206 for the next write to the FIFO. As also noted above, in-use count register 210 indicates the number of bytes to be read from the FIFO. An in-use count of 00000h indicates a FIFO empty condition, while a count of 10000h indicates a full FIFO condition. The low threshold register 216 for that FIFO is set to the number of bytes desired to generate a low threshold interrupt, while the corresponding high threshold register 214 is set to the number of bytes desired to generate a high threshold interrupt. Workstation 116 writes data to the selected FIFO via a write to the FIFO range for that FIFO. After each write to the FIFO, both the index pointer register 210 and the in-use count register 212 are appropriately incremented. The graphics adapter bus 202 (more particularly, a graphics processor 204 coupled to the bus 202) reads the data in the FIFO directly from global memory 206 using its own read/write pointer, which is either stored in local memory (not separately shown) associated with the graphics processor 204 or calculated from the values stored in the index pointer register 210 and in-use count register 212 for that FIFO. The graphics processor 204 attached to bus 202 then updates the in-use count register 212 for that FIFO by writing to the subtract register 226 to indicate the number of bytes read. When transferring data in the opposite direction, from the graphics adapter bus 202 to the workstation 116 via I/O bus 108, the selected FIFO is initialized by first writing to the corresponding FIFO control register 222, setting the transfer direction bit to 1 to indicate an inbound data transfer and clearing the corresponding index pointer register 210 and in-use count register 212. After it has been cleared, the in-use count register 212 is loaded with the value 64K by loading this value in the corresponding add register 224. The index pointer stored in register 210 concatenated with the global memory pointer stored in FIFO register 208 now indicates the location in global memory 206 for the next read of the FIFO by the workstation 116. In the inbound transfer mode, in contrast to the outbound transfer mode, an in-use count of 10000h stored in register 212 indicates a FIFO empty condition and count of 00000h indicates a full FIFO condition. The number of bytes remaining to be read from the FIFO can be found by subtracting the value stored in in-use count register 212 from 64K (10000h). The low threshold register 216 for the selected FIFO is set to 10000h (64K) minus the number of bytes desired to generate a low threshold interrupt, while the high threshold register 214 is set to 10000h (64K) minus the number of bytes desired to generate a high threshold interrupt. A graphics processor 204 attached to the graphics adapter bus 202 writes data for the FIFO directly into global memory 206 using the same read/write pointer which, as noted above, may either be stored in local memory (not separately shown) associated with the graphics processor or calculated from the values stored in index pointer register 210 and in-use count register 212. The graphics processor 204 then updates the in-use count register 212 by again writing to the subtract register 226, this time indicating the number of bytes written. The workstation 116 reads data from the FIFO via a read of the FIFO range from that FIFO. After each read from the FIFO, both the index pointer register 210 and the in-use count register 212 for that FIFO are automatically incremented. In both the outbound and inbound modes of data transfer, the contents of the low and high threshold registers 216 and 214 are continually compared with those of the in-use count register 212 for the same FIFO, and the portion of status register 232 allocated to that FIFO is updated after an access to the FIFO range or to any of registers 212, 214, 216, 222, 224 or 226. In system 100, the software overhead of accessing FIFOs 250-256 is minimized through the use of high and low threshold interrupts. These interrupts allow processes running on the workstation processor 102 to write data to a FIFO without first having to query the adapter 110 to determine whether there is enough room. As data is written from the workstation 116 to the adapter 110, the FIFO fills. As the data is processed by the adapter 110, the FIFO empties as indicated by the in-use count. Whenever the amount of data in the FIFO exceeds the high threshold, a high interrupt is generated. Likewise whenever the amount of data goes below the low threshold, a low interrupt is generated. These interrupts are handled by an independent process running on the workstation processor 102, called an interrupt handler, which is invoked whenever an interrupt is generated by the adapter 110. By properly maintaining the threshold values and enables, the interrupt handler can stop and start the application writing to the FIFO without the application being aware of it. All together, these controls allow applications to transfer data blindly to a FIFO, but automatically stop executing when there is no more room in the FIFO. This lets other tasks be performed in the system. The application will automatically start executing again when room is available in the FIFO. When an application running on workstation processor 102 is about to write to one of the FIFOs 250-256, it registers itself with the interrupt handler via a system call. This lets the interrupt handler know which process to start and stop, and prevents other applications from using the FIFO until this one is done with it. After registering itself with the interrupt handler, the application is free to access the FIFO. When high and low threshold interrupts occur, care must be taken to prevent rapid-fire interrupts from occurring as the data in the FIFO fluctuates across a threshold. Care must also be taken to ensure that any stopped applications will be started. These problems are solved jointly by the hardware and the interrupt handler. Initially, a FIFO is set up with the high threshold enabled and the low threshold disabled. As data is written to the FIFO from the workstation 116, the hardware described above moves the data into global memory 206 and increments the corresponding in-use count register 212. When a graphics processor 204 (more particularly, a process running on that processor) detects data in the FIFO, it reads the data and decrements the in-use count register 212 via subtract register 226. If the workstation 116 writes enough data to the FIFO for the in-use count to exceed the high threshold, a high threshold interrupt is generated and, at the same time, the high threshold is disabled to prevent further high threshold interrupts from occurring. At this point, both the high and low thresholds are disabled. The interrupt handler now processes the interrupt, paces the writing application, and ensures that the high and low thresholds for the FIFO are put into the proper state of enablement for the system to continue running. By enabling the low interrupt threshold and stopping the application, the workstation processor 116 becomes available for performing other tasks while the adapter 110 processes the data in the FIFO. When it decrements the in-use count stored in register 212 so that it is less than the low threshold, a low threshold interrupt is generated, and the low threshold is automatically disabled to prevent subsequent interrupts. Summarizing the above, on outbound transfers from the workstation 116 to the adapter 116, the FIFO generates a high threshold interrupt (if enabled) if the in-use count stored in register 212 reaches or exceeds the high threshold stored in register 214 and generates a low threshold interrupt (if enabled) if the in-use count reaches or goes below the low threshold stored in register 216. The interrupt handler running on the workstation processor 102 responds to a high threshold interrupt by suspending the writing application, disabling the high threshold interrupt by writing to high threshold interrupt enable register 218, and enabling the low threshold interrupt by writing to low threshold interrupt enable register 220. The interrupt handler responds to a low threshold interrupt by resuming the writing application, disabling the low threshold interrupt by writing to low threshold interrupt enable register 220, and enabling the high threshold interrupt by writing to high threshold interrupt enable register 218. On inbound transfers from the adapter 110 to the workstation 110, the FIFO generates a high threshold interrupt (if enabled) if the in-use count stored in register 212 reaches or goes below the high threshold stored in register 214 and generates a low threshold interrupt (if enabled) if the in-use count reaches or exceeds the low threshold stored in register 216. (As already noted, on inbound transfers the counts have an inverted significance.) The interrupt handler running on the workstation processor 102 responds to a low threshold interrupt by suspending the reading application, disabling the low threshold interrupt by writing to low threshold interrupt enable register 220, and enabling the high threshold interrupt by writing to high threshold interrupt enable register 218. The interrupt handler responds to a high threshold interrupt by resuming the reading application, disabling the high threshold interrupt by writing to high threshold interrupt enable register 218, and enabling the high threshold interrupt by writing to high threshold interrupt enable register 220. Through the use of automatic threshold disabling and predefined interrupt enabling as described above, required access to and manipulation of the graphics adapter 110 and processing path length are greatly minimized during interrupts. Furthermore, automatic starting and stopping of an application minimizes software overhead for accessing the FIFO and improves the utilization of the workstation processor 102. Some graphics operations require data to be read from the adapter 110 and put into workstation memory 104. To accommodate this, the graphics adapter FIFOs 250-256 are, as noted above, bidirectional and can move data in either direction between the workstation 116 and the graphics adapter 110. The provision of multiple FIFOs permits the handling of graphical commands separately from graphical data. Separating the commands from the data in the manner allows two graphics adapter processors 204 to work in parallel. Thus, one processor can be processing the graphical data of a particular command from the data FIFO, while the other processor is working on the next command in the command FIFO. When graphical data is written to the adapter 110 from the workstation 116, FIFOs 250-256 operate as described above in the preceding paragraphs. However when data is to be read from the adapter 110, it becomes necessary to resynchronize the workstation 116 and adapter 110, transfer the data, and return the FIFO to the normal state for writing to the adapter 110. When an application running on the workstation processor 102 has to perform a graphical operation that requires reading data from the adapter 110, it writes an appropriate command into the command FIFO. Since the application cannot know if the command has been processed yet, it calls the adapter device driver (a process running concurrently on the workstation processor 102) and requests that it (i.e. the application) be stopped in the same fashion that an application would be stopped after a high threshold interrupt. When the read command is processed by the adapter 110, the process running on the adapter processor 204 that will put data into the data FIFO sets the FIFO's in-use count to its maximum value, causing a high threshold interrupt. However, since the original application is already asleep, the interrupt handler merely changes the threshold enables so that the low threshold interrupt is enabled. As the adapter 110 moves the data into the FIFO, it decrements the in-use count. While this reverses the actual meaning of the count, it serves to use the existing controls and interrupt logic to achieve maximum throughput and minimum overhead. When the in-use count falls below the low threshold, a low threshold interrupt is generated. (In this particular mode of operation, the transfer direction bit in the control register 222 of the data FIFO remains at 0, hence the usual significance of the low threshold, even though the transfer direction is inbound). As in the case of a low threshold interrupt during a write operation, the interrupt handler wakes up the stopped application, enables the high threshold interrupt, and lets the workstation and adapter processors 102 and 204 work in parallel. As the workstation 116 reads data from the FIFO, the FIFO hardware increments the in-use count. As the adapter 110 puts data into the FIFO, the in-use count is decremented. If the adapter 110 fills the FIFO, it stops and waits for more room. If the application reads enough data for the in-use count to exceed the high threshold, the interrupt handler stops the application, enables the low threshold and lets other tasks be performed until the data becomes available. When the adapter 110 finishes the operation, a read data finish interrupt is generated. There are two conditions under which this interrupt will occur: one is that the application is stopped, waiting for a low threshold interrupt to restart it; the other is that the application is running, expecting a high threshold interrupt to stop it or expecting to finish reading the data. If the application is stopped, the read data finished interrupt will cause the interrupt handler to restart it. The FIFO thresholds are left with the low threshold enabled. The application will then run until all of the data is read. This leaves the in-use count at its maximum value. To put the FIFO into its usual write data state, the application sets the in-use count to its minimum value. This causes a low threshold interrupt to be generated. As in all low threshold interrupts, the interrupt handler enables the high threshold, but, since the application is already running, it does not have to be started. The adapter 110 is now in its usual write data state. If the application was running at the time of the read data finished interrupt, the interrupt handler would disable the high threshold interrupt, enable the low threshold interrupt, and return. The operation proceeds in the same fashion as when the application was asleep and restarted by the read data finished interrupt. When managing the shared use of the graphics adapter 110 among multiple applications, the operating system for the workstation 116, which also runs on the workstation processor 102, must itself access the adapter. As described above, FIFOs 250-256 control applications via the high and low threshold interrupts. When the adapter 110 is taken from one process and given to another, the current state of the adapter is saved and the state changed to how the other process had it the last time it was running. Through the use of hardware-maintained FIFO controls, the operating system can turn off the threshold interrupts, keeping the application quiet, and access a FIFO itself. The operating system need only poll the FIFO in-use count stored in register 212 to ensure that enough room exists in the FIFO. When the operating system has finished accessing the adapter 110, the threshold interrupts are reenabled and the applications permitted to run. Together, the threshold interrupts are used to control the applications accessing the adapter 110; the hardware-maintained pointers and counters allow the operating system to access a FIFO without the application knowing it.	Apparatus for controlling a FIFO buffer (200) to transfer data in a selected direction between a first line (111) and a second line (202), said buffer having a first transfer mode in which data is transferred from said first line to said second line and a second transfer mode in which data is transferred from said second line to said first line, comprising: means (212) for storing a buffer count indicating the amount of data in said buffer; means (276) for incrementing said count in either of said modes in response to the transfer of data between said first line and said buffer; means (276) for decrementing said count in either of said modes in response to the transfer of data between said second line and said buffer; means (284) for suspending the transfer of data between said first line and said buffer; and means (284) for resuming said transfer of data between said first line and said buffer; characterised in that: said means for suspending the transfer of data is responsive to the determination of a predetermined relation between said count (212) and a first threshold (214, 216); and said means for resuming said transfer of data is responsive to the determination of a predetermined relation between said count (212) and a second threshold (216, 214). An apparatus as claimed in claim 1 wherein said count (212) ranges between a minimum count (216) and a maximum count (214) and said apparatus further comprises: means for initializing said buffer count in accordance with said transfer mode, said buffer count being initialized at said minimum count in said first transfer mode and being initialized at said maximum count in said second transfer mode. An apparatus as claimed in claim 1 or claim 2 in which said transfer of data is from said first line (111) to said buffer (200), said first threshold being a high threshold (214) and said second threshold being a low threshold (216). An apparatus as claimed in claim 1 or claim 2 in which said transfer of data is from said buffer (200) to said first line (111), said first threshold being a low threshold (216) and said second threshold being a high threshold (214). An apparatus as claimed in claim 1 or claim 2 in which said first line (111) is associated with a DMA controller (106). An apparatus as claimed in claim 1 or claim 2 in which said first line (111) is associated with a central processor (102). An apparatus as claimed in claim 1 or claim 2 in which said suspending means (284) generates a first interrupt signal and said resuming means (284) generates a second interrupt signal. A method of controlling a FIFO buffer (200) to transfer data in a selected direction between a first line (111) and a second line (202), said buffer having a first transfer mode in which data is transferred from said first line to said second line and a second transfer mode in which data is transferred from said second line to said first line, comprising the steps of: storing a buffer count indicating the amount of data in said buffer; incrementing said count in either of said modes in response to the transfer of data between said first line and said buffer; decrementing said count in either of said modes in response to the transfer of data between said second line and said buffer; suspending the transfer of data between said first line and said buffer; and resuming said transfer between said first line and said buffer; characterised in that: said step of suspending the transfer of data is responsive to the determination of a predetermined relation between said count (212) and a first threshold (214,216); and said step of resuming the transfer of data is responsive to the determination of a predetermined relation between said count and a second threshold (216,214). A method as claimed in claim 8 wherein said count (212) ranges between a minimum count and a maximum count and said method further comprises the step of: initializing said buffer count in accordance with said transfer mode, said buffer count being initialized at said minimum count in said first transfer mode and being initialized at said maximum count in said second transfer mode. A method as claimed in claim 8 or claim 9 in which said transfer of data is from a first line to said buffer, said first threshold being a high threshold (214) and said second threshold being a low threshold (216). A method as claimed in claim 8 or claim 9 in which said transfer of data is from said buffer to a first line, said first threshold being a low threshold (216) and said second threshold being a high threshold (214).	IBM; INTERNATIONAL BUSINESS MACHINES CORPORATION	BISCHOFF GARY; MILOT PAUL JOSEPH; SEGRE MARC; SPENCER JEFFREY SCOTT; WILSON LESLIE ROBERT; BISCHOFF, GARY; MILOT, PAUL JOSEPH; SEGRE, MARC; SPENCER, JEFFREY SCOTT; WILSON, LESLIE ROBERT
EP-0489505-B1	489,505	EP	B1	EN	19,940,727	1,992	20,100,220	new	F16B21	null	F16B37, B23K9, B29C65, F16B21, F16B5	F16B 21/07, R16B5:12	Metal weld stud and plastic clip	The combination of a metal stud (3) having a projecting head for welding to a receptor surface and a resilient clip (10) for mounting on said stud (3) and retained by said projecting head (6) is characterised in that the underside of said head has a tapered shoulder (7) which reduces progressively to the diameter of said stud, in that said clip has a retaining hole (11) of which the intenal diameter increases correspondingly from a diameter equal to that of the stud whereby it engages the tapered shoulder under said head when the clip is applied to the stud and in that said clip is provided with at least two retaining members (13) which contact said receptor surface to urge the clip into close engagement with the tapered shoulder under the head of the stud. The clip is easily mounted on the stud by direct pressure and provides a more positive location of the clip on the stud.	The present invention relates to the combination of a metal weld stud having a projecting head for welding to a receptor surface together with a resilient clip for mounting on said head and retained by said projecting head (DE-A-2 744 294). The resilient clip is commonly formed of plastics material and is provided with a slightly undersized undercut opening which is forced over the projecting head and thus engages the projecting head to retain the clip on the stud. It is an object of the present invention to provide such a stud-and-clip combination which permits the clip to be easily mounted on the stud by direct pressure and which provides a more positive location of the clip on the stud when it is welded to a receptor surface. According to the present invention, a metal stud having a projecting head for welding to a receptor surface and a resilient clip for mounting on said stud and retained by said projecting head is characterised in that the underside of said head has a tapered stepwise shoulder which reduces step-by-step to the diameter of said stud, in that said clip has a retaining hole of which the internal diameter increases correspondingly from a diameter equal to that of the stud whereby it engages the tapered shoulder under said head when the clip is applied to the stud and in that said clip is provided with at least two retaining members which contact said receptor surface to urge the clip into close engagement with the tapered shoulder under the head of the stud. The clip is applied to the stud in an axial direction so that the longitudinal axes of the stud and of the clip are aligned. In a preferred embodiment of the invention, said tapered shoulder reduces to the diameter of the stud in at least three steps and the retaining hole of the clip increases in corresponding steps from a internal diameter equal to the diameter of the stud whereby it engages the stepped shoulder under said head when the clip is applied. The flexibility of the plastic clip and the height of the steps and their configuration provide a wide degree of tolerance of accommodating variations between the stud and the receptor surface. In previously known stud-clips, the underside of the projecting head extends normally from the stud. In order that the invention can be better understood a preferred embodiment will now be described by way of example with reference to the accompanying drawings in which:- Figure 1 is a part section a clip and stud according to the invention showing the stud mounted on the clip, and Figure 2 is a plan view of the clip shown in Figure 1. In the drawings, weld stud 3 is welded through zone 2 to receptor surface 4. Stud 3 has a cylindrical stem 5 and a projecting head 6 at its outward (with respect to the weld) end. The underside of projecting head 6 has a tapered shoulder 7 reducing progressively to the diameter of stem 8 of stud 3 by a series of three steps 9, 9′, 9″. Clip 10 has a mounting aperture 11, the inner surface of the aperture being formed as a series of steps 12, 12′, 12″ which correspond to the steps 9, 9′, 9″ of shoulder 7. Two resilient arms 13 extending from clip 10 contact receptor surface 4 at 14 and serve to urge the stepped surface of mounting aperture 11 into close contact with the stepped shoulder 7 of weld stud 3. This firmly locates clip 10 in position on stud 3 and obviates the possibility of sliding between the stud and clip. The resilience of the plastics material from which clip 10 is formed enables the narrowest part of aperture 11 to be forced over the widest part of lead 6 and when the clip 10 is in position over head 6, the resilience of arms 13 pressing against receptor surface 4 urges the steps 12, 12′, 12″ of the clip into firm contact with the steps 9, 9′, 9″ of tapered shoulder 7.	A metal stud (3) having a projecting head for welding to a receptor surface and a resilient clip (10) for mounting on said stud (3) and retained by said projecting head (6) characterised in that the underside of said head has a stepwise, tapered shoulder (7) which reduces step-by-step to the diameter of said stud, in that said clip has a retaining hole (11) of which the intenal diameter increases correspondingly from a diameter equal to that of the stud whereby it engages the tapered shoulder under said head when the clip is applied to the stud and in that said clip is provided with at least two retaining members (13) which contact said receptor surface to urge the clip into close engagement with the tapered shoulder under the head of the stud. A metal stud and a resilient clip according to claim 1, wherein said tapered shoulder (7) reduces to the diameter of the stud (3) in at least three steps and the retaining hole (11) of the clip (10) increases in corresponding steps from a intenal diameter equal to the diameter of the stud (3) whereby it engages the stepped shoulder under said head when the clip (3) is applied.	EMHART INC; EMHART INC.	BAUM HEINZ OTTO; REINDL JOHANN; BAUM, HEINZ OTTO; REINDL, JOHANN
EP-0489507-B1	489,507	EP	B1	EN	19,940,720	1,992	20,100,220	new	A61M16	null	A61M1, A61M16, A61M27	K61M16:04F1B, A61M 16/04, K61M16:04A7	Endotracheal tube	A cuffed tracheal tube 1 has a suction lumen 14 extending along the tube and opening through a suction aperture 19 immediately adjacent the upper, proximal end of the cuff 12. The inflatable cuff 12 is attached to the external surface of the tube by collars 23 and 24. The proximal collar 24 is everted within the inflatable portion 25 of the cuff 12 so that it does not extend beyond the inflatable portion and so that the maximum amount of secretions can be removed through the suction aperture 19.	This invention relates to medico-surgical tubes of the kind having a cuff embracing the tube with an inflatable portion of the cuff shaped to seal the outside of the tube with the wall of a body cavity within which the tube is inserted, the cuff being attached to the tube by respective collar portions at opposite ends of the cuff, a suction lumen extending along the tube to the region of the proximal end of the cuff and a suction aperture opening from the lumen to the exterior of the tube immediately adjacent the proximal end of the cuff. Such cuffed tubes can present a problem in that secretions produced above the cuff in the trachea, or other body channel in which the tube is located, will be prevented from flowing along the channel and will thereby collect above the cuff, providing a site for the accumulation of bacteria and infection. Various proposals have been made previously for removing such secretions by providing a suction aperture above the cuff. In US-A-4,607,635 there is described a tracheal tube having a channel which opens at various locations along its length and through which a suction catheter can be inserted to remove secretions at any desired location above the cuff. In US-A-4,305,392 there is described a tracheal tube with a bulbous chamber above the cuff in which secretions are collected for removal through a suction lumen extending through the wall of the tube. The problem with both of these tubes is that it is not possible to remove secretions that collect immediately above the cuff. This is because the cuff is conventionally attached to the wall of the tube by means of short collars at opposite ends of the cuff, which are adhered to the tube and extend above and below the cuff. The length of the collar above the cuff defines the closest distance by which the suction aperture can be spaced from the cuff, because any attempt to form a suction aperture through the collar would weaken the join of the cuff to the tube and possibly lead to leakage from the cuff. In US-A-4,840,173 there is suggested a way in which secretions close to the cuff could be removed, by providing a suction tube which projects over the proximal collar of the cuff. This, however, would have the disadvantage of being relatively complex and expensive to make and provides an undesirable projection from the side of the tube which could irritate the delicate surface of the trachea. There is also the risk that the end of the suction tube may damage the cuff or become blocked by the cuff. This risk can be reduced by making the upper end of the cuff more rigid, but this is a further complication in the construction of the tube. It is an object of the present invention to provide a medico-surgical tube which can be used to avoid the above-mentioned disadvantages. According to one aspect of the present invention there is provided a medico-surgical tube of the above-specified kind, characterised in that the proximal end of the cuff is folded back so that a part at least of the inflatable portion of the cuff overlies the proximal collar portion so that the proximal collar portion does not extend beyond the inflatable portion of the cuff. The suction lumen preferably extends along the tube within the wall thickness of the tube. The external surface of the proximal collar portion is preferably attached to the tube. The internal surface of the distal collar portion may be attached to the tube. The cuff may be shaped to seal with the trachea and the suction lumen is suitable to be utilized to remove secretions that collect in the trachea above the cuff. An endotracheal tube, in accordance with the present invention, will now be described, by way of example, with reference to the accompanying drawings, in which: Figure 1is a side elevation view of the tube; Figure 2is an enlarged cross sectional view of a part of the tube; Figure 3is an enlarged transverse section along the line III - III of Figure 1; and Figure 4is an enlarged side elevation of a part of an alternative tube. With reference first to Figures 1 to 3 there is shown an endotracheal tube assembly 1 with its distal, patient end 10 in trachea 2 of a patient and with its proximal, machine end 11 projecting from the patient's mouth. An inflatable cuff 12 encompasses the outside of the tube close to its patient end 10 and serves to seal the tube with the trachea. The tube 1 has a primary lumen 3 which opens at both ends of the tube and provides a gas passage for ventilation of the patient's lungs. The tube 1 is of a semi-flexible plastics material and may be made by a conventional extrusion process with two secondary lumens 13 and 14 extending axially along the tube within the wall thickness. Both lumens 13 and 14 are closed at the two ends of the tube such as by heat sealing or by plugs inserted into the lumens. One of the secondary lumens 13 provides a passage for inflation and deflation of the cuff 12 and opens through the outside wall of the tube 1 via an aperture 15 which opens into the interior of the cuff. The inflation lumen 13 is sealed below the aperture 15. Close to the machine end of the tube, a small-diameter inflation line 16 has one end joined in the inflation lumen 13 to that the inflation lumen continues through the inflation line. At the other end of the inflation line 16, there is provided a conventional inflation indicator 17 and coupling 18 by which a syringe (not shown) can be connected to supply air, via the inflation lumen, to inflate the cuff 12. The other secondary lumen 14 is a suction lumen which opens close to its distal end through a suction aperture 19 in the outside wall of the tube 1 located immediately adjacent the cuff 12. The suction lumen 14 is closed on the distal side of the suction aperture 19 such as by a plug 20 inserted in the lumen 14. Close to the proximal, machine end of the tube 1, a small-diameter suction line 21 has one end joined into the suction lumen 14 so that the suction lumen continues through the suction line. At its other end, the suction line 21 has a coupling 22 by which connection can be made to a suction pump and collection vessel (not shown). The cuff 12 is attached to the outside wall of the tube 1 in a manner different from that in conventional tubes. The cuff 12 is a thin-walled blow moulding of PVC or a similar plastic and is of tubular shape and circular section having two collar portions 23 and 24 at opposite ends. The internal diameter of the collar portions 23 and 24 is the same as the external diameter of the tube 1. Between the two collars 23 and 24, over the major part of its length, the cuff 12 has a diameter which is greater than that of the tube 1 so that, when assembled on the tube this forms an inflatable portion 25 of the cuff which has a substantially constant diameter along its entire length, when inflated within the trachea. The distal, patient end collar 23 is joined to the tube in the conventional manner so that it extends beyond the inflatable portion 25 and has its internal surface bonded to the external surface of the tube 1, such as by means of a solvent. The opposite, proximal or machine end collar 24 is joined in a different manner by everting it, so that it is folded inside the inflatable portion 25 and is bonded to the tube 1 by what was originally the outside surface of the collar. In this way, the inflatable portion 25 of the cuff 12 overlies the proximal collar 24 of the cuff. It can be seen that this enables the suction aperture 19 to be located immediately adjacent the inflatable portion 25 of the cuff 12 so that any secretions from the upper part of the trachea which collect above the cuff can be removed by suction through the aperture 19 with very little secretions, if any, remaining above the cuff. The tube 1 is inserted in the trachea in the usual way, with the cuff 12 deflated. When correctly positioned, the cuff 12 is inflated by means of a syringe connected to the inflation line coupling 18 with a measured amount of air, so as to inflate the cuff to the desired pressure and produce an effective seal with the trachea. Ventilation can then be carried out by connecting the tube 1, at its machine end, to a conventional ventilation/anaesthetic machine. Periodically, a suction pump or similar device, such as a syringe, is connected to the coupling 22 of the suction line 21, to remove secretions that have collected in the trachea above the cuff 12. Alternative constructions of cuff are also possible in which the inflatable portion of the cuff is folded back to overlie the collar, so that the collar does not extend beyond the inflatable portion. For example, with reference to Figure 4, there is shown a cuff 12′ in which the proximal end collar 24′ has its inside surface bonded to the tube, the wall of the cuff being folded back over the collar to extend in a proximal direction and then being folded back in the opposite direction. This results in an annular space 26′ between the collar 12′ which is closed, such as by an adhesive 27′ to prevent entry of secretions.	A medico-surgical tube (1) having a cuff (12) embracing the tube with an inflatable portion of the cuff shaped to seal the outside of the tube with the wall of a body cavity within which the tube is inserted, the cuff being attached to the tube by respective collar portions (23,24) at opposite ends of the cuff, a suction lumen (14) extending along the tube to the region of the proximal end of the cuff, and a suction aperture (19) opening from the lumen to the exterior of the tube immediately adjacent the proximal end of the cuff, characterised in that the proximal end of the cuff (12) is folded back so that a part at least of the inflatable portion (25) of the cuff overlies the proximal collar portion (24) so that the proximal collar portion (24) does not extend beyond the inflatable portion (25) of the cuff. A medico-surgical tube according to Claim 1, characterised in that the suction lumen (14) extends along the tube (1) within the wall thickness of the tube. A medico-surgical tube according to Claim 1 or 2, characterised in that the external surface of the proximal collar portion (24) is attached to the tube (1). A medico-surgical tube according to any one of the preceding claims, characterised in that the internal surface of the distal collar portion (23) is attached to the tube (1). A tracheal tube according to any one of the preceding claims, characterised in that the cuff (12) is shaped to seal with the trachea (2), and that the suction lumen (14) is suitable to be utilized to remove secretions that collect in the trachea above the cuff.	SMITHS INDUSTRIES PLC; SMITHS INDUSTRIES PUBLIC LIMITED COMPANY	TURNBULL CHRISTOPHER STRATTON; TURNBULL, CHRISTOPHER STRATTON
EP-0489509-B1	489,509	EP	B1	EN	19,970,521	1,992	20,100,220	new	B22C15	B22C9	B22C15	B22C 15/28	Method of manufacturing core and mold	A method of manufacturing a core and a mold using self-hardening molding sand or gas-hardening molding sand, wherein the self-hardening molding sand or the gas-hardening molding sand is charged in a core pattern or a flask while applying three-dimensional jolt, and a method of manufacturing a core and a mold using self-hardening molding sand, wherein air flow is precipitated by sucking the self-hardening molding sand in a core pattern or a flask.	The present invention relates to a method of manufacturing a core and a mold, and more particularly to a method of manufacturing a core and a mold using self-hardening molding sand. A core means a part which forms the shape of a hollow portion of a casting product, and is generally manufactured with a sandmold. The configuration of the core is multifarious depending on the casting product. Manufacture of a core using self-hardening molding sand has been heretofore performed by, for example, hand molding, by a machine, such as a jolt machine and a two-dimensional jolt molding machine, and by filling a mold utilizing air (a blowing method). The method of filling molding sand utilizing air is used widely in mass production foundries as a method of molding a core with comparatively medium and small sized mass products as its objects. In the small quantity production of a variety of products in which self-hardening molding sand is used for the core, the core is generally manufactured by hand molding only or a joint operation of molding by a machine (such as a jolt machine and a two-dimensional jolt molding machine) and that by hand. Fig. 7 shows a method of manufacturing a core by hand molding. In Fig. 7, reference numeral 1 denotes a core pattern, 2 denotes self-hardening molding sand, and 9 denotes a rammer or a sand rammer. The self-hardening molding sand 2 is charged into the core pattern 1 in an appropriate quantity, rammed with the rammer or the sand rammer 9 and left as it is until it self-hardens. Fig. 8 shows a method of manufacturing a core using a two-dimensional jolt molding machine, in which 1 denotes a core pattern, 2 denotes self-hardening molding sand and 6' denotes a two-dimensional jolt molding machine. The core pattern 1 is placed on the two-dimensional jolt molding machine 6', the self-hardening molding sand 2 is charged in an appropriate quantity into the core pattern 1, and the two-dimensional jolt molding machine 6' is operated to shake the pattern,so as to improve the filling density of the self-hardening molding sand 2. However, it is impossible to fill the self-hardening molding sand 2 to corner angle portions A1, A2, A3, A4, A5, A6 and others of the core pattern only with the shaking force of the two-dimensional jolt molding machine 6'. Therefore, supplementary hand molding for filling the self-hardening molding sand 2 to the corner angle portions A1, A2, A3, A4, A5, A6 and others of the core pattern 1 with a rammer or a sand rammer 9 becomes necessary. After the core is manufactured, the core is taken out of the core pattern 1 after leaving it as it is until the self-hardening molding 2 hardens,similarly to hand molding shown in Fig. 7. Such a method of manufacturing a core has problems as follows. When a core having a complicated configuration is molded, it is required to ram the core by hand in order to realize the configuration of the core with certainty and to obtain a required core density. Thus, in case of a core pattern having such a complicated configuration that ramming of the core by hand is difficult, the core is split. Therefore, after manufacture of the core is completed there occur such problems as that assembling the split cores is more time consuming, dimensional accuracy of the core deteriorates, and burrs occur on the cast product. Further, it is necessary to leave the core as it is for a certain period of time until the self-hardening molding sand hardens in the core pattern after manufacture of the core is completed. As a result, there are such problems as increased core molding periods, variation in time between the hardening and ejection of cores, and deformation of cores at the time of ejection or after ejection (varying depending on ambient conditions). A hand molding method and a molding method with a two-dimensional jolt molding machine are also adopted for the manufacture of a sandmold casting using self-hardening casting sand. In these manufacturing methods, the pattern is taken out of a flask after standing by for several tens of minutes to several hours until a chemical reaction between a resin for caking mixed in the molding sand and a hardening agent progresses and the mold hardens after the molding of the self-hardening mold is completed. Fig. 15 is a partial longitudinal sectional side view showing a method of manufacturing a self-hardening mold by hand molding, in which numeral 11 denotes a pattern, 12 a flask, 13 self-hardening molding sand, 17 a roller conveyor, 22 a sand rammer and 24 a surface plate. In Fig. 15, the flask 12 is placed on the surface plate 24 on the roller conveyor 17, the pattern 11 is placed in the flask 12, and the self-hardening molding sand 13 is charged in an appropriate quantity in a void portion, formed with the pattern 11 and the flask 12 and is rammed with the sand rammer 22. After the mold is manufactured through repetitive operations of charging of the self-hardening molding sand 13 and ramming with the sand rammer 22, the mold is left as it is until it hardens. Fig. 16 is a partial longitudinal sectional side view showing a method of manufacturing a self-hardening mold using a two-dimensional jolt molding machine, in which numeral 11 denotes a pattern, 12 denotes a flask, 13 denotes self-hardening molding sand, 14 denotes a vibrating table, 15 denotes air springs, 16 denotes shakers, 17 denotes a roller conveyor, 23 denotes a riser wood pattern and 24 denotes a surface plate. In Fig. 16, the flask 12 mounted on the surface plate 24 is placed on the vibrating table 14 of the two-dimensional jolt molding machine, the pattern 11 is placed in the flask 12, the self-hardening molding sand 13 is charged in the void portion formed with the pattern 11 and the flask 12, and it is intended to improve the filling density of the self-hardening molding sand 13 by shaking the two-dimensional jolt molding machine. In this case, filling at a root portion of the riser wood pattern 23 and the like is not sufficient only by molding with shaking on the two-dimensional jolt molding machine. Therefore, it is also required to perform supplementary hand molding operation with a sand rammer or a rammer. Further, in the event that there is an attachment on the pattern, filling at the lower part of the attachment is liable to be insufficient, and thus hand operation is necessary in a similar manner to the above-described case. After the mold is manufactured in such a manner, ejection is performed, that is, the pattern 11 and the riser wood pattern 23 are taken out after leaving the mold as it is until the self-hardening molding sand 13 hardens similarly to the case of hand molding. According to the conventional methods of manufacturing a self-hardening mold shown in Fig. 9 and Fig. 10, there are such problems as follows. First of all, it is required to increase the filling density of the self-hardening molding sand and to reduce the unevenness thereof in order to secure dimensional accuracy of a casting and to eliminate seizure, sand contamination and the like which are defects in casting complicating the fettling. However, it is insufficient by the conventional method, viz., the mold manufacturing method by hand molding or a two-dimensional jolt molding machine. Further, the ejection time of the self-hardening mold depends on the atmospheric temperature, the sand temperature, the humidity, the quantity of resin added, the type of hardening agent, the quantity of a hardening agent added and the like. Therefore, it is difficult to control the ejection time, and such troubles as damage to the pattern and damage and deformation of the mold occur. Furthermore, since the period for leaving the mold untouched in keeping with hardening from the completion of the molding to the ejection of the self-hardening mold is long, there is a drawback of obstructing productivity, too. On the other hand, if the hardening agent is adjusted so as to shorten the ejection time, the problem is caused that hardening starts before the molding operation, and the period during which the molding sand can be used, viz., the spendable period is reduced by a large margin, thus making it difficult to produce a good mold. There is known from JP-A- 6210345 a vacuum molding and casting method wherein no-binder sand (i.e. plain sand without a binder or water) is introduced into a molding box over a pattern, with a heat film placed therebetween over the surface of the pattern. The interior of the box being connected to a vacuum so as to draw the film onto the pattern surface. The molding box and sand is then subjected to two-dimensional jolting/vibration at the same time as the interior space of the box is subjected to sub-atmospheric pressure. The difference in pressure between that of the atmosphere and said vacuum causes hardening of the sand in the mold. a molten metal is introduced to the mold while the mold is held in the hardened state by the differential pressure. There is also known from JP-A- 630 52741 a method of forming a casting mold using a technique similar to that of JP-A- 6210345 described hereinbefore, wherein a differential pressure is applied across a mass of free-flowing, no binder sand whereby to ensure that this takes up the shape of a forming box and is held rigid in that condition. Two-dimensional jolting is again sufficient because of the free-flowing nature of this type of plain sand. It is an object of the present invention to solve the above-described problems when a core and a mold are manufactured using self-hardening molding sand. More particularly, it is an object of the present invention to provide a method of manufacturing a core in which problems in molding performance and in points of quality of the core and the casting have been solved. Further, it is a second object of the present invention to provide a method of manufacturing a self-hardening mold in which molding workability and workmanship of a self-hardening mold are excellent and problems in point of quality of a cast casting product can be solved. In accordance with a first aspect of the present invention, there is provided a method of manufacturing a cast core, comprising introducing self-hardening sand into a hollow core pattern, subjecting the core pattern and the self-hardening sand therein to three-dimensional jolting whereby to promote complete filling of the hollow core pattern with said sand, and removing air and moisture from the core pattern, and hence from said sand, by means of a suction apparatus to promote the hardening of the core. In the method of manufacturing a core, the molding sand flows into every nook and corner of the mold and minute filling is performed by applying three-dimensional jolting to the pattern when the self-hardening molding sand is charged or after being charged in the core pattern. The moisture contained in the molding sand and the moisture generated by chemical reaction of the caking agent are removed by speeding up air flow by applying suction to the filled molding sand, thus accelerating hardening. According to the above described method of manufacturing a core, it is possible to obtain the following effects: (1) The core molding period can be reduced to 1/3 to 1/5 of that by a conventional method. (2) A ramming operation on the core by hand can be discontinued completely. (3) The applicable range of molding the core as one body is enlarged considerably. As a result, assembly and dimension check operations of a core become no longer required. (4) Burrs on a casting disappear due to integration of the core, thus making it possible to reduce fettling periods sharply. (5) Hardening period of the core is reduced to 1/2, and productivity of the core is improved. (6) Hardening of the core being uniform and good, the accuracy of the core is improved and the dimensional accuracy of a casting is also improved. Further, reduction of finishing cost is also made possible. In accordance with a second aspect of the invention, there is provided a method of manufacturing a cast mold, comprising introducing self-hardening sand into a hollow casting frame, subjecting the casting frame and self hardening sand therein to three-dimensional jolting whereby to promote filling of the hollow casting frame with said sand, and reducing the air pressure in the casting frame whereby to assist in removing moisture from the sand, generated during the hardening reaction, and to thereby promote the hardening of the casting mold. The invention is described further hereinafter, by way of example only, with reference to the accompanying drawings, in which:- Fig. 1 is a longitudinal sectional view of an apparatus according to a first embodiment of the present invention; Fig. 2 is a longitudinal sectional view of an apparatus according to a second embodiment of the present invention; Fig. 3 is a longitudinal sectional view of an apparatus according to a third embodiment of the present invention; Fig. 4 is a longitudinal sectional view of an apparatus according to a fourth embodiment of the present invention; Fig. 5 is a longitudinal sectional view of an apparatus according to a fifth embodiment of the present invention; Fig. 6 is a partial longitudinal sectional side view of an apparatus according to sixth, seventh and eighth embodiments for executing a method of manufacturing a self-hardening mold of the present invention; Fig. 7 is a longitudinal sectional view of an apparatus for executing a conventional method of manufacturing a core; Fig. 8 is a longitudinal sectional view of another apparatus for executing a conventional method of manufacturing a core; Fig. 9 is a partial longitudinal sectional side view of an apparatus for executing a conventional method of manufacturing a self-hardening mold; Fig. 10 is a partial longitudinal sectional side view of another apparatus for executing a conventional method of manufacturing a self-hardening mold; Examples of manufacturing a core using self-hardening molding sandEmbodiment - 1In the first embodiment shown in Fig.1, a core pattern 1 provided with a reduced-pressure suction box 3 or reduced-pressure suction means for core hardening is installed on a vibrating table of a three-dimensional jolt molding machine 6. After self-hardening molding sand 2 mixed at a separate location is added into the core pattern 1 in an appropriate quantity (such as 1/2 of the total sand quantity), the three-dimensional jolt molding machine 6 is actuated and jolts are applied in three mutually perpendicular directions, i.e., X-axis, Y-axis and Z-axis, so as to fill the self-hardening molding sand 2 in the core pattern. The three-dimensional jolt molding machine 6 is then stopped, and an appropriate quantity (for example, 1/4 of the total sand quantity) of molding sand is charged in the core pattern, and the three-dimensional jolt molding machine 6 is re-actuated. The remaining quantity portion (for example, 1/4) of the self-hardening molding sand 2 is then charged in the core pattern 1, and jolt filling is performed again. Immediately after core molding is completed, a reduced-pressure suction unit 8 is operated for several minutes, and the core is sucked via a suction pipe 7 and the reduced-pressure suction box 3 so as to cause an air flow in the mold, thereby to remove by dehydration the moisture in the self-hardening molding sand 2 and the moisture generated when a caking agent reacts chemically, thus promoting hardening. Next, the particular operation of the present embodiment will be described. The shaking forces (frequencies) along the X-, Y- and Z-axes of the three-dimensional jolt molding machine 6 were set at 50 hertz, respectively, a core pattern 1 having a core weight of 30 Kg was installed on the vibrating table, 1/2 of the total sand quantity of the furan molding sand 2 was charged in the core pattern 1, and jolting was applied for 10 seconds. Then 1/4 of the total sand quantity of the furan molding sand 2 was charged in the core pattern 1 and jolted for 20 seconds, and a little over 1/4 of the total sand quantity of the furan molding sand 2 was charged further in the core pattern 1 and jolted for 30 seconds. After the core pattern was completed, the reduced-pressure suction unit 8 was actuated (for 5 minutes) so as to harden the core by speeding up air flow in the mold by sucking the core. As to the ejected core, even a projected core print approximately 100 mm long was filled completely, and a good core which had been hardened up to the central part uniformly was obtainable. Table 1 shows hardening characteristics when air flow rate in the mold was accelerated for hardening by sucking the furan self-hardening sand. Hardening Characteristics by Suction of Furan Self-Hardening Sand Resin Hardening agent Suction Proof pressure Type % Type % after 0.5 Hr after 1 Hr after 24 Hr 340B1C-1440no02.837.5 340B1C-1440yes3.99.440.8 340B1TK-340no5.211.836.0 340B1TK-340yes13.628.239.5 Note) Tested sand: Kaketsu Fusen No. 5 Ambient temperature: 28°C Humidity: 90% RH Behavior of hardening: Uniform hardening to the depth Embodiment - 2Fig. 2 shows a second embodiment. A core pattern 1 provided with intercommunicating pores 4 for reduced-pressure suction at portions A1, A2, ..., A6 where self-hardening molding sand 2 could not be filled in recessed portions of the core pattern 1 was installed on a three-dimensional jolt molding machine 6, the furan molding sand 2 was charged in the core pattern 1 while actuating a reduced-pressure suction unit 8, and the three-dimensional jolt molding machine 6 provided jolt for about 60 seconds keeping pace with the above, thus manufacturing the core. As the result of executing hardening by suction thereafter in a similar manner as the first embodiment, a good core was obtainable. Embodiment - 3Referring to Fig.3, after a core pattern 1 provided with holes 5 for sand replenishment each 15 mm square at recessed portions A1, A2, A4 and A5 of the core pattern 1 was installed on a three-dimensional jolt molding machine 6, 1/2 of the total sand quantity of furan molding sand 2 was charged in the core pattern 1 and jolted for about 20 seconds. Then, the furan molding sand was charged in a supplemental manner through an upper part and holes 5 for sand replenishment of the core pattern 1 with jolt by the three-dimensional jolt molding machine 6 and was jolted for about 40 seconds. As the result of actuating a reduced-pressure suction unit 8 so as to promote hardening by suction after molding of the core was completed, a good core was obtainable. Embodiment - 4Fig. 4 shows a fourth embodiment in which a core is hardened by sucking under reduced pressure from an upper part of a core pattern. A core pattern 1 provided with intercommunicating pores 4 for reduced-pressure suction and holes 5 for sand replenishment (omitted depending on the configuration of the core) is installed on a vibrating table of a three-dimensional jolt molding machine 6. A core is molded by shaking with the three-dimensional jolt molding machine 6 while charging self-hardening molding sand 2 mixed at a separate location in the core pattern 1 in parts by appropriate quantities. As the result of operating a reduced-pressure suction unit not shown for several minutes after molding of the core was completed, accelerating air flow in the mold by sucking the core through a suction pipe 7 provided at the upper part of the core pattern 1, removing the moisture in the self-hardening molding sand 2 and the moisture generated at time of chemical reaction, and promoting hardening, the ejection period of the core could be reduced by half as compared with a conventional self-hardening method, and uniform hardening up to the depth of the core was realized. Reference number 10 denotes a clamp in Fig.4. Embodiment - 5Fig. 5 shows a fifth embodiment in which hardening is made by sucking under reduced pressure from a side of a core pattern. The adding method and the shaking point of self-hardening molding sand 2 are similar to those in the fourth embodiment. Suction under reduced pressure was performed through the side portion of the core pattern 1, but satisfactory results similar to the fourth embodiment were obtainable in points of ejection period and hardened state. Examples of manufacturing a mold using self-hardening molding sandFig. 6 shows an apparatus suitable for working of a method of manufacturing a self-hardening mold of the present invention. Fig. 6 is a partial longitudinal sectional side view, in which 11 denotes a pattern, 12 denotes a flask and 13 denotes self-hardening molding sand, in which normal temperature self-hardening furan resin as a caking agent of the molding sand of a sandmold casting and a hardening agent are mixed. 14 denotes a vibrating table of a three-dimensional jolt molding machine, 15 denotes air springs, 16 denotes shakers, and 17 denotes a roller conveyor which conveys a surface plate 24 on which a flask 12 is placed. 18 denotes a vertical working cylinder, 19 denotes a surface plate for suction under reduced pressure, 20 denotes a suction pipe and 21 denotes a control board of a pressure reducing unit. A method of manufacturing a self-hardening mold of the present invention using the apparatus of Fig.6 will now be described. Embodiment - 6A flask 12 placed on the surface plate 24 of Fig.6 was placed on the vibrating table 14 of the conventional two-dimensional jolt molding machine shown in Fig. 16, a pattern 11 was placed in the flask 12, furan self-hardening molding sand 13 was charged in a void portion formed by the pattern 11 and the flask 12, and the shakers 16 of the two-dimensional jolt molding machine were actuated thereby to fill the molding sand 13. Then, this assembly was conveyed into a pressure reducing unit shown in Fig. 6, and was brought into a close contact with the upper surface of the flask 12 by lowering the surface plate 19 for reduced-pressure suction provided with a reduced-pressure suction mechanism by means of a vertical working cylinder 18. Thereafter, a pressure reducing pump (not shown) was operated for five minutes and the pressure inside the flask 12 was reduced down to 200 mmHg through suction pipes 20. After approximately 30 minutes had elapsed, the mold was ejected and the hardening state thereof was investigated. As a result, it was found that the ejection period could be reduced by half as compared with that in which no pressure reduction was made, and a good mold which was hardened uniformly up to the depth of the mold and had no deformation was also obtainable. Embodiment - 7A flask 12 is placed via the surface plate 24 on the vibrating table 14 of the three-dimensional jolt molding machine shown in Fig. 6 and a pattern 11 to which a riser wood pattern 23 is fitted is installed therein. After charging an appropriate quantity (for example, 3/4 of the total sand quantity) of furan self-hardening molding sand 13 mixed by a sand mixer in a void portion formed by the pattern 11 and the flask 12, the shakers 16 of the three-dimensional jolt molding machine were actuated, jolt in three directions of X-axis, Y-axis and Z-axis was applied, and the furan self-hardening molding sand 13 was charged in the flask 12. Then, an appropriate quantity (for example, 1/4 of the total sand quantity) of furan self-hardening molding sand 13 was charged in the flask 12, and jolt filling was performed. After molding of the mold was completed, the mold was conveyed into the pressure reducing unit through the roller conveyor 17. Next, a surface plate 19 for reduced-pressure suction provided with a reduced-pressure suction mechanism was lowered by a vertical working cylinder 18 so as to be brought into close contact with the upper surface of the flask 12, a pressure reducing pump not shown was actuated for several minutes (for example, about 5 minutes) so as to reduce the pressure in the flask 12 (for example, 150 mmHg to 250 mmHg) through a suction pipe 20, and the moisture contained in the furan self-hardening molding sand 13 and the moisture generated at time of chemical reaction between furan resin which is a caking agent mixed with the molding sand and a hardening agent were evaporated thereby to be removed by dehydration through the suction pipe 20. Furthermore, the mold ejected after being left as it was for about 30 minutes showed a good mold having no deformation, and the hardening period was not only reduced by half, but also the filling density was high, and which was hardened uniformly up to the central part thereof, as compared with a conventional mold left as it was with no pressure reduction. Table 2 shows reduced-pressure suction hardening characteristics of the furan self-hardening molding sand. Reduced-Pressure Suction Hardening Characteristics of Furan Self-Hardening Molding Sand Resin Hardening agent Reduced-pressure Tensile strength (kg/cm2) Type wt% Type wt% after 30 m. 1 Hr 24 Hr 340B1.0C-1440no02.837.5 340B1.0C-1440yes3.99.440.8 340B1.0TK-340no5.211.836.0 340B1.0TK-340yes13.628.239.5 Note) Wt% of hardening agent is shown with a ratio to resin. Tested sand: Kaketsu Fusen No. 5 Ambient temperature: 28°C Humidity: 90% RH Degree of pressure reduction: -150 mmHg Behavior of hardening: Uniform hardening to the depth of the mold (in case of reduced-pressure hardening)	A method of manufacturing a cast core, comprising introducing self-hardening sand into a hollow core pattern, subjecting the core pattern and the self-hardening sand therein to three-dimensional jolting whereby to promote complete filling of the hollow core pattern with said sand, and removing air and moisture from the core pattern, and hence from said sand, by means of a suction apparatus to promote the hardening of the core. A method of manufacturing a core according to claim 1, wherein small holes communicating with said suction apparatus are provided at corner portions within the core pattern so as to facilitate filling the molding sand within said corner portions. A method of manufacturing a core according to claim 1, wherein holes for sand replenishment are provided at recessed portions of the core pattern where it is difficult to fill the molding sand so as to facilitate filling the molding within said recessed portions. A method of manufacturing a core according to claim 3, wherein small holes communicating with said suction apparatus are provided at corner portions within the core pattern so as to facilitate filling the molding sand within said corner portions. A method of manufacturing a cast mold, comprising introducing self-hardening sand into a hollow casting frame, subjecting the casting frame and self hardening sand therein to three-dimensional jolting whereby to promote filling of the hollow casting frame with said sand, and reducing the air pressure in the casting frame whereby to assist in removing moisture from the sand, generated during the hardening reaction, and to thereby promote the hardening of the casting mold.	KAO QUAKER CO; MITSUBISHI HEAVY IND LTD; KAO QUAKER CO., LTD.; MITSUBISHI JUKOGYO KABUSHIKI KAISHA	HIRAMA YASUYOSHI; KOSHIISHI KUNIO; MATSUURA HIROSHI; NAGAI KIYOTAKA; OGAWA KYOZABURO; OHATA MASAAKI; SANO HIROAKI; YASUKUNI TAKASHI; HIRAMA, YASUYOSHI; KOSHIISHI, KUNIO; MATSUURA, HIROSHI; NAGAI, KIYOTAKA; OGAWA, KYOZABURO; OHATA, MASAAKI; SANO, HIROAKI; YASUKUNI, TAKASHI
EP-0489510-B1	489,510	EP	B1	EN	19,970,402	1,992	20,100,220	new	G01R31	H04L25	G01R31	S06F201:280, G01R 31/319S3	Active distributed programmable line termination for in-circuit automatic test receivers	A system (210) for providing receiver termination in automatic test equipment (ATE) wherein the automatic test equipment (ATE) is capable of testing a plurality of devices under test (DUT). The automatic test equipment has a plurality of receivers (40) each of which is connected to the receiver termination system (210) of the present invention. The system (210) selectively connects each receiver termination to one of a plurality of devices under test (DUT). Each of the receiver terminations is connected between one of the automatic test equipment receivers and the analog multiplexor (MUX) and provides a high reference voltage clamping value for clamping signals appearing on the input to the receiver at the high reference value tailored for the specific device under test (DUT). It also provides a low reference voltage for clamping signals appearing on the input of the receiver at a low reference voltage value tailored to the device under test (DUT). An analog reference control (310) is connected to each of the plurality of receiver terminations (300) and delivers to each receiver termination high and low reference voltage clamping values tailored for each device under test (DUT) connected to the receiver termination. A state machine (330) controls the delivery of the high and low reference clamping voltage values to the receiver terminations.	BACKGROUND OF THE INVENTION1. Field of the Invention -The present invention relates to termination of transmission lines and, in particular, the present invention relates to receiver termination of devices-under-test (DUTS) in automatic testing equipment (ATE). 2. Statement of the Problem -The termination of transmission lines represents an area of signal analysis that has been well studied. See, for example, Javid and Brenner, Analysis Transmission and Filtering of Signals, Transmission Lines 1-Transients , Pages 334-347, 1981 (Robert E. Krieger Publishing Co., Inc., Malabar, FL). The goal of ATE systems is to provide a test interface to a large number of different types of DUTs. The ATE system applies a stimulus to the DUT and then looks for an appropriate signal response. For digital DUTs, the ATE system drivers drive the correct logic levels for a valid 1 or 0 to the inputs of the DUT and then the digital receivers in the ATE system look for a valid 1 or 0 at the outputs. In Figure 1a, a typical device-under-test (DUT) interconnected through a fixture and a printed circuit (PC) board 20 with an automatic test equipment (ATE) system 30 containing a receiver 40 and a driver 60. Receiver 40 in an ATE system (generally indicated at 30) probes the DUT 10 in order to determine the function of the circuit without interfering with the operation of the circuit. This normally implies keeping the input 50 to the receiver at a high impedance. However, the connection of the receiver 40 to the DUT 10 adds some parasitic capacitance Cp to ground thereby partially affecting the operation of the DUT. An optional three state driver 60, shown in dotted lines, may be selectively interconnected by means of a switch 70 to the input 50 to drive a signal into the DUT. The ATE system 30 contains a number of receivers 40 and drivers 60 and will be discussed more fully with respect to Figure 2. In Figure 1a, when the receiver 40 input impedance is high compared to the impedance Z0 of the fixture in PC board 20 and the source output resistance Rs is low (compared to Z0) then the waveform from the DUT at the receiver input 50 will overshoot. This results in a classic ringing problem. If Rs is small, a larger voltage (hence, more current) will be delivered down the transmission line by the DUT. In other words, the waveform at the receiver 40 overshoots the source voltage Vs from the DUT and then undershoots below Vs. The amount of current initially sent down the line is determined by the instantaneous impedance seen at the Rs - Zo interface. As the waveform travels down the transmission line it then encounters the Zo - input 50 of receiver 40 interface. The receiver 40 typically is of much higher impedance than Zo thereby causing the voltage waveform to overshoot. (Note: The initial voltage sent down the line is VsZoRs+Zo when Rs is small, a good approximation for many of these high speed DUTs.) Eventually, the ringing damps down to a steady state value of Vs. In an ATE system, one of the problems is to design the receiver 40 such that it is capable of interfacing with many different DUTs having varying output impedances in a fashion to minimize the ringing problem. Hence, a low cost, easy to implement design for receiver 40 is needed. The problem of ringing is further enhanced when short wire length PC fixtures 20 are required because of the high speed of the digital circuits found in the DUTs (i.e., this assumes a lossy transmission line). Hence, a need also exists in the design of a receiver 40 that provides minimum impact on the DUT 10 (that is, having no DC loading and no degradation of AC performance) but which is inexpensive and easy to implement. There are several ways to conventionally terminate a receiver 40 for ATE equipment and these are illustrated in Figures 1b through 1d. In Figure 1b, a resistive load RL is connected from input 50 of the receiver 40 to ground. The resistor RL equals Z0. This particular termination works well provided the DUT can output a sufficient amount of current (I = Vs ÷ (RL + Rs + Rdc)) and provided Rs is small compared to RL + Z0. Rdc is the lumped resistance of the transmission line. Furthermore, there is no mismatch or reflection at the receiver input 50 since RL = Z0. One disadvantage of the prior approach of Figure 1b is that the DUT 10 must be able to supply the aforesaid value of current to the transmission line 20 when driving high. Many DUTs 10 cannot supply that amount of current. In Figure 1c, a second prior art solution for terminating a receiver 40 in an ATE system 30 is shown. A resistor RL which is equal to Z0 is terminated on the variable drive 60. A second resistance RA is added at the output 80 of the DUT 10. The addition of resistor RA further isolates the DUT 10 from the ATE system 30. But the addition of resistor RA also means that the parasitic capacitance CpDUT becomes more important. If a correct value of RA can be found, the DUT 10 can be adequately isolated from the ATE 30. The problems with the prior art approach shown in Figure 1c are substantial. For some DUTs 10 there is no good value for RA. The presence of parasitic capacitance CpDUT can potentially limit the speed of the ATE in conducting the test. Furthermore, driver 60 now must drive through both RL and RA which may be a problem when overdriving (a lot of current may be required). Overdriving occurs when the driver 60 drives a node to a known state regardless of where an enabled upstream device may wish to drive the node. Finally, the implementation of Figure 1c requires RA to be physically close to the DUT 10 which involves fixturing problems. In Figure 1d, the most common technique which is frequently used in industry is set forth. Here, a resistor RL is connected in a series connection to a capacitor CL which connects the input 50 of receiver 40 to ground. Capacitor CL isolates the resistor RL from ground. Hence, the resistor RL does not DC load the DUT 10 but the capacitor CL will add to the receiver input capacitance which can limit test speed. The clear advantage of the approach of Figure 1d is that the resistor RL is only present in the circuit when a signal transition from the DUT 10 occurs at the input 50. Termination is only present when the signal at the input 50 is changing state. Hence, no DC loading. One disadvantage with the prior art approach of Figure 1d requires that Z0 must be well controlled as inductance of the line 20 can form a tank circuit with RL and CL which would cause oscillations. Furthermore, CL will add to the receiver 40 additional parasitic capacitance and increase the effective input capacitance presented to the DUT thereby limiting the speed and performance of the DUT 10. A need therefore exists for a receiver which can be selectively programmed to a specific DUT 10 which will provide a necessary termination at the input 50 to absorb energy from ringing. The design of this circuit must not interfere with the acquisition of a valid high or low signal from a wide variety of different types of DUTs 10. Figure 2 illustrates a typical prior ATE system capable of interfacing with a number of DUTs 10. In Figure 2, the ATE system 30 includes a set of analog multiplexors (MUX0 - MUXI) (e.g., relays) wherein each multiplexor is interconnected over a fixture and PC board 20 to a plurality of DUTs 10 (DUTA - DUTN). Other prior art approaches use different techniques to connect the receivers to an individual DUT (such as changing fixtures, etc.). Hence, each receiver termination 50 can be selectively connected by the multiplexor to a discrete DUT 10 in a set of DUTs 10. A measurement can then be taken by the receiver 40 of the signal output of the connected DUT. The receiver termination 210 in Figure 2 may constitute any one of the above prior art approaches fully discussed in Figure 1. The DUTs 10 as shown in Figure 2 may be of a number of different logic families. These different logic families will have different valid logic thresholds. For example, transistor-transistor logic (TTL) has a signal threshold of 2.0 volts and complementary metal oxide semiconductor (CMOS) has a signal threshold of 4.0 volts, both for a valid digital 1. Furthermore, the output impedance of each logic family is also different. Hence, a need exists for each receiver to have active termination thresholds so as to adjust to the signal characteristics of the DUT being tested. Since many different logic families may be represented in the DUTs 10, ATEs are presently available wherein each receiver 40 has programmable thresholds on a per receiver basis (e.g., receiver high, receiver low, drive high, drive low). This capability is called per-pin programmable logic threshold in the industry. Finally, a need exists to provide distributed programmable clamps on a per-pin basis so as to provide an active termination for the receivers 40. 2. Results of a Patentability Search -A patentability search was directed in the field of the invention to the solution of the above problem. The results of the patentability search generated the following patents: Muench, Jr.3,600,6348-17-71 Andrews, Jr.3,660,6755-2-72 Dasgupta et al.3,832,5758-27-74 Davis4,450,3705-22-84 Slaughter4,943,7397-24-90 U.S. Patent 3,660,675 sets forth a design for terminating a low output impedance source by adding a series termination when the device is sinking, in a diode (no series termination) when the device is sourcing. U.S. Patent 4,450,370 sets forth an active termination for a transmission line involving a tri-state buffer enabled by a strobe signal. The output of the tri-state buffer is tied through a resistive element which is used to help match the line impedance of the transmission line. U.S. Patent 3,832,575 sets forth a data bus transmission line termination circuit which is programmable to either a low impedance state for connection to the terminal end of the data bus or to a high impedance state for connection to an intermediate portion of the data bus. U.S. Patent 3,600,634 issued to Muench, Jr. sets forth a protective control circuit against transient voltages utilizing a pair of solid state gate controlled AC switches. This patent deals with an over voltage circuit which shunts around a load for protection if an over voltage occurs. U.S. Patent 4,943,739 sets forth a non-reflecting transmission line termination which contains a reflection attenuator connected between the signal line and the ground line or signal line and the power line. The attenuator clamps the voltage of digital signals between ground potential and the supply line voltage. This invention is the most pertinent of the patents uncovered in the search to the solution of the above problem. However, this invention is not applicable to the environment of ATE systems. The signal swing of '739 must be close to Vcc or to ground and, therefore, is not appropriate for use in an ATE. The '739 patent does not deal with the situation involving different types of DUTS - where, for example, the Vcc is not always the same. Furthermore, the '739 approach requires a third line for Vcc, does not provide for high currents, and does not handle the situation where Vcc is less than ground. 3. Solution to the Problem -The present invention provides a solution to the needs set forth in Figures 1 and 2 by providing an active distributed programmable line termination for the receiver 210 which is fully programmable on a per-pin basis in an ATE system. The present invention provides a receiver termination which extracts energy from the output DUT signal only when the signal has passed a defined threshold level. Two embodiments of the present invention are set forth. In the first embodiment, the termination voltage is tied to the per-pin programmable (distributed) receiver threshold while the second embodiment allows the termination voltages to be programmed independently on a per-pin basis. Both embodiments provide per-pin programmability of the terminated voltages. Furthermore, the present invention eliminates AC loading caused when the edges of the DUT signal are going through a transition and provide only small DC loading which is present only when the signal from the DUT has exceeded the termination voltage value. SUMMARY OF THE INVENTIONA system for providing programmable active receiver termination in automatic test equipment wherein the automatic test equipment is capable of testing a plurality of devices under test is as specified in claim 1 hereinafter. The automatic test equipment has a plurality of receivers each of which is connected to the receiver termination system of the present invention. The system is preferably connected to an analog multiplexor which selectively connects each receiver termination to one of a plurality of devices under test. In one embodiment, each of the receiver terminations is connected between one of the automatic test equipment receivers and the multiplexer and provides a high reference voltage for clamping signals appearing on the input to the receiver at the high reference voltage tailored for the specific device under test. It also provides a low reference voltage for clamping signals appearing on the input of the receiver at a low reference voltage clamping value tailored to the device under test. An analog reference control is connected to each of the plurality of receiver terminations and delivers to each receiver termination high and low reference voltage clamping values tailored for each device under test connected to the receiver termination. A state machine controls the delivery of the high and low reference clamping voltage values to the receiver terminations. DESCRIPTION OF THE DRAWINGFIGURE 1 are prior art representations of circuits for terminating a transmission line; FIGURE 2 is a prior art representation of a conventional ATE system; FIGURE 3 sets forth the first embodiment of the termination system of the present invention; FIGURE 4 sets forth the second embodiment of the termination system of the present invention; FIGURE 5 are graphical representations of the signals at various locations in the first embodiment of the automatic test system of the present invention; FIGURE 6 sets forth graphical representations of the signals corresponding to a different frequency than that set forth in Figure 5; and FIGURE 7 sets forth graphical representations of the signals for testing an ACT family of DUTs. DETAILED SPECIFICATION 1. First Embodiment of a Receiver Termination Block -In Figure 3, the first embodiment of a receiver termination block (RTB) 300 is shown interconnected with an analog reference control 310. The analog reference control 310 is interconnected with a number of receiver termination blocks. With reference back to Figure 2, if there are i receiver terminations, then the analog reference control 310 would interface with i receiver termination blocks 300. This is shown in Figure 3 for RTBi. The analog reference control 310 outputs termination voltages as distributed per-pin programmable receiver thresholds, RHI and RLO. However, as shown in Figure 3, the termination voltages can also be tied to set reference levels, CHI and CLO. Whether programmable receiver thresholds RHI and RLO or set reference levels CHI and CLO are utilized, is dependent upon the settings of switches 320a and 320b. The CHI and CLO signals are provided for those DUTs 10 which do not ring and which cannot drive small dc loads in the termination. Hence, CHI and CLO are outside the programming range of the receiver thresholds (i.e., CHI > RHIMAX and CLO < RLOMIN). a. Analog Reference Control 310The analog reference control 310 incorporates a state machine 330, a digital to analog converter 340, an amplifier 350, and an integrated sample-and-hold circuit 360. The state machine 330 is interconnected over lines 332 to the digital to analog converter 340 which in turn is connected over lines 342 to the amplifier 350. Amplifier 350 in turn is connected over line 352 to the integrated sample-and-hold circuit 360. Address and enable information is delivered over lines 334 to the integrated sample-and-hold circuit 360. The integrated sample-and-hold circuit delivers the RLO and RHI threshold levels to the receiver termination blocks (RTBo - RTBi). As will be evident in the following, the analog reference control 310 provides per-pin voltages (RHI and RLO) which are used as references by the receiver termination blocks to individually configure the receiver termination block to test a particular DUT 10 so as to minimize ringing. Each different DUT type will have its own RHI and RLO reference voltages. Each analog reference voltage is separately programmable within a valid output range which in the preferred embodiment is negative 5.5 volts to positive 5.5 volts. The valid range of receiver levels is negative 3.5 volts to positive 5.0 volts. The state machine 330 cycles through all possible addresses so as to refresh each sample-and-hold 360 which in the preferred embodiment is every five microseconds with an actual switch 362 closure time of 1.6 microseconds. The address and enable information is delivered over lines 334 to the address decoder and switch select 364 which activates switches over lines 366. The state machine 330 is implemented on an ASIC which incorporates a random access memory (RAM), not shown. The state machine 330 conventionally operates to cycle through each address of the sample-and-hold circuit 360 which in the preferred embodiment constitutes 48 separate addresses. For each address, the state machine further provides data to the digital-to-analog converter 340. This data is delivered from the RAM lines 332, this data constitutes the necessary digital information to provide the analog threshold voltage signals amplified by amplifier 350 on lines 352. The state machine 330 also provides the address for the sample-and-hold circuit 360 on lines 334 and an enable signal also on lines 334 that closes the addressed switch 362 from the analog line 352 to the addressed hold capacitor 368. Hence, an address is delivered out from the state machine 330 on lines 334 to the address decoder and switch select 364. Simultaneously an output from the RAM internal to the state machine 330 is delivered on lines 332 to the digital-to-analog converter 340 which delivers the analog threshold value to the integrated sample-and-hold circuit 360. After the appropriate address setup time on 334 and analog voltage setting time (on 352), the switch 362 becomes activated and the analog value appearing on line 352 is delivered into a holding capacitor 368 for subsequent delivery as RHI or RLO to the addressed receiver termination block 300. In the preferred embodiment, 3.2 microseconds are provided for the voltage to become stable on line 352 before the enable signal on line 334 loads the value into the holding capacitor 368. The enable signal stays active for 1.6 microseconds allowing the hold capacitor 368 to be charged to the correct threshold value. An additional 200 nanoseconds of hold time is then encountered after the enable becomes inactive and then the state machine provides the address and data for the next hold capacitor. The digital-to-analog converter 340 and the amplifier 350 operate as follows. The digital-to-analog converter 340 is of the type that provides a current output. The digital-to-analog converter 340 converts the data being inputted on lines 332 from the state machine 330. In the preferred embodiment, the digital-to-analog converter 340 utilizes a twelve digital bit input running off of a ten volt reference. The output of the digital-to-analog converter 340 feeds two operational amplifiers 350, not shown. The first operational amplifier swings between 0 to minus ten volts depending upon the data on lines 332 and the second operational amplifier inverts the result of the first and level shifts the signal so that it runs minus 5.5 volts to plus 5.5 volts. For simplicity, only a single amplifier 350 is shown in Figure 3. The integrated sample-and-hold circuit 360 utilizes a decoder multiplexor 364 which selects one of the 48 sample-and-holds (based upon six binary bits). The enable bit from the state machine 330 closes the internal FET switch 362 from the analog input 352 from the digital-to-analog converter 340. Closure allows the internal hold capacitor 368 to be selectively charged, as discussed above. The voltage at the hold capacitor 368 is buffered from receiver termination blocks 300 with a low current unity gain operational amplifier 369. It is to be expressly understood that while a preferred design for the analog reference control is shown that other designs that selectively deliver RHI and RLO reference voltages to the receiver termination block could also be used and would fall under the teachings of the present invention. b. Receiver Termination Block 300The receiver termination block 300, as shown in Figure 3, is connected to the fixture and PC board 20 at its input 50. This corresponds to the conventional prior art circuits of Figure 1. Likewise, the receiver termination block 300 is interconnected to the analog reference control 310 over lines RHIo and RLOo. Finally, the receiver termination block 300 delivers to the receiver outputs GTH and GTL from receiver 390. In the receiver termination block 300 are the analog switches 320, a high current unity gain buffer 370, and the high and low threshold comparators 380. The diode 372a is connected through resistor R1 to the output of buffer 370a. The output of buffer 370a is connected to resistor R1 and through capacitor C1 to ground. Likewise, the output of buffer 370b is connected to resistor R2 and through capacitor C2 to ground. The output of resistor R2 is also connected to the input of diode 372b. The RHI threshold signal is delivered into the high threshold comparator 380a whose output is a greater-than-high (GTH) indication. The RHI signal is also delivered through analog switch 320b into buffer 370a. Likewise, RLO is delivered into the input of the comparator 380b whose output is a greater-than-low (GTL) indication. RLO is also delivered into the input of the buffer 370b. The analog switches 320 allow the termination voltage to be tied to RHI and RLO or to CHI and CLO. CHI and CLO are voltages which will insure that the clamps can be turned off by programming the termination voltages beyond the valid programming range of RHI and RLO. The analog switches 320 are digitally controlled by the control register 322 over lines 322a and 322b. The control register 322 is selectively loaded over lines 324 by the operator of the ATE system. Switches 320 are preferably DG211-a digitally controlled FET switches. The high current unity gain buffers 370a and 370b provide a solid high current voltage source to the RTB. The buffers 370a and 370b are implemented as an operational amplifier with an external current boost transistor in the feedback loop, not shown. Resistors R1 and R2 are current limit resistors which isolate their respective capacitors C1 and C2 from their respective high current buffer amplifiers 370a and 370b and prevent excessive currents from being drawn through the circuit if RLO is greater than RHI. This is accomplished without adding an RC time constant to RIN. In the present invention, when RHI (or RLO) is changed, the capacitor C1 adjusts to the new voltage level. The isolation from the high current amplifier 370a and 370b keeps the voltage at the receiver input (RIN) from pulling around the voltage source when high speed pulses are stuffed into the termination 50. The isolation resistors R1 and R2 further protect the clamps from damage when RHI < RLO. Finally, the isolation resistors R1 and R2 will limit the DC load seen by the DUT when the clamps are on. The capacitors C1 and C2 provide charge storage and high frequency bypassing. The size of these capacitors is dictated by the necessary high frequency response (i.e., good high frequency bypassing) and settling time requirements when the termination voltages are changed. In the preferred embodiment, these capacitors have values in the range of 0.1 µF to 2.2 µF. The diodes 372a and 372b are Schottky barrier diodes in a conventionally available dual SOT-23 package. The diodes must function to turn on fast. The dual threshold receiver 390 is driven by the voltage at the receiver input (RIN). Dual threshold receiver 390 is essentially a voltage window receiver which uses the two comparators 380 to compare against a valid high threshold RHI and a valid low threshold RLO. Receiver outputs, as given by GTH and GTL determine the state of the receiver input RIN as follows: VALID HIGH:RIN > RLO implies GTL = 1, RIN > RHI implies GTH = 1 VALID LOW:RIN < RLO implies GTL = 0, RIN < RHI implies GTH = 0 WINDOW ERROR:RIN > RLO implies GTL = 1, RIN > RHI implies GTH =0 A window error is considered an error state as the input is between the valid high (RHI) and valid low (RLO) threshold: RIN < RLO implies GTL = 0 RIN > RHI implies GTH = 1 This state should never occur and is therefore undefined (this condition means RHI < RLO). Resistor R3 has two functions. First it isolates the voltage at the receiver input RIN from electrostatic discharge and overvoltage conditions and it helps limit the current when the termination is on. Hence, the output voltage from the DUT 10 appearing at 50 will be clamped to RHI + Iohmax x (R1 + R3) + 0.3 volts high and RLO - Iolmax x (R2 + R3) - 0.3 volts low. Where: RHI =valid high threshold programmed for receiver (e.g., normal TTL logic families + 2.0 volts) RLO =valid low threshold programmed for receiver (e.g., normal TTL logic families = 0.8 volts) Iohmax =maximum high-level output current supplied by DUT Iolmax =maximum low-level output current supplied by DUT The 0.3 volts in the above equations are attributable to the drop across diodes 372. While a preferred design has been provided for the receiver block termination 300 of Figure 3, it is to be expressly understood that any suitable design functioning as described above would fall under the teachings of the present invention. 2. Second Embodiment of Receiver Termination Block -In Figure 4 a second embodiment of the receiver termination block 300 of the present invention is set forth. Where possible, like components have been numbered with the same numerals as in Figure 3. The operation between the two embodiments is identical except as follows. In Figure 4, the termination voltages represented by Vcl (V clamp low) and Vch (V clamp high) are also delivered from the analog reference control 310. Hence, the second embodiment allows complete per-pin programmability of the termination voltage independent of the receiver threshold voltage. Accordingly, the state machine 330 and the integrated sample-and-hold circuit 360 are suitably expanded to allow for the delivery of four analog voltage values per receiver termination block. Hence, the second embodiment allows complete per-pin programmability of the termination voltage independent of the receiver threshold voltage. This allows additional flexibility and fine tuning at the termination voltage for optimum performance. The trade-offs in the second embodiment to provide this fine tuning results in the delivery of four rather than two reference voltages and the complexity of the analog reference control is greater and more costly. 3. Operation of the Present InventionThe following illustrates the operation of the first embodiment, but is to be understood that this could also apply to the second embodiment. In the first embodiment, the signal positions B through H are shown in Figure 3 based upon a signal outputted from the DUT 10 indicated by A in Figure 2. In Figure 5, the representations of oscilloscope pictures for testing a DUT composed of ACT (i.e., Advanced CMOS with TTL compatible inputs) parts are shown in graphs A through B. ACT devices have a full CMOS swing (0.4 to 4.8 volts) on their outputs while being compatible with TTL on their inputs (0.8 to 2.0 volts). The measurement setup for Figure 5 is as follows. A 74ACT00 is connected through a standard fixture onto an ATE PC board which contains a receiver with the termination as shown in embodiment one (see Figures 2 and 3) to reference probe points as given by A, B, C, D, E, F, G, and H. The DUT, an 74ACT00, in DIP package is driven by a Hewlett Packard 80013B pulse generator at a frequency of 7.5 MHz. The power supplies on the DUT are set to 5.0V. Since the device is of the ACT family, the receiver thresholds are programmed to RLO = 0.8V and RHI = 2.0V rather than the default CMOS levels of RLO = 0.4V. and RHI = 4.0V. Hence switches 320b and 320c are set to deliver RHI and RLO. Figure 5, graph A, shows the waveform at the DUT (refer to Figure 2 - Point A) with the clamps on. The vertical axis has a scale of 2 volts per grid, the timescale is 30 nsec/div. This is also the trigger for the oscilloscope - an HP 54110D digital oscilloscope. Graphs B1 and B2 of Figure 5 show the DUT waveform at the receiver RIN input (point B of Figure 3). B1 shows the case where the termination of the present invention is not present (i.e., ringing) while B2 shows the case where the termination is present. The ringing without termination in B1 is 1.76 volts as shown by line 504 and the ringing with termination is 0.78 volts as shown by line 506. Note that the rising edge 500 does not ring as much as the falling edge 502 between the two graphs B1 and B2. For this particular voltage swing there is a secondary effect, inherent in a protection circuit in the receiver, that absorbs some of the energy. For CMOS with lower supplies (3.3v logic) the ringing will be much greater on the rising edge (i.e., similar to what is displayed on the falling edge of graph B1). Note that the diode 372 and capacitor C are not ideal. This non-ideality shows up as a finite turn-on time which allows these fast edges to overshoot slightly the first time and ring once. Note that the peak of the ring (as shown by 506 in Figure B2) never reaches the RLO threshold of 0.8 volts. If further improvement becomes necessary a faster diode and better capacitor C can be chosen to reduce the single ring and the voltage 506. This implementation was the best cost-performance trade-off. The example of Figure 5 also represents the worst performance configuration. Changing the fixture, DUTs, PC board, and grounding to DUTs PC board also improves the performance as characterized by the ringing seen at the receiver. Figure 5, graph C shows the voltage at point C of about 0.52 volts, between diode 372b and capacitor C2 of Figure 3. This is the normal voltage at point C (the RLO termination) for a reasonable ATE test frequency of 7.5 MHz. (This voltage will move somewhat as the capacitor charges and discharges at lower frequency as displayed in Figure 6, graph C.) Figure 5, graph D shows the output at the voltage source 370b of about 0.968 volts. Notice that this point is a little noisy. This noise is from circuitry switching and impinging upon the non-ideal voltage source (i.e., AC bandwidth does not equal infinity). The trace length on the PC board through the isolation resistor and to the filter capacitor can reach upwards of fourteen inches. Such noise can be minimized by proper routing of grounds and signals. Figure 5, graph E shows the RLO voltage of 0.96 volts as programmed into the termination circuit 300. Notice that this voltage is 200 millivolts above the peak voltage seen in graph B2. Figure 5, graphs F, G, and H show similar points on the high side of the termination. Graph F is the voltage of 3.92 volts between diode 372a and capacitor C1 of Figure 3. This is the voltage that sets the point where the diode 372a will turn on. Graph G is the voltage output (2.16 volts) of the high current buffer amplifier while graph H is the RHI voltage input of 2.16 volts to the buffer amplifier and receiver. Notice that the voltage of graph F is somewhat above the voltage of graphs G and H. This is because as the diode 372a is on more and more the capacitor tends to charge up. Therefore, at higher frequencies the termination point will tend to move away from the threshold increasing the difference in voltage between the clamp value and receiver threshold voltage. This implies that there is more noise margin and the DUT is more lightly loaded. The voltages shown in Figure 5, graph C acts the same way - only the magnitude is smaller. Figure 5 illustrates the operation of the present invention of Figure 3. The valid high and low thresholds of RHI = 2.0 volts and RLO = 0.8 volts are delivered to the termination block 300 by the analog reference control 310. These values correspond to the specified values of TTL. Hence, receiver 390 uses these values in comparators 380 to generate the GTH and GTL signals (i.e., when the voltage at B exceeds RHI = 2.0 volts it is a valid high). However, the rising edges of the digital signal are clamped at a predetermined high voltage value (based on RHI, which, for example in Figure 5, Graph F is 3.92 volts) to minimize ringing. Likewise, the falling edges of the digital signal are clamped at a predetermined low voltage value (based on RLO, which, for example in Figure 5, Graph C is 0.52 volts). The digital signal between these clamping values is not affected. The graphs of Figure 6 use the same measurement setup as Figure 5 (voltage is 2 volts per division with a time base of 50 microseconds/division). The only difference is the frequency at which the DUT is switching - now only 4.5 KHz - rather slow for an ATE but certainly possible for some cases. Graph A is again the DUT waveform as shown at point A of Figure 2. Graph B, of Figure 6, shows the DUT waveform at point B, the receiver input - RIN. Notice at this lower frequency the lessening of the load on the DUT as the capacitor charges (most noticeable on the positive going pulse). Graphs C and F of Figure 6 shows the capacitor C charging and discharging. Charging takes place through the diodes 372 respectively. Discharging takes place through resistors R2 and R1. There is no adverse affects on the termination circuit or the receiver input, RIN, at startup or low frequency operation. Figure 7 shows a blowup of the ringing at the receiver input (voltage is 2 volts per division and the time base is 10 nsec/division). The top signal of Figures 7a-7d shows the DUT waveform at A on Figure 2 while the bottom waveform shows the waveform at part B of Figure 3. Figures 7a and 7b illustrate the rising and falling edges of an 74ACT00 (same setup/measurement technique as used in Figures 5 and 6) with the termination turned off (programmed to CHI and CLO) Figures 7c and 7d are the equivalent waveforms with the termination turned on. Notice the difference in the bottom waveforms B of 7a and 7c. There is distinctly less overshoot and lessening in the DC level achieved by the part. Likewise, the bottom waveforms of 7b and 7d can be compared. Here a dramatic decrease in ringing can be observed. Finally, note the top waveforms of the pairs 7a and 7c, 7b and 7d are not affected by the presence or absence of the termination. This implies that the DUT is fully capable of driving the small load presented by the termination. It is to be expressly understood that the claimed invention is not to be limited to the description of the preferred embodiment but encompasses other modifications and alterations within the scope of the claims.	A system (210) for providing active receiver termination in automatic test equipment (ATE), said automatic test equipment (ATE) being capable of testing a plurality of devices under test (DUTS), said automatic test equipment (ATE) having a plurality of receivers (40), each of said receivers (40) being connected to said receiver termination system (210), said plurality of devices under test (DUT) being connected over individual fixture interface transmission lines (Z0) with said receiver termination system (210), said system (210) for providing receiver termination comprising: a plurality of receiver terminations (300), each of said receiver terminations being connected between one of said automatic test equipment receivers (30) and an individual device under test (DUT), an analog reference control (310) connected to each of said plurality of receiver terminations (300) for delivering to each of said plurality of receiver terminations (300) programmed reference voltage clamping values for enabling each said receiver termination (300) to provide line termination for said individual device under test (DUT) connected to the aforesaid receiver termination so as to minimize ringing. A system (210) according to Claim 1 when connected to an analog switch (MUX0), and a subset (DUTA-DUTN) of said plurality of devices under test (DUT) being connected over said individual fixture interface transmission lines (Z0) with each said receiver termination system (210), each said device under test (DUT) delivering digital signals on said transmission line (Z0), said plurality of receiver terminations (300) each being connected between one of said automatic test equipment receivers (30) and said analog switch (MUX0), said analog reference control (310) being connected to each of said plurality of receiver terminations (300) for delivering to each of said plurality of receiver terminations (300) programmed high and low reference voltage values for enabling each said receiver termination (300) to provide proper line termination by clamping said digital signals above said high reference voltage and below said low reference voltage for the individual device under test (DUT) connected by said analog switch (MUX0) to the aforesaid receiver termination (300). A system (210) according to Claim 2 wherein said analog reference control (310) comprises: a state machine (330) , said state machine (330) containing said plurality of said high and low reference voltage clamping values corresponding to the different logic-family types of said devices under test (DUT), means (340) receptive of each said high and low reference digital voltage clamping value for converting each of the aforesaid values into a corresponding high and low analog reference voltage clamping value. A system (210) according to Claim 2 wherein each of said plurality of receiver terminations (300) comprise: first means (310a, 370a, R1, C1, 372a) receptive of said high reference voltage value for clamping signals appearing on the input to said receiver (300) at said high analog reference voltage clamping value, second means (320c, 370b, R2, C2, 372b) receptive of said low reference voltage value for clamping signals appearing on the input to said receiver (300) at said low analog reference voltage clamping value. A system (210) according to Claim 4 wherein each of said first and second clamping means (310a, 320c, 370a, 370b, R1, R2, C1, C2, 372a, 372b) comprises: an amplifier (370) for receiving said high or low reference voltage clamping value, a resistor (R1, R2) having one end connected to the output of said amplifier, a capacitor (C1, C2) connecting ground to the other end of said resistor, a diode (372) having its anode connected to said other end of said resistor and having its cathode connected to said input of said receiver. A method for providing active termination (210) for a transmission line (Z0) carrying digital signals from a device (DUT) connected at one end of said transmission line (Z0), said method comprising the steps of: clamping the rising edge of each of the digital signals from the device (DUT) at the termination (RIN) to a predetermined high voltage value, when the voltage of the rising edge exceeds the predetermined high voltage the aforesaid step of clamping directs the current in the digital signal away from said transmission line (Z0) to minimize ringing on the transmission line (Z0), and clamping the falling edges of each of said digital signals from the device (DUT) to a predetermined low voltage value, when the voltage of said falling edge of the digital signal exceeds the predetermined low voltage the aforesaid step of clamping directs the current from the digital signal away from the transmission line (Z0) to minimize ringing on the transmission line (Z0).	HEWLETT PACKARD CO; HEWLETT-PACKARD COMPANY	ALCORN BARRY A; ALCORN, BARRY A.
EP-0489511-B1	489,511	EP	B1	EN	19,960,228	1,992	20,100,220	new	G06F11	G06F11	G01R31	G01R 31/3185S7, G01R 31/3185S5	Method and apparatus for diagnosing failures during boundary-scan tests	An apparatus for diagnosing faults in a device (16, see Fig. 3) equipped with boundary-scan test capability includes means (including microprocessor 22, state capture RAM 26, 28, vector formatters 30A-30F, and driver/receiver hybrids 32A-32F, 34A-34F) whereby a boundary-scan tester can store serial test data upon detection of a fault in a device under test (DUT). The test data corresponding to the frame vector associated with the fault is formatted so that all information from the parallel tester inputs and the TAP scan registers can be simultaneously analyzed. A method for diagnosing faults is also disclosed.	Field of the InventionThe present invention relates generally to methods and apparatuses for performing in-circuit testing of digital components. More particularly, the invention is related to a method and apparatus for diagnosing faults in a device having boundary-scan test capability. Background of the InventionIn-circuit testing is used to test integrated circuit devices to ensure, among other things, that the various components of a particular device under test (DUT) are properly interconnected. In addition, in-circuit testing techniques are used to ensure that the various integrated circuit devices mounted together on a common circuit board are properly interconnected. The primary advantage of in-circuit testing is that the DUT can be tested without physically disconnecting it from its surrounding circuitry. This translates into significant savings in both time and cost. The Institute of Electrical and Electronic Engineers (IEEE) boundary-scan standard specifies test logic that can be incorporated into an integrated circuit device to provide standardized approaches to testing the device using in-circuit testing techniques. See IEEE standard 1149.1. This standard is fully described in the document entitled IEEE Standard Test Access Port and Boundary-Scan Architecture, published by the IEEE. The boundary-scan technique involves the inclusion of a shift-register stage (contained in a boundary-scan cell) adjacent to each component pin so that signals at component boundaries can be controlled and observed using scan testing principles. Figure 1 illustrates an exemplary implementation for a boundary-scan cell 10 that could be used for an input or output terminal of an integrated circuit. Depending upon the control signals M and S/L , applied to the multiplexers 12A, 12B, data can either be loaded into the scan register from the SI port, or driven from the register through the SO port of the cell into the core integrated circuit of the component. The operation of this boundary-scan cell is more fully described in the above-referenced IEEE standard document. Figure 2 illustrates how a number of boundary-scan cells 10A, 10B, 10C, etc., may be interconnected to each other and to a core integrated circuit 18, to form a boundary-scan device 16, i.e., a device equipped with boundary-scan test capability, as defined by the above-referenced IEEE standard. As shown in Figure 2, the boundary-scan cells for the pins of a component 16 are interconnected so as to form a shift-register chain around the border of the integrated circuit 18, and this chain is provided with serial input and output connections TDI , TDO and appropriate clock and control signals (not shown). To allow the components to be tested, the boundary-scan register can be used as a means of isolating on-chip system logic from stimuli received from surrounding components while an internal self-test is performed. Alternatively, if the boundary-scan register is suitably designed, it can permit a limited slow-speed status test of the on-chip system logic since it allows delivery of test data to the component and examination of the test results. Note also that by parallel loading the cells at both the inputs and outputs of a component and shifting out the results, the boundary-scan register provides a means of observing the data flowing into the component through its input pins and a means of delivering data from the component through its output pins. This mode of operation is valuable for fault diagnosis since it permits examination of connections not normally accessible to the test system, e.g., the connection (i.e., trace) between an external input terminal 11A of the device and an input 18A to the core integrated circuit 18. The precise sequence of signals that needs to be input to these TAP (Test Access Port) inputs is unimportant as far as the present invention is concerned. It is important to note, however, that during various types of testing it is often necessary to drive and receive data to/from both the parallel inputs to these shift registers and to/from the TDI/TDO terminals. For example, as alluded to above, this is necessary during an important test called a connect test, i.e., a verification that all of the internal input and output terminals of the chip are properly connected to the board. In order to perform the connect test, certain signals must be presented to the board nets via test drivers, certain signals must be received from the board via test receivers, certain signals must be driven to TDI and the various control ports of the scan cells 10A, 10B, etc., from test drivers, and certain signals must be received via TDO by the test receivers. A problem with this testing procedure is that data from all of the test receivers is strobed in at the same time. This parallel input is called an input vector and it represents a sample of activity from some group of board nets at a particular point in time. Now, in order to detect and diagnose a fault in the device, it is necessary to analyze all of the date from a given point in time at once. If a failure is detected at some point, the test is halted and the failure analysis printed. However, in the case of a boundary scan device, while the parallel data inputs to a device may all be sampled at the same time as the parallel tester inputs (i.e. the data outputs of the device), the input data to the core integrated circuit 18, sampled by the scan cells, is not available to the tester until additional control vectors have been input to the TAP to shift out this information. Therefore, if a fault is detected at some tester input, the information necessary for a complete fault analysis is not available at that time. The data captured by the respective scan cells must be clocked out and this serialized data lined up with the appropriate parallel data taken from the tester inputs. This is difficult to do with known test receivers since they are not designed to store serial data. Accordingly, the object of the present invention is to provide a method and apparatus by which a test comparator (receiver) can be connected to a storage device and this data then re-formatted so that all information from both the parallel tester inputs and the boundary-scan cells may be simultaneously analyzed to isolate faults in the DUT. Summary of the InventionThe present invention provides a boundary-scan tester for diagnosing faults in a DUT having boundary-scan test capability. An embodiment of the invention includes a driver/receiver head for driving the input terminals of the DUT with a parallel input vector and receiving a corresponding parallel output vector from the output terminals of the DUT. Further, the tester includes means for comparing the received output vector with its expected value and providing a failure signal when the actual vector is not equal to the expected vector. A sequence controller, comparing means, receives the failure signal and in response thereto transmits control signals to the DUT via the driver/receiver head. The control signals cause actual data captured by boundary-scan cells associated with the respective input and output terminals of the DUT to be serially shifted out to the driver/receiver. A state capture RAM, coupled to the driver/receiver, stores the input/output vectors and serial boundary-scan cell data. The stored data is thereby made available for analysis to isolate the fault. In a most preferred embodiment of the invention, the tester further includes means for driving input terminals of the DUT with a series of parallel input vectors and, upon detection of a fault, computing a vector number identifying the particular input and output vectors present on the terminals of the DUT at the time the fault was detected. In addition, a most preferred embodiment further includes means for repeating a boundary-scan test, upon the detection of a fault, up to the same input vector present at the time the fault was detected, and means for providing the comparing means with the expected output vector. An alternative embodiment of the invention provides a method, which can be carried out by the above apparatuses, for diagnosing a fault in a DUT having boundary-scan test capability. This method comprises the steps of driving input terminals of the DUT with a sequence of vector frames and receiving output data from output terminals of the DUT, comparing the output data with expected output data and determining whether a fault exists, and, if a fault is detected, storing portions of the input and/or output data and performing the following steps: repeating the test up to the end of the vector frame by which the fault was detected, storing portions of the output data from that frame, and analyzing the stored input and output data to isolate the fault. The preferred embodiment includes additional steps, which are described below. Brief Description of the DrawingsFigure 1 is a block diagram of a known boundary-scan cell. Figure 2 is a block diagram of a known device having boundary-scan test capability. Figure 3 is a block diagram of a boundary-scan tester in accordance with the present invention. Figure 4 is a flowchart of a method of diagnosing faults in a device under test having boundary-scan test capability, in accordance with the present invention. Detailed Description of the Preferred Embodiments Preferred embodiments of the invention will now be described with reference to Figures 3 and 4, wherein like numerals represent like elements or steps. Referring now to Figure 3, a boundary-scan tester 20 for diagnosing faults in a device under test (DUT) 16 comprises a microcomputer controller coupled with memory elements and program code, together composing the sequence controller 22 illustrated in the drawing. The sequence controller 22 is programmed to output a series of vector addresses to a group of test head drivers and receivers, each of which comprises a vector formatter 30A through 30F, an associated driver 32A through 32F, and an associated receiver 34A through 34F. (Note that the number of test head drivers in the group will vary in accordance with the number of DUT input/output terminals to be tested.) In addition, a vector counter register 24 is provided. The vector counter may be preloaded with an integer value from the sequence controller 22, and may thereafter be decremented to zero. Upon reaching zero, the vector counter 24 outputs a signal over line 24A. This enables the sequence controller 22 to be programmed to halt the outputting of vectors after a given number of vectors has been output, as described more fully below. Also as described more fully below, the sequence controller 22 can be programmed to provide expected data to the vector formatters 30A through 30F for performing fault detection. The vector formatters 30A, 30B, etc., include means for comparing vectors received from the output terminals 10F, 10G, 10H, 10I, 10J of the DUT, via the receivers 34A, 34B, etc., with corresponding expected vectors provided by the sequence controller, and providing a pass/fail signal, indicating when a failure is detected, to the sequence controller over the respective or-tied lines 31A through 31F. As mentioned above, the sequence controller 22 can be programmed to either halt on receiving the failure signal or to ignore it. Finally, memory denoted state capture RAM 26, 28 is controllably coupled to the vector formatters 30A, 30B, etc., via switching means 33A through 33F such that the actual data received from the DUT and corresponding expected data can be stored for later analysis. Coupling of the state capture RAM 26, 28 to the vector formatters 30A, 30B, etc., is controlled by the respective vector formatters in response to control signals from the sequence controller 22. In a preferred embodiment, data stored in the state capture RAM 26, 28 begins at address zero and continues up to the size of the RAM, after which it cycles back to address zero, overlaying previously stored data. In a most preferred embodiment, expected data is stored in a first block of memory 26, and actual data is stored in a second block of memory 28. The switching means 33A through 33F are each preferably controllable switches available from Hewlett-Packard® Company, Palo Alto, CA, as part number HP 0490-1688. Drivers 32A through 32F and receivers 34A through 34F are each preferably hybrid driver/receivers available from Hewlett-Packard® Company as part number HP 03066-66561. Vector formatters 30A through 30F are each preferably format chips available from Hewlett-Packard® Company as part number HP 1SG80076. Referring now to Figure 4, a method of diagnosing faults in a device equipped with boundary-scan test capability includes the following steps: First, a series of input vectors are presented to the input terminals of the DUT 16, step 40, and a corresponding series of output vectors is received from the output terminals, step 42. This series of I/O vectors comprises a number of frame vectors , each of which includes a combined I/O vector transmitted to and received from the DUT 16 at a particular instant of time, and a series of vectors designed to scan in to an out from the boundary-scan cells 10A, 10B, etc. This serial data is scanned in to the TDI port and out of the TDO port of the DUT and received by receiver 34F, as shown in Figure 3. Note that the boundary-scan cell information is scanned out without altering the parallel input/output vectors to/from the terminals of the DUT 16. A frame vector is therefore composed of NY+X parallel vectors, where N is the number of boundary-scan cells 10A, 10B, etc., in the DUT, Y is the number of vectors required to shift data one position in the chain of boundary-scan cells and X is the number of vectors required to cause the test access port controller to latch the parallel outputs and receive the parallel inputs. Typically, Y will be 1, but is not limited thereto. Next, for each I/O vector in the series, the received output vector is compared with an expected vector based upon the corresponding input vector, step 44. If a fault is detected, i.e., if there is a difference between either received vector and its corresponding expected value, as determined at step 46, step 48 is executed. If no fault is detected, a determination is made of whether the test is complete, step 56, and if not, the test continues with successive vectors in the series. If a fault is detected, the test is halted (i.e., the sequence controller is halted) and the I/O vector by which the fault was detected is stored in memory associated with the sequence controller , step 48. Next, the vector number corresponding to the last vector in the vector frame where the fault occurred is stored in vector counter 24, step 50. The sequence controller is then set to ignore the pass/fail signal and halt on the vector counter 24 being decremented to zero. The test sequence is repeated and all data associated with the frame vector by which the fault was detected is saved in the state capture RAM 26, 28, step 52. The stored data is then analyzed to isolate the fault, step 54. In the analysis, the state capture RAM is read and the last NY+X vectors (the data from the failing frame vector) are examined for differences between the actual and expected data. Any differences can be correlated with a fault associated with a particular boundary-scan cell, and therefore a particular position, in the DUT. Finally, it is noted that the invention is not intended to be limited to the preferred embodiments discussed above. For example, the drivers, receivers, switches, etc., described may be embodied in various devices capable of performing equivalent functions, within the context of the invention, to those described. In addition, it is not necessary that all of the data in the stored vector frames be saved, since some of the data is of no use in the fault isolation analysis. Accordingly, reference should be made to the following claims for determining the true scope of the invention.	A boundary-scan tester for diagnosing a fault in a device under test (DUT) (16) having boundary-scan cells (10A-10F) coupled to respective input/output terminals thereof, the boundary-scan tester comprising : (a) driver/receiver means (32A-32F, 34A-34F) for driving input terminals of the DUT (16) with a parallel input vector and receiving a corresponding parallel output vector from output terminals of the DUT; (b) comparing means (30A-30F, 31A-31F), coupled to said driver/receiver means (32A-32F, 34A-34F), for comparing said output vector with an expected output vector and providing a failure signal indicative of the result thereof and defining a fault; (c) control means (22), coupled to said driver/receiver means (32A-32F, 34A-34F) and said comparing means (30A-30F, 31A-31F), for receiving said failure signal and in response thereto transmitting control signals to the DUT (16) via said driver/receiver means, said control signals causing data captured by the boundary-scan cells (10A-10F) associated with the respective input and output terminals of the DUT to be serially shifted out to said driver/receiver means; and (d) storage means (26, 28), coupled to said driver/receiver means (32A-32F, 34A-34F), for storing said input and output vectors and said serial boundary-scan cell data, the stored data being analyzable to isolate the fault. The boundary-scan tester recited in claim 1, further characterized in that said control means (22) comprises computing means for driving input terminals of the DUT (16) with a series of parallel input vectors and, upon the detection of a fault as indicated by said failure signal, computing a vector number identifying the particular input and output vectors present on the terminals of the DUT at the time the fault was detected. The boundary-scan tester recited in claim 2, wherein said control means (22) further comprises means for repeating a boundary-scan test up to the last vector in the vector frame present at the time the fault was detected. The boundary-scan tester recited in claim 1, further characterized by: (e) second control means, coupled to said comparing means, for providing said comparing means with said expected output vector. The boundary-scan tester recited in claim 1, 2, 3 or 4, characterized in that: said driver/receiver means (32A-32F, 34A-34F) comprises a Hewlett Packard® part number HP 1SG80076 format chip and a Hewlett Packard® part number HP 03066-66561 driver/receiver hybrid. A method for diagnosing a fault in a device under test (DUT) (16) having boundary-scan cells (10A-10F) coupled to respective input/output terminals thereof, comprising the steps of: (a) driving input terminals of the DUT with an input vector (40) and receiving an output vector from output terminals of the DUT (42); (b) comparing said output vector with an expected output vector (44) and determining whether a fault exists in the DUT (46), and, if a fault is determined to exist, then storing said input and output vectors (48) and performing the following steps; (c) repeating the test up to the end of the vector frame by which the fault was detected and storing portions of the output data from that frame (52); and (d) analyzing the stored data to isolate the fault (54). The method recited in claim 6, further characterized by the step of storing a vector number upon detection of a fault (50), the vector number identifying the last vector in the vector frame present on the terminals of the DUT at the time the fault was detected. The method recited in claim 6, further characterized by the step of repeating the boundary-scan test, upon the detection of a fault, up to the last vector in a vector frame present at the time the fault was detected (52). The method recited in claim 6, further characterized by the step of determining the expected output vector prior to performing step (b). The method recited in claim 6 or 7, further characterized by the steps of: repeating the boundary-scan test, upon the detection of a fault, up to the last vector in a vector frame present at the time the fault was detected (52); and determining the expected output vector prior to performing step (b).	HEWLETT PACKARD CO; HEWLETT-PACKARD COMPANY	POSSE KENNETH E; POSSE, KENNETH E.
EP-0489515-B1	489,515	EP	B1	EN	19,950,920	1,992	20,100,220	new	A23G1	A23G1	A23G1	A23G 1/10, A23G 1/40, A23G 1/16	Process for the production of chocolate	A process for the production of chocolate which contains erythritol or maltitol as sweetener includes a dry conching step which is carried out at a temperature of at least 65°C preferably 65 to 100°C suitably for a period of time in the range 6 to 16 hours. The maltitol which may be used must have a purity greater than 90%, preferably greater than 95% especially about 99%.	The present invention relates to the production of chocolate, in particular to the production of sugarless chocolate having dietetic properties. The essential components of a conventional chocolate formulation are cocoa nib , ie the roasted cocoa bean with shell and germ removed, sugar and cocoa butter additional to that contained in the nib. Cocoa nib is approximately 55% cocoa butter, the balance being proteins, carbohydrates, tannins, acids etc. The cocoa butter content of the chocolate controls its setting characteristics and largely governs its cost, and while the ratio of cocoa nib to sugar determines the type of chocolate, the cocoa butter content varies according to the application. Thus, bitter sweet chocolate has a ratio of nib to sugar of 2:1 while sweet chocolate has a ratio of 1:2. Moulding chocolate may have a fat content of 32%, covering chocolate 33 to 36%, chocolate for hollow goods 38 to 40% and chocolate for covering ice-cream 50 to 60 %. The typical preparation of chocolate involves four stages. In the first stage the ingredients are mixed together in a process which also involves grinding or rubbing eg. on a multiple roll press to provide a smooth fluid paste. The ingredients may be added sequentially and in particular the cocoa butter may be added step-wise to control the viscosity of the composition. The sugar may also be pre-ground to a smaller particle size to reduce the length of time required in the grinding/rubbing of the chocolate mixture. Most chocolate, and certainly all good quality product, is subjected after mixing to the process of conching in which the chocolate mixture is subjected to mechanical working to give the chocolate a fuller and more homogeneous flavour. Other ingredients such as flavours eg vanilla and extra cocoa butter may be added at this stage if desired. A frequently added additional ingredient is lecithin or other emulsifier which improves the flow properties of the chocolate and thereby enables the mount of cocoa butter to be reduced. The third stage of the chocolate preparation is called tempering in which nuclei are provided in the liquid chocolate composition to facilitate the rapid crystallisation of its fat content on cooling. The final appearance of the chocolate, its texture and keeping properties depend upon correct tampering stage conditions. After tempering, the chocolate may finally be cast into moulds to set or may be used in an enrobing process to produce chocolate coated confectionery etc. The present invention is concerned in particular with the conching step in the process described in the preceding paragraph. The changes taking place during conching are subtle and not completely understood. What is certain is that the texture of the chocolate is improved and the flavour changed to the extent that without conching the taste of the chocolate is generally commercially unacceptable. The kneading action during the conching process and the maintenance of an elevated temperature together cause evaporation of moisture and volatile acids such as acetic acid, destroy harsh flavours and reduce astringency, probably due to modification of tannins. There are two types of conching operation called, dry conching and wet conching. In wet conching all of the cocoa butter and other ingredients such as lecithin are added early in the process to maintain the fluidity of the mass which is then mechanically worked for a prolonged time eg. 20 or 30 hours or more and at a relatively low temperature eg 40°C up to 60°C. The dry conching process on the other hand is operated for a shorter time eg up to 20 hours but at a higher temperature eg. above 60°C and usually about 80°C and in this case the extra cocoa butter and other ingredients are added towards to the end of the conching period eg. about one hour before the end of the period. The conventional chocolate composition uses sucrose as sweetener but many other sweeteners have been proposed and some have been used to provide for example dietary type chocolate for diabetics, and slimmers. One class of replacement sweetener for sucrose in chocolate is the so-called sugar alcohols in particular sorbitol, maltitol and mixtures of sugar alcohols known as hydrogenated starch hydrolysates. Sugar alcohol sweeteners, besides contributing fewer calories to the chocolate than the equivalent quantity of sucrose are also far less cariogenic. The disadvantages of using sugar alcohol sweeteners is that in general it is only possible to carry out the conching of the chocolate composition at temperatures below 55°C and for sorbitol in particular the temperature must not rise above 40°C. Thus, in the publication of the paper entitled Zuckerfreie Pralinen - Zuckerfreie Füllungen und Schokolademassen presented at the International Conference Inter-Praline 87' in June 1987 at the Zentralfachschule der Deutschen Süsswarenwirtschaft, Solingen it is reported that at temperatures above 40°C conching of chocolate containing sorbitol leads to agglomeration of the mixture and in two compositions containing maltitol and xylitol the conching is carried out at 35 to 38°C. Similarly, in chapter 4 of Developments in Sweeteners -3 entitled MALBIT and its applications in the Food Industry on page 95 the conching temperatures for chocolate compositions containing maltitol are given as 46°C. The experience of the chocolate industry is that the relatively low temperatures required for the conching of chocolate compositions containing sugar alcohol sweeteners necessitates wet conching for a very long conching time eg up to 24 hours and even then the flavour development is not as satisfactory as when a higher conching temperature is possible. We have now found however that there are two sugar alcohols which can be used as part or all of the chocolate sweetener and which permit the composition to be dry conched at an elevated temperature. These sugar alcohols are erythritol and maltitol with the proviso that the maltitol must be more than 90% pure. Erythritol is a symmetrical molecule and is therefore normally available as the meso-form. References to erythritol in the remainder of this specification and in the claims will mean the meso-form. Accordingly, the present invention is a process for the production of a chocolate composition comprising a sugar alcohol sweetener which includes a conching step and is characterised in that the conching step is dry conching carried out at a temperature above 65°C and the sugar alcohol is erythritol or maltitol in which the maltitol has a purity greater than 90%, preferably greater than 95% and especially about 99%. Preferably, the temperature of the dry conching is in the range 65 to 100°C more preferably in the range 75 to 85°C. At these temperatures the conching time is suitably up to 20 particularly up to 16, especially 6 to 16 hours. Japanese patent publication 104243 of 1990 describes the production of a chocolate of cool mouth feel by using erythritol as the sweetening agent. The temperature at which the chocolate was conched is not however given in this publication although the mixing of the ingredients is said to have taken place at 60°C. The process of the present invention uses a chocolate composition which contains erythritol or maltitol, preferably in an amount in the range 30 to 60% by weight of the composition, more preferably in the range 40 to 60% by weight, particularly in the range 45 to 55% by weight. The composition may contain 30 to 60%, preferably 30 to 50% , more preferably 35 to 45% by weight cocoa nib; and 10 to 20%, preferably 10 to 15% by weight cocoa butter in addition to the cocoa butter contained in the cocoa nib. In general, the use of erythritol or maltitol as the sweetener in the chocolate provides a product of similar appearance and organoleptic properties to an equivalent sucrose based chocolate but containing 2 to 15% by weight less cocoa butter than the latter the 2 to 15% being made up by the equivalent amount of erythritol or maltitol. Cocoa nib, cocoa butter and erythritol or maltitol are essential components of the chocolate compositions according to the present invention but there may also be present other ingredients, particularly an emulsifier such as lecithin, preferably in an amount 0.1 to 0.5% by weight, a synthetic sweetener eg. aspartame in amounts to taste eg 0.01 to 0.05% by weight and any desired flavour eg. vanilla. Before reaching the conching stage according to the invention the chocolate composition is first formed by mixing the various ingredients and may then be refined by gentle milling to reduce the crystal size of the components. The mixing of the ingredients may be effected by kneading the erythritol or maltitol, suitably in solid form, and preferably crystalline with cocoa nib and at least part of the additional cocoa butter at a temperature suitably in the range 25 to 60°C, preferably 30 to 40°C. The conching step may be carried out in equipment conventionally used for this purpose at the temperatures and for the times described earlier in this specification. Finally, the chocolate after conching is tempered to give the required viscosity and flow characteristics the preferred temperature between 25° and 35°C being similar to that used for sucrose based chocolate. Since dietetic chocolate containing sorbitol must be tempered over a low, restricted and critical temperature range (eg. 22-23°C) the use of erythritol or maltitol is advantageous since in this respect it may be used in the conventional sucrose based chocolate process without the need for modification. After tempering, the chocolate may be cast into moulds or otherwise processed depending upon the application in question. The invention will now be further illustrated by reference to the following Examples. Example 1Two compositions were prepared comprising Composition A Composition B Cocoa nib %3942 Additional cocoa butter % 13 13.5 Erythritol %47.7- Sucrose %-44.2 Lecithin %0.280.28 Vanillin %0.020.02 Aspartame %0.03All percentages are based on the weight of the final composition. The preparation of the chocolate took place as follows : 1) Mixing in both Compositions, the cocoa nib, 23% of the added cocoa butter and the erythritol/sucrose were ground and mixed together to form a homogeneous mass at a temperature of 30 to 40°C. 2) Refining Composition A from step (1) was gently milled on a five roller mill and after one pass the desired average particle size of 20 to 40 µm was achieved. Composition B required a longer residence time on the rollers and cooling water had to be fed at an increased rate to the rollers compared with Composition A. The temperature in this stage was 25° to 45 °C. 3) Conching Conching took place in a rotary concher of the Petzholdt type. Composition A was conched at 80°C for 16 hours and composition B at 60°C for 22 hours. The remaining cocoa butter and the lecithin were added to composition A after 14 hours and 15 hours respectively and to composition B after 20 and 21 hours respectively. 4) Tempering Both compositions were tempered by reducing the temperature of the conched mass to 28 to 31°C in order to induce the crystallisation of the fat in the chocolate in its stable beta-form. The products of tempering were cast into moulds and after cooling were evaluated orgoleptically by a taste panel and visually after a storage period of three months. Both products had excellent gloss, good breaking properties and mouth feel. After six months storage at ambient temperature no bloom was observed on the products. Example 2A composition was prepared comprising Cocoa nib42 % Additional cocoa butter13.5 % 99% pure crystalline maltitol44.2 % Lecithin0.28 % Vanillin0.02 % All percentages are based on the weight of the final composition. The preparation of the choclate took place as is described in Example 1. The conching temperature was 80°C and the conching time 10 hours. The second part of the additional cocoa butter was added after 8 hours of conching and the lecithin and vanillin after 9 hours of conching. The chocolate product was evaluated by a taste panel and was judged to be of good quality with good appearance and excellent mouth feel. A similarly acceptable product was obtained by using a 93% pure maltitol but when an 87.5 % pure maltitol was used the chocolate produced had a gritty mouth feel and during preparation lump formation was observed which required an increasing mixing force to eliminate. Example 3A composition was prepared comprising Cocoa nib11.4 % Additional cocoa butter23.4 % Erythritol42.5 % Whole milk powder22.4 % Lecithin0.3 % All percentages are based on the weight of the final composition. The preparation of the chocolate took place by the method described in Example 1, the milk powder being added during the mixing stage. The conching took place at 70°C for 10 hours with the additional cocoa butter being introduced after 8 hours of conching and the lecithin after 9 hours of conching. The milk chocolate product was evaluated by a taste panel and was judged satisfactory in every respect. Example 4A composition was prepared comprising Cocoa nib11.2 % Additional cocoa butter25.4 % 99% pure crystalline maltitol41.3 % Whole milk powder21.8 % Lecithin0.3 % The preparation of the chocolate took place as is described in Example 3. Once again a satisfactory product was obtained.	A process for the production of chocolate comprising a sugar alcohol as sweetener in which after mixing the chocolate ingredients the composition is submitted to a conching step characterised in that the conching step is dry conching carried out at a temperature of at least 65°C, preferably in the range 65°-100°C and the sugar alcohol is erythritol or maltitol in which the maltitol has a purity greater than 90%, preferably greater than 95% especially about 99%. A process according to claim 1 characterised in that the conching temperature is in the range 75° to 85°C. A process according to claim 1 or claim 2 characterised in that the conching is carried out for a period of up to 16 hours, especially 6 to 16 hours. A process according to any one of the preceding claims characterised in that the chocolate composition comprises 30 to 60% by weight erythritol or maltitol , preferably 40 to 60% by weight, particularly 45 to 55% by weight, the other components of the composition comprising cocoa nib and cocoa butter in addition to the cocoa butter contained in the cocoa nib. A process according to claim 4 characterised in that the chocolate composition contains 30 to 60 % by weight cocoa nib and 10 to 20% by weight cocoa butter in addition to the cocoa butter contained in the cocoa nib. A process according to claim 4 or claim 5 characterised in that the chocolate composition also contains a emulsifier such as lecithin. A process according to any one of claims 4 to 6 characterised in that the chocolate composition contains an intense sweetener eg. aspartame.	CERESTAR HOLDING BV	GONZE M; RAPAILLE A; VAN DER SCHUEREN F; GONZE, M.; RAPAILLE, A.; VAN DER SCHUEREN F.
EP-0489516-B1	489,516	EP	B1	EN	19,950,607	1,992	20,100,220	new	A61B5	A61M25	A61M16, A61M25, A61B5	K61M16:04B2, A61B 5/03, A61M 25/10E	Pressure monitors and tube assemblies	A monitor 10 for measuring the pressure in the cuff 2 on a tracheal tube 1 is clipped onto a coupling 7 at the end of an inflation indicator balloon 8. A silicon strain gauge pressure sensor 14 is urged resiliently against one side of the balloon, the other side of which rests on a base plate 12. The sensor 14 provides an output to a numeric display 18 representative of pressure in the balloon 8 and hence in the cuff 2.	This invention relates to a cuffed medico-surgical tube assembly including a cuff pressure monitor and a cuffed medico-surgical tube of the kind for insertion into a body cavity and having a flexible inflation indicator located externally of the body communicating with the cuff and inflated on inflation of the cuff, the pressure monitor having an electrical pressure sensor and a display on which is provided a display representation indicative of pressure in the cuff. Such features are known from US-A-4,134,407. The invention is more particularly concerned with assemblies including a cuffed endotracheal tube or tracheostomy tube. Tracheal tubes are used to transmit anaesthetic or ventilation gases to a patient, such as during surgery, or to provide an airway to the trachea when the patient is breathing spontaneously. These tubes often have a cuff around the tube close to the patient end, which is inflated to seal with the trachea so that gas flow is confined within the tube. The cuff is inflated and deflated via a small-bore lumen extending along the tube within its wall, which opens into the cuff close to the distal or patient end and is connected to one end of an inflation line close to the proximal or machine end of the tube. The other end of the inflation line extends outside the patient and has a connector and an inflation indicator in the form of an inflatable balloon the interior of which communicates with the interior of the inflation line. The cuff is initially deflated and, after insertion of the tube into the trachea, is inflated by means of a syringe or similar device coupled to the connector, which administers a measured volume of air. This causes inflation of the cuff and the indicator. The indicator provides visual evidence to the clinician of the state of inflation of the cuff. These tubes may remain in place for some time and the pressure within the cuff can change during this time. The pressure may increase because of diffusion of anaesthetic gases through the wall of the cuff. Alternatively, the pressure may decrease because of leakage. Although the inflation balloon indicates large changes in pressure of the cuff, it is not sensitive to small changes in pressure. It is desirable to be able to maintain the cuff at the correct pressure because too high a pressure can lead to damage to the tracheal lining, whereas too low a pressure can allow leakage of gas between the tube and the trachea. Pressure gauges are available which can be coupled to the connector at the machine end of the inflation line but these are generally bulky and expensive. Their size and weight make them unsuitable for attachment to a tube long term. The pressure gauge can be incorporated into the syringe used to inflate the cuff, as described in EP-A-0396353. It is an object of the present invention to provide an alternative pressure monitor that can be used to monitor cuff pressure. According to one aspect of the present invention there is provided an assembly of the above-specified kind, characterised in that the monitor includes a U-shape housing extending around and supported by the inflation indicator, that the housing has a plate extending on one side of the inflation indicator, and that a spring mounted on the housing resiliently urges the pressure sensor in contact with the opposite side of the inflation indicator so that change in inflation of the indicator thereby causes a change in the output of the pressure sensor and hence a change in the display representation. The inflation indicator is preferably a flexible balloon. The monitor may be removable from the inflation indicator and may have a clip that fastens onto a coupling at one end of the inflation indicator. The pressure sensor preferably includes a silicon strain gauge. The display is preferably a numeric display and may be a liquid crystal display. A cuff pressure monitor and a tube assembly including the monitor in accordance with the present invention, will now be described, by way of example, with reference to the accompanying drawings, in which: Figure 1is a side elevation view of the assembly; Figure 2is a sectional side elevation view of the monitor to a larger scale; and Figure 3is a transverse section along the line III - III of Figure 2. With reference first to Figure 1, there is shown a conventional cuffed endotracheal tube 1 having an inflatable cuff 2 extending around the tube close to its patient end 3. The interior of the cuff 2 communicates with an inflation lumen 4 extruded along the length of the tube 1 within its wall. Towards the machine end 5 of the tube, one end of an inflation line 6 is connected into the lumen 4. The inflation line 6 is flexible and, in use extends out of the patient's mouth. At its other end, the inflation line 6 has a coupling 7, which may include a valve (not shown), and an inflation indicator 8 in the form of a flexible balloon or envelope sealed to one end of the coupling. The interior of the inflation indicator 8 communicates with the inflation line 6 and cuff 2 so that the indicator is inflated when the cuff is inflated. As so far described, the tube is conventional. With reference now also to Figures 2 and 3, the pressure monitor 10 is removably clipped onto the outside of the coupling 7 at the machine end of the inflation line 6 and encompasses the inflation indicator 8. The pressure monitor 10 is contained in a plastic housing 11 of U-shape in section which has a flat base-plate 12 and an upper assembly 13 spaced from the base-plate by a short distance. The upper assembly 13 includes an electrical pressure sensor 14, such as including a silicon strain gauge, which is carried on a resilient, spring support 15 and projects downwardly towards the base-plate 12. The electrical output of the pressure sensor 14 is supplied to a processor 16 which performs various conventional calibration, scaling and calculation operations on its input and provides display driver signals on line 17 to a multi-segment liquid crystal display LCD 18. Other displays could be used. To the left of the upper assembly 13, the housing 11 is formed into a spring clip 19 which overlies and projects downwardly towards the base plate 12. The pressure monitor 10 also has a panel 20 on its side on which can be written pressure readings taken at different times. Alternatively, each pressure reading could be stored electronically within the processor 16. In use, the pressure monitor 10 is clipped onto the coupling 7, so that the spring clip 19 firmly locates on the coupling, and so that the inflation indicator 8 lies between the base plate 12 and the upper assembly 13. The pressure sensor 14 is urged vertically downwards by the support 15 to contact the upper surface of the exterior of the inflation indicator 8. The output of the pressure sensor 14 depends on the pressure within the inflation indicator 8, and hence on the pressure within the cuff 2. The pressure monitor 10 can be clipped onto the coupling and inflation indicator either before or after the cuff 2 is inflated, following intubation into the trachea. The display 18 can provide an indication of pressure in the cuff 2 on any standard pressure scale, or on an arbitary numeric scale. Alternatively, the indication of pressure could be provided on a non-numerical display, such as, for example, a bar graph display. Preferably each tube has its own pressure monitor 10 which is clipped in place when the tube is inserted and remains in place until the tube is removed. The nurse or anaesthetist can check the pressure reading periodically and, if the cuff pressure is too high or low, air can be inserted into or withdrawn from the cuff using a syringe inserted into the coupling 7 in the usual way. This operation of correcting the pressure in the cuff can be carried out whilst the monitor is in place. Alternatively, the pressure monitor 10 could be carried around in the pocket of the nurse or other user and clipped in place on different tubes as and when they are being checked. The pressure monitor 10 could include a visual or audible alarm that signals when the cuff pressure exceeds predetermined limits. The pressure monitor is not limited to use on tracheal tubes but could be used on other medico-surgical tubes having a cuff that is inflated to seal the tube with the body cavity and a flexible inflation indicator communicating with the cuff.	A cuffed medico-surgical tube assembly including a cuff pressure monitor (10) and a cuffed medico-surgical tube (1) of the kind for insertion into a body cavity and having a flexible inflation indicator (8) located externally of the body communicating with the cuff and inflated on inflation of the cuff, the pressure monitor (10) having an electrical pressure sensor (14) and a display (18) on which is provided a display representation indicative of pressure in the cuff (2), characterised in that the monitor (10) includes a U-shape housing (11) extending around and supported by the inflation indicator (8), that the housing (11) has a plate (12) extending on one side of the inflation indicator (8), and that a spring (15) mounted on the housing resiliently urges the pressure sensor (14) in contact with the opposite side of the inflation indicator (8) so that change in inflation of the indicator (8) thereby causes a change in the output of the pressure sensor(14) and hence a change in the display representation. An assembly according to Claim 1, characterised in that the inflation indicator is a flexible balloon (8). An assembly according to Claim 1 or 2, characterised in that the monitor (10) is removable from the inflation indicator (8). An assembly according to any one of the preceding claims, characterised in that the monitor (10) has a clip (19) that fastens onto a coupling (7) at one end of the inflation indicator (8). An assembly according to any one of the preceding claims, characterised in that the pressure sensor includes a silicon strain gauge (14). An assembly according to any one of the preceding claims, characterised in that the display is a numeric display (18). An assembly according to any one of the preceding claims, characterised in that the display is a liquid crystal display (18).	SMITHS INDUSTRIES PLC; SMITHS INDUSTRIES PUBLIC LIMITED COMPANY	CRAWLEY BRIAN; TURNBULL CHRISTOPHER STRATTON; CRAWLEY, BRIAN; TURNBULL, CHRISTOPHER STRATTON
EP-0489517-B1	489,517	EP	B1	EN	19,961,227	1,992	20,100,220	new	C08K5	C08L73	C08K5, C08L73	C08K 5/00S+L73/00, C08K 5/15+L73/00	Stabilised polyketone composition	A polymer composition stabilised against degradation during melt processing which comprises (a) a major amount of a polymer of carbon monoxide and at least one olefin (b) a minor effective amount of a first stabiliser comprising an aluminium trialkoxide, an aluminium phenoxide or an aluminium containing hydrolysis product of such compounds and (c) a minor effective amount of a second stabiliser comprising an organic epoxy containing compound. The aluminium trialkoxide is suitably aluminium isopropoxide and the organic epoxy containing compound is for example epoxidised soybean oil.	The present invention relates to a stabilised polymer composition containing a copolymer of carbon monoxide and one or more olefins. In particular the invention relates to compositions containing such copolymers which exhibit good stability in processes during which the composition is melted and subsequently solidfied. The preparation of random copolymers of a minor amount of carbon monoxide and a major amount of ethylene by catalysed radical polymerisation has been known for some years. More recently it has been found that linear alternating copolymers of carbon monoxide and one or more olefins, hereafter called polyketones, can be prepared by contacting the reactants with a Group VIII metal catalyst preferably comprised of palladium and a bidentate phosphine, see for example EP 121965. The polyketones prepared by this process, whilst being thermoplastics, suffer from the disadvantage that they have relatively high melting points close to temperatures at which they undergo chemical degradation. This causes a problem since the materials are thus difficult to process using conventional melt technology. In order to overcome this problem a number of potential approaches have been explored. EP 213671 teaches that polyketones comprised of carbon monoxide, ethylene and alpha olefin (eg propylene) units have lower melting points than corresponding materials comprised only of carbon monoxide and ethylene units. Whilst this approach goes some way to alleviating the problem, there is still a need to improve further the melt processing stability of polyketones if they are to be processed successfully on a commercial scale. Methods of further improving melt processability have centred around a) the blending of polyketones with other polymers, b) the addition of plasticisers and c) the use of additives claimed to interfere with the degradation reactions which the polyketones undergo. The first two types of approach suffer in that relatively large amounts of the second polymer or plasticiser are required, a consequence of which is that there is a general deterioration in the physical, mechanical and barrier properties of the polyketone. An example of the third type of approach is disclosed in EP 310166. This patent teaches the addition of an aluminium alkoxide or a derivative thereof. Examples of preferred additives are those having the general formula Al(OR)3 where each R is independently C1 to C12 alkyl. A disadvantage of this approach is, however, that it has only limited effectiveness. For example, we have found that whilst there is a stability increase in using 1% of such materials with the polyketones, there is no substantial further benefit obtained when higher levels are used. A related patent, US 4950703 teaches the use of aluminium phenoxide and ring substituted derivatives thereof. Another example of this approach is taught in US 3948832. According to this patent, organic epoxy-containing compounds are useful stabilisers for ethylene/carbon monoxide copolymers although the experimental evidence is rather qualitative. Our investigations have shown that these materials are not very effective stabilisers for melt processing. Epoxy-containing compounds are also referred to in United States Statutory Invention Registration H732 published 6th February 1990. Japanese Kokai 58194937 (Chemical Abstracts No. 100 157618p (1984)) teaches the use of aluminium isopropylate together with a Ba-Zn stabiliser, phosphite esters, epoxidised soyabean oil and phenol antioxidants to improve the thermal stability and processability of carbon monoxide-ethylene-vinyl acetate copolymers. Finally EP 326224 teaches the use of a combination of an aluminium alkoxide and an aromatic amine to improve melt flow processability. The use of sterically hindered phenols and C5 to C30 mono- or polycarboxylic acid amides are also taught as being useful. To summarise, the prior art discussed above, whilst teaching the use of aluminium alkoxides on the one hand and epoxy containing compounds on the other, makes no suggestion that it would be desirable to use both together to stabilise polyketones. It has now been found that when both these additives are added to polyketones, the resultant compositions exhibit a marked and unexpected improvement in melt processability which is over and beyond that expected on the basis of their individual effects. According to the present invention there is therefore provided a polymer composition stabilised against degradation during melt processing which comprises (a) a major amount of a polyketone having a linear alternating structure of units derived from carbon monoxide and units derived from one or more olefins (b) a minor effective amount of a first stabiliser comprising an aluminium trialkoxide, an aluminium phenoxide or an aluminium containing hydrolysis product of such compounds and (c) a minor effective amount of a second stabiliser comprising an organic epoxy containing compound which is (1) free of substituents which could adversely effect the properties of the polymer compositions, (2) not substantially volatile at the processing temperature and (3) does not fume at this temperature. The stabilised polymer compositions of the present invention have a number of advantages over those disclosed in the prior art. Firstly the combination of the two stabilisers provides an enhanced stabilisation of melt flow rate over that which can be achieved with either of the stabilisers individually. Secondly, addition of the epoxy containing compound allows better control over the melt temperature on processing and improves the performance of the aluminium alkoxide. Finally the addition of the aluminium alkoxide reduces the level of epoxy-containing compound required to produce a given level of stabilisation and thus reduces the detrimental effects on mechanical, physical and barrier properties of the polyketone caused by the presence of high levels of this additive. However the use of the combination of the stabilisers defined above is particularly effective when applied to polyketones. For the purposes of this patent, polyketones are defined as linear polymers having an alternating structure of (a) units derived from carbon monoxide and (b) units derived from one or more olefins. Suitable olefin units are those derived from C2 to C12 alpha-olefins and substituted derivatives thereof and styrene or its alkyl substituted derivatives. It is preferred that such olefin or olefins are selected from C2 to C6 normal alpha-olefins and it is particularily preferred that the olefin units are either derived from ethylene or most preferred of all from ethylene and one or more C3 to C6 normal alpha-olefin eg propylene. Amongst these most preferable materials,it is further preferred that the molar ratio of ethylene units to C3 to C6 normal alpha-olefin units is greater than or equal to 1 most preferably between 2 and 30. The polyketones described above are suitably prepared by the processes described in EP 121965 or modifications thereof. In general terms, this comprises reacting carbon monoxide and the chosen olefin(s) at elevated temperature and pressure with a catalyst which is preferably comprised of palladium, a bidentate phosphine such as a C2 to C6 bis(diphenylphosphino)alkane and an anion which either does not coordinate to the palladium or coordinates only weakly. Example of such anions include p-toluensulphonate, tetrafluoroborate, borosalicylate and the like. The process is suitably carried out at a temperature in the range 50 to 150°C, a pressure in the range 25 to 75 bar gauge and in a solvent such as methanol, acetone, THF and the like. As regards the first stabiliser this is suitably for example an aluminium alkoxide having the general formula Al(OR)3 where the R groups are independently C3 to C36 alkyl groups or substituted derivatives thereof. Preferably the R groups are independently C3 to C12 alkyl groups or substituted derivatives thereof. The alkyl groups may contain primary, and/or secondary and/or tertiary carbon atoms as the case may be. Most preferred examples of such first stabilisers are compounds having the general formula given above where the R groups are identical secondary alkyl groups having 3 to 8 carbon atoms. Of these compounds, most preferred of all is aluminium trisisopropoxide. Alternatively, the first stabiiser can be an aluminium phenoxide of formula (Z)3-xAl(OR1)x where the Z groups are independently phenoxide or substituted phenoxide, the R1 groups are independently C1 to C10 alkyl, preferably C1 to C10 branched alkyl, and x is 0, 1 or 2. Preferred examples of this class are those compounds where the phenoxide group is di- or trisubstituted at the 2,6-; 2,4-; 3,5- or 2,4,6- positions with C3 to C5 branched alkyl especially tertiary alkyl, eg tert-butyl groups. The amount of first stabiliser used should be in the range 0.1 to 10 parts per hundred parts by weight of the composition for effectiveness, preferably 0.3 to 3 most preferably 0.5 to 1.5. Turning to the second stabiliser this can in principle be any organic compound containing one or more epoxy groups and which is (1) free of substituents which could adversely effect the properties of the polymer compositions, (2) not substantially volatile at the processing temperature and (3) does not fume at this temperature. The organic compound can be aliphatic, including cycloaliphatic, or aromatic but preferably does not have olefinic unsaturation which is subject to oxidative degradation. Preferred examples of such compounds are epoxy substituted ethers, esters, phosphonates and the like as well as high molecular weight polymers which are epoxy substituted. Most preferred compounds are those comprised of at least 6 carbon atoms including 1,2-epoxyoctadecane, styrene epoxide, butyl-epoxy stearate, epoxidised polybutadiene, poly(alkylglycidyl)ethers, p-chlorophenoxypropylene oxide, dicyclopentadiene diepoxide, diglycidyl ether of bisphenol A, epoxidised fatty acid triglycerides such as epoxidised soybean oil and the like. The amount of second stabiliser used should be in the range 0.1to 15 parts per hundred parts by weight of the composition for effectiveness, preferably 0.5 to 6. In addition to adding the first and second stabilisers to the polymer in discrete form, it is possible to react the first and second stabilisers together beforehand to produce a reaction product which itself can be used as a stabiliser. Such a reaction can be carried out by reacting the two stabilisers together in a suitable non-reactive solvent, eg a hydrocarbon solvent, under reflux conditions. Thereafter the solvent can be removed and the product dried if so desired. The amount of reaction product used should be in the range 0.3 to 3 parts per hundred parts by weight of the composition preferably 0.5 to 1.5. The stabilisers or their reaction product can be incorporated into the polyketone by essentially any known method as this is not deemed to be critical, provided that intimate mixing is achieved. For instance, providing they do not interfere with the polymerisation reactions, they may be incorporated into the polymerisation mixture prior to or during polymerisation. Alternatively, they may be mixed with the polymer after the polymerisation is complete by direct mixing with the polymer powder or by adding as a solution in a suitable solvent which is subsequently volatilised out of the composition. Intimate mixing is then achieved when the polymer is molten by shearing in a batch mixer or continuous extruder. In addition to the components defined above, the composition may contain further additives such as antioxidants, blowing agents, mould release agents and other materials conventional in the art. The improved stability of the composition of the present invention compared to the original polyketone manifests itself as an improvement in melt flow rate and in particular a maintenance of melt flow rate over a long period of time. The compositions of the present invention may be readily melt processed and hence can be used in the manufacture of containers forfood and drink, automotive parts, wires, cables and structural items for the construction industry. The following Examples now illustrate the invention. Comparative Test A A sample of polyketone (an ethylene - propylene - carbon monoxide terpolymer having an intrinsic viscosity of 1.65 dlg-1, measured in m-cresol at 30°C, and a peak melting point of 208°C as measured by Differential Scanning Calorimetery) was processed in a laboratory batch melt mixer (Brabender Plasticorder) with a rotor speed of 60 rpm and an initial temperature of 217±2°C. Mixing was carried out under a nitrogen blanket achieved by a flow of nitrogen passing through the rotor shaft and over the top of the ram. The melt flow of the polymer was measured using a Davenport Melt Index Tester at 240°C with a 21.6 kg load. The melt flow was taken as the 30 second flow 3 minutes after charging the polymer into the barrel of the instrument at temperature. Otherwise standard procedures were followed (ASTM D 1238-86). The melt flow rate of the unprocessed polyketone was measured as 53g/10 minutes whilst after processing for 20 minutes in the batch melt mixer the product would not flow at all. Comparative Test B, C, D and EThe procedure of Comparative Test A, was followed except that only Reoplast 39 (ex Ciba Geigy - epoxidised soybean oil) or only aluminium isopropoxide (ex Aldrich) was added manually to the polyketone prior to processing. The melt flow rates after 30 minutes processing together with related data are given in the Table. Examples 1 and 2The procedure of Comparative Test A was followed except that in these experiments mixtures of stabilisers were used. The melt flowrates after 30 minutes processing together with related data are given in Table 1. Examples 1 and 2 show an increase in melt flow rate after 30 minutes as compared to the unstabilised materials. In addition, the degree of stabilisation is clearly greater than that achieved with either of the two stabilisers alone (compare Example 2 with Comparative Tests C and E). The increase in melt temperature and rotor torque over 30 minutes is also given, indicating the extent to which crosslinking has taken place in each case. Comparative Test F and Examples 3 and 4Four batches of polyketone powder, intrinsic viscosities in the range 1.42 to 1.52 dlg-1, as measured in m-cresol at 30°C, and melting points in the range 191-195°C, as measured by the peak of the DSC endotherm on scanning at 10°C min-1, were dry blended by mechanical shaking. The melt flow rate of the powder mixture was approximately 40 g/10 min at 240°C and 5kg. Material from this powder blend was processed on the Brabender Plasticorder and behaviour was monitored over 30 minutes. Processing was carried out with a rotor speed of 60 rpm and an initial temperature of 215°C. Details of processing responses and melt flow index after processing, measured at 240°C with a 5kg load, are given in Table 2. Polymer was processed without any additives (CTF) with 1 pph aluminium isopropoxide (Aldrich) (CTG) 0.3 pph aluminium isopropoxide and 0.7 pph. Rheoplast 39 by Ciba Geigy, an epoxidised soyabean oil (Ex.4) and 1 pph of a reaction product of aluminium isopropoxide and Reoplast 39 (Ex.3). The reaction product was prepared as follows. MethodA 100cm3 round bottom flask fitted with a 10cm distillation column and condenser was flushed with nitrogen. Aluminium isopropoxide (2.756g), Rheoplast 39 (6.50g) and dry toluene (50cm3) was placed into the flask through a stream of nitrogen. The mixture was heated to mild reflux for one hour then the reaction temperature was increased and a distillate collected (5.69g). The distillate was analysed by gas liquid chromatography and contained isopropanol (0.375g). The mixture was cooled to room temperature and the distillation apparatus removed. The remaining solvent was removed in vacuo at 40 C. The product was further dried in vacuo at 40°C for one day. Additives Minimum Torque (gm) Final Torque (gm) Final Melt Temp (°C) Melt Flow Rate (g/10 min) CTFNone59012902310 CTG1pph aluminium isopropoxide58072022019 Ex31pph AIP/Rheoplast Reaction Product57072022116 Ex40.3pph AIP + 0.7pph Rheoplast56069022017 Example 3 shows that the two stabilisers can be reacted together before use and that the reaction product is an effective stabiliser.	A polymer composition stabilised against degradation during melt processing which comprises (a) a major amount of a polyketone having a linear alternating structure of units derived from carbon monoxide and units derived from one or more olefins (b) a minor effective amount of a first stabiliser comprising an aluminium trialkoxide, an aluminium phenoxide or an aluminium containing hydrolysis product of such compounds and (c) a minor effective amount of a second stabiliser comprising an organic epoxy containing compound which is (1) free of substituents which could adversely effect the properties of the polymer compositions, (2) not substantially volatile at the processing temperature and (3) does not fume at this temperature. A polymer composition as claimed in claim 1 wherein the amount of the first stabiliser is in the range 0.3 to 3 parts per hundred parts by weight of the polymer composition. A polymer composition as claimed in claim 2 wherein the amount of first stabiliser is in the range 0.5 to 1.5 parts per hundred parts by weight of the polymer composition. A polymer composition as claimed in claim 1 wherein the amount of the second stabiliser is in the range 0.5 to 6 parts per hundred parts by weight of the polymer composition. A polymer composition as claimed in claim 1 wherein the first stabiliser is an aluminium trialkoxide having the general formula Al(OR)3 where the R groups are independently C3 to C12 alkyl. A polymer composition as claimed in claim 5 wherein the R groups are identical C3 to C8 secondary alkyl groups. A polymer composition as claimed in claim 1 wherein the first stabiliser is an aluminium phenoxide of formula (Z)z-xAl(OR1)x wherein the Z groups are independently phenoxides which are di- or tri-substituted at the 2,6-; 2,4-; 3,5-, or 2,4,6- positions with C3 to C5 branched alkyl groups, the R1 groups are independently C1 to C10 alkyl and x is 0, 1 or 2. A polymer composition as claimed in claim 1 wherein the second stabiliser is selected from the group consisting of 1,2-epoxyoctane, styrene epoxide, butyl-epoxy stearate, epoxidised polybutadiene, poly(alkylglycidyl)ethers, p-chlorophenoxypropylene oxide, dicyclopentadiene diepoxide, diglycidyl ether of bisphenol A, epoxidised fatty acid triglycerides and epoxidised soybean oil. A polymer composition as claimed in claim 1 wherein the units derived from one or more olefins are derived from ethylene and a C3 to C6 normal olefin. A polymer composition as claimed in claim 9 wherein the C3 to C6 normal olefin is propylene.	BP CHEM INT LTD; BP CHEMICALS LIMITED	DAVIDSON NEIL SHEARER BP CHEMI; DAVIDSON, NEIL SHEARER, BP CHEMICALS LIMITED
EP-0489518-B1	489,518	EP	B1	EN	19,970,312	1,992	20,100,220	new	C08K9	C08L83	C08L83, C08K9	C08K 9/06+L83/04, C08L 83/04+B4S+C8+F	Extrudable curable organosiloxane compositions exhibiting reduced compression set	Cured organosiloxane elastomers exhibiting compression set values of 25% or less with no adverse affect on other physical properties are prepared from organosiloxane compositions curable by a platinum-catalyzed hydrosilation reaction and containing a reinforcing silica filler that has been treated with at least one organosilicon compound that is a hexaorganodisilazane wherein two of the silicon-bonded hydrocarbon radicals are alkenyl. The hexaorganodisilazane constitutes from 1 to 4.6 weight percent of the organosilicon compounds used to treat the silica filler and the molar ratio of silicon-bonded hydrogen atoms to alkenyl radicals in the curable composition is from 0.8 to 2.0, preferably from 1 to 1.5.	This invention relates to extrudable organosiloxane compositions. More particularly, this invention relates to extrudable organosiloxane compositions that can be cured by a platinum-catalyzed hydrosilation reaction to form elastomers exhibiting superior physical properties, particularly compression set tear strength and durometer hardness values, without sacrificing other desirable properties such as tensile strength and processability of the curable composition. EP-A-0374951 relates to an addition reaction-type silicone composition particularly suitable for coating rollers used in electrophotographic copying apparatus, printers or other image forming apparatus. The silicone composition may comprise a silicone compound which is an addition reaction-type silicone rubber prepared from a dimethylpolysiloxane having a vinyl group, a methylhydrogen polysiloxane and a platinum-base catalyst, and in addition comprises a reactive group-containing modified silicic acid powder which has had its surface modified with an alkylsilane, hexamethyldisilazane, a dimethylsilicone oil, or a mixture thereof, an unsaturated group-containing silane compound and an inorganic fine powder carrying a surfactant. Furthermore, EP-A-0042208 discloses a method for the preparation of hydrophobic reinforcing silica fillers which are treated with at least one hydrophobe agent which is selected from the group consisting of RnSiZ4-n, (R3Si)2NH, (R3Si)2O, (R2SiO)x, (R2SiNH)x, R'O(R2SiO)yR', (R3Si)2NR and (R2SiNR )x wherein each R is selected from the group consisting of aliphatic hydrocarbon radicals of from 1 to 6 inclusive carbon atoms, halogenated alkyl radicals of 1 to 10 inclusive carbon atoms and phenyl radicals, each R' is hydrogen or R , each R is a alkyl radical of 1 to 4 inclusive carbon atoms, each Z is -OR', -NHR , or -NR / 2, n has an average value of from 2 to 3 inclusive, x has an average value of from 3 to 6 inclusive, y has an average value of from 1 to 12 inclusive, the amount of said hydrophobe agent present being sufficient to provide at least 0.05 moles of hydrophobe agent per mole of theoretical SiO2 units present in said alkyl silicate. The present inventors have discovered how to decrease the compression values of organosiloxane elastomers prepared by curing compositions comprising a liquid diorganoalkenylsiloxy terminated polydiorganosiloxane, an organohydrogensiloxane as the curing agent, a reinforcing silica filler and a platinum-group metal-containing hydrosilation catalyst. They have accomplished this by using sym-tetramethyldivinyldisilazane as at least a portion of the organosilicon compounds used to treat the reinforcing silica filler and by maintaining the molar ratio of silicon-bonded hydrogen atoms to vinyl or other ethylenically unsaturated hydrocarbon radicals in the curable composition within the range of from 0.8 to 2. An objective of this invention is to define a class of liquid curable organosiloxane compositions that can be cured to yield elastomers exhibiting a value for compression set, measured in accordance with ASTM test procedure D395, of 30 percent or less without sacrificing other desired physical properties of the cured elastomer, including tear strength and durometer hardness. A preferred class of the present compositions can be transported by pumping using conventional equipment. The present compositions are cured using a platinum-catalyzed hydrosilation reaction. This invention provides an improved curable and extrudable organosiloxane composition comprising the product obtained by mixing to homogeneity, (A) 100 parts by weight of a first diorganoalkenylsiloxy terminated polydiorganosiloxane in which the only alkenyl radicals present on the non-terminal silicon atoms thereof result from impurities present in the starting materials or due to rearrangements occuring during preparation, represented by the formula: YR1 2SiO(R2 2SiO)xSiR1 2Y in which Y represents an alkenyl radical containing from 2 to 10 carbon atoms, R1 and R2 are individually monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals containing from 1 to 20 carbon atoms, R1 and R2 are substantially free of ethylenic unsaturation and x represents a degree of polymerization equivalent to a viscosity of up to 20 Pa·s at 25°C; (B) an amount sufficient to cure said composition of an organohydrogensiloxane that is miscible with (A) and contains an average of more than two silicon-bonded hydrogen atoms per molecule, where the organic groups present in (A) and (B) are monovalent hydrocarbon or halogenated hydrocarbon radicals; (C) an hydrosilation catalyst consisting essentially of a platinum-group metal or a compound thereof, the concentration of said catalyst being sufficient to promote curing of said composition at a temperature of from ambient to 250°C, wherein in order to ensure sufficient miscibility the silicon-bonded hydrocarbon radicals that are present in the highest concentration in ingredients (A), (B) and (C) are selected from the same class, and (D) from 10 to 60 weight percent, based on the weight of said composition, of finely divided silica as the reinforcing filler which is treated with more than one organosilicon compounds, characterised in the presence of a sym-tetraalkyldialkenyldisilazane as from 1 to 5 weight percent, preferably 1 to 4.6 weight percent of the organosilicon compounds used to treat said filler and a molar ratio of silicon-bonded hydrogen atoms in said organohydrogen-siloxane to alkenyl radicals in all polydiorganosiloxanes present in said curable composition of from 0.8 to 2.0. The inventive features considered responsible for the low values of compression set that characterize cured elastomers prepared from the present curable compositions are (1) the type of organosilicon compounds used to treat the reinforcing silica filler, from 1 to 5 weight percent of which are disilazanes containing two silicon-bonded alkenyl radicals, such as sym-tetramethyldivinyldisilazane, and (2) a molar ratio of silicon-bonded hydrogen atoms to alkenyl radicals (referred to as the SiH/alkenyl ratio) of from 0.8 to 2.0, preferably from 1 to 1.5. The accompanying examples demonstrate an increase in compression set values outside of these ranges even when using the filler treating agents of this invention. Preferred compositions include calcium oxide or hydroxide to further reduce compression set as taught in U.S Patent No. 4,301,056 for peroxide cured silicone rubber. Compression set is typically determined using ASTM test procedure D395. In accordance with method B of this procedure a sample of cured elastomer of known thickness (A), typically 1.25 cm., is compressed to 75 percent of its initial thickness (B) in a suitable clamping device and then heated at a temperature of 177°C. for 22 hours. The sample is then allowed to stand for 0.5 hour under ambient conditions, at which time its thickness (C) is measured. Compression set values are calculated using the formula [(A-C)/(A-B)]x100, where A represents the thickness of the initial sample prior to compression, B represents the thickness to which the sample is compressed during the test procedure and C represents the thickness of the sample following recovery from compression. Low values of compression set are required for certain end-use applications during which the cured elastomer is compressed between two mating surfaces to serve as a seal or gasket. The ingredients of the present compositions will now be discussed in detail. The polydiorganosiloxane containing only terminal alkenyl radicals is referred to hereinafter as ingredient A. This ingredient exhibits a viscosity of from 5 to 100 Pa·s and contains vinyl or other alkenyl radicals only at the terminal positions of the molecule. When it is desired to increase the values of certain physical properties, such as tensile and tear strength, exhibited by cured elastomers prepared from the curable compositions of this invention, the compositions preferably contain from 0.5 to 30 percent based on the combined weight of alkenyl-substituted polydiorganosiloxanes of a second diorganoalkenylsiloxy-terminated polydiorganosiloxane, referred to hereinafter as ingredient A', that contains alkenyl radicals on from 1 to 5 mole percent of the non-terminal repeating siloxane units. Cured elastomers prepared using preferred compositions of this invention exhibit tear strength values of 35-45 kilonewtons/meter. Experimental data for elastomers prepared using compositions of this invention containing optional ingredient A' and an embodiment of ingredient A exhibiting a viscosity of up to 20 Pa·s demonstrate that the tear strength of the elastomer reaches a maximum as the concentration of ingredient A' approaches 3 percent, based on the combined weight of ingredients A and A' and decreases with increasing concentration of ingredient A' beyond the 3 percent level. The alkenyl radicals present in ingredients A and A' contain from 2 to 10 carbon atoms. Preferred alkenyl radicals are terminally unsaturated and include, but are not limited to, vinyl, allyl and 5-hexenyl. The silicon-bonded organic groups present in ingredients A and A', in addition to alkenyl radicals, are the monovalent hydrocarbon or substituted hydrocarbon radicals described in detail in the following portions of this specification. The term essential absence of non-terminal alkenyl radicals used to describe-ingredient A means that the only alkenyl radicals present on the non-terminal silicon atoms of this ingredient result from impurities present in the reactants used to prepare this ingredient or from undesired rearrangements occurring during preparation of this ingredient. Ingredient A is a diorganoalkenylsiloxy-terminated polydiorganosiloxane and can be represented by the average general formula YR1 2SiO(R2 2SiO)xSiR1 2Y where Y represents an alkenyl radical as defined in a preceding section of this specification, R1 and R2 are individually monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals, R1 and R2 are substantially free of ethylenic unsaturation and x represents a degree of polymerization equivalent to a viscosity of up to 20 Pa·s at 25°C. In preferred embodiments, the viscosity of ingredient A is from 5 to 15 Pa·s. The R1 and R2 radicals bonded to the silicon atoms of ingredient A contain from 1 to 20 carbon atoms and can be identical or different. Because ingredient A is an extrudable liquid at 25°C., at least one of the R2 radicals on each of the non-terminal silicon atoms is lower alkyl, most preferably methyl. The remaining R2 radical can be alkyl such as methyl or ethyl; substituted alkyl such as chloromethyl, 3-chloropropyl or 3,3,3-trifluoropropyl; cycloalkyl such as cyclohexyl; or aryl such as phenyl. Most preferably, any R1 and R2 radicals other than methyl are phenyl or 3,3,3-trifluoropropyl, this preference being based on the availability of the intermediates used to prepare these polydiorganosiloxanes and the properties of cured elastomers prepared by curing compositions containing these polymers. Methods for preparing the liquid polydiorganosiloxanes used as ingredients A and optional ingredient A' of the present compositions by hydrolysis and condensation of the corresponding halosilanes or cyclic polydiorganosiloxanes are sufficiently disclosed in the patent and other literature that a detailed description in this specification is not necessary. Optional ingredient A' is a liquid diorganoalkenylsiloxy-terminated polydiorganosiloxane that can be represented by the average general formula Y'R3 2SiO(R4 2SiO)y(Y'R4SiO)zSiR3 2Y'In this formula, Y' represents an alkenyl radical as defined for the Y radical of ingredient A, R3 and R4 are selected from the same group of monovalent hydrocarbon radicals and substituted monovalent substituted hydrocarbon radicals as R1 and R2. Because ingredients A and A' should be miscible with one another, the silicon-bonded hydrocarbon radicals present in these ingredients should be selected from the same class, i.e. lower alkyl. These hydrocarbon radicals, including Y and Y' are preferably identical. The degree of polymerization represented by the sum of y and z is equivalent to a viscosity of from 0.1 to 10 Pa·s, preferably from 0.1 to 1 Pa·s, and the ratio z/(y+z) is from 0.01 to 0.05, which specifies the requirement for this ingredient that from 1 to 5 mole percent of the non-terminal repeating units contain a vinyl radical. The degree of polymerization of ingredient A' is preferably less than the degree of polymerization of Ingredient A. Preferred embodiments of ingredient A include but are not limited to dimethylvinylsiloxy-terminated polydimethyl-siloxanes, dimethylvinylsiloxy-terminated polymethyl-3,3,3-trifluoropropylsiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane/3,3,3-trifluoropropylmethylsiloxane copolymers and dimethylvinylsiloxy-terminated dimethylsiloxane/methylphenylsiloxane copolymers. Preferred embodiments of optional ingredient A' encompass all of the preferred polydiorganosiloxanes for ingredient A with the addition of from 1 to 5 mole percent of non-terminal organoalkenylsiloxane units, where the preferred organic group are alkyl containing from 1 to 4 carbon atoms, fluoroalkyl such as 3,3,3-trifluoropropyl and aryl such as phenyl. The vinyl radicals present in these preferred embodiments of ingredients A and A' can be replaced by other ethylenically unsaturated radicals such as allyl and 5-hexenyl. The organosiloxane compositions of this invention are cured by a platinum catalyzed hydrosilation reaction. The curing agent is an organohydrogensiloxane containing an average of more than two silicon-bonded hydrogen atoms per molecule. The organohydrogensiloxane contains from as few as four silicon atoms per molecule up to an average of 20 or more and can have a viscosity of up to 10 Pa·s or higher at 25°C. The repeating units of this ingredient include but are not limited to HSiO1.5, R5HSiO and/or R52HSiO0.5 in addition to one or more of monoorganosiloxy, diorganosiloxane, triorganosiloxy and SiO4/2 units. In these formulae, R5 represents a monovalent hydrocarbon or halocarbon radical as defined hereinabove for the R radical of ingredient A. One preferred class of organohydrogensiloxanes are copolymers consisting essentially of the repeating units R3SiO1/2, R2SiO, RHSiO and RSiO3/2 units, where the R radicals are free of ethylenic unsaturation and are individually selected from monovalent hydrocarbon and halogenated hydrocarbon radicals and the RSiO3/2 units constitute from 0.5 to 50 mole percent of the copolymer. Copolymers of this type can be prepared by a controlled hydrolysis of a mixture comprising the corresponding organosilicon halides, such as the chlorides or the corresponding alkoxides. These and other methods for preparing the preferred organohydrogensiloxanes of this invention are sufficiently well known that a detailed description is not required in this specification. A second preferred class of organohydrogensiloxanes contain repeating units represented by the formulae R52HSiO1/2 and SiO4/2. The concentration of R52HSiO1/2 units is equivalent to a concentration of silicon-bonded hydrogen atoms in the copolymer of from 0.5 to 5 weight percent. Proper curing of the present compositions requires that ingredients A, B and C be miscible with one another. To ensure sufficient miscibility the silicon-bonded hydrocarbon radicals that are present in the highest concentration in these ingredients should be selected from the same class, e.g. alkyl radicals. These hydrocarbon radicals are preferably identical. In particularly preferred compositions, these hydrocarbon radicals are methyl or combinations of methyl with either 3,3,3-trifluoropropyl or phenyl. The molar ratio of silicon-bonded hydrogen atoms to vinyl or other alkenyl radicals, referred to as the SiH/vinyl ratio, in combination with the use of a hexaorganodisilazane containing alkenyl radicals as at least a portion of the silica treating agent are critical with respect to the compression set values of the cured elastomer. For the present curable compositions, the SiH/vinyl ratio is from 0.8 to 2.0, optionally from 0.8 to 1.5. The optimum ratio for particular compositions will be determined at least in part by the molecular weights of ingredients A and optional-ingredient A', the type of curing agent and the concentration of any resinous organosiloxane copolymer described hereinafter. To minimize the compression set values in preferred compositions of this invention, this ratio is from about 1 to 1.5. The optimum range of this ratio for other curable compositions of this invention can readily be determined by those skilled in the art with a minimum of experimentation. Hydrosilation reactions are typically conducted in the presence of a catalyst (Ingredient C) that is a metal from the platinum group of the periodic table or a compound of such a metal. Platinum, rhodium and compounds of these metals have been shown to catalyze hydrosilation reactions. Platinum compounds such as hexachloroplatinic acid and particularly complexes of these compounds with relatively low molecular weight vinyl-containing organosiloxane compounds are preferred catalysts because of their high activity and compatibility with the organosiloxane reactants. These complexes are described in U.S. Patent No. 3,419,593 that issued to David N. Willing on December 31, 1968. Complexes with low molecular weight organosiloxanes wherein the silicon-bonded hydrocarbon radicals are vinyl and either methyl or 3,3,3-trifluoropropyl are particularly preferred because of their ability to catalyze a rapid curing of the elastomer at temperatures of at least about 70°C. The platinum containing catalyst can be present in an amount equivalent to as little as one part by weight of platinum per one million parts of curable composition. Catalyst concentrations equivalent to from 5 to 50 parts of platinum per million of curable composition are preferred to achieve a practical curing rate. Higher concentrations of platinum provide only marginal improvements in curing rate and are therefore economically unattractive, particularly when the preferred catalysts are used. Mixtures of the aforementioned vinyl-containing reactants, curing agents and platinum-containing catalysts may begin to cure at ambient temperature. To obtain a longer working time or pot life , the activity of the catalyst under ambient conditions can be retarded or suppressed by addition of a suitable inhibitor. Known platinum catalyst inhibitors include the acetylenic compounds disclosed in U.S. Patent No. 3,445,420, which issued on May 20, 1969 to Kookootsedes et al. Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors that will suppress the activity of a platinum-containing catalyst at 25°C. Compositions containing these catalysts typically require heating at temperatures of 70°C. or above to cure at a practical rate. If it is desired to increase the pot life of a curable composition under ambient conditions, this can be accomplished using an olefinically substituted siloxane of the type described in U.S. Patent No. 3,989,667, which issued on November 2, 1976 to Lee and Marko. Cyclic methylvinylsiloxanes are preferred. Inhibitor concentrations as low as one mole of inhibitor per mole of platinum will in some instances impart satisfactory storage stability and cure rate. In other instances, inhibitor concentrations of up to 500 or more moles of inhibitor per mole of platinum are required. The optimum concentration for a given inhibitor in a given composition can readily be determined by routine experimentation and does not constitute part of this invention. To achieve the high levels of tear strength and other physical properties that characterize cured elastomers prepared using the compositions of this invention, the compositions must contain a reinforcing silica filler. This type of filler is treated with more than one of the known silica treating agents to prevent a phenomenon referred to as creping or crepe hardening during processing of the curable composition. Any finely divided form of silica can be used as the reinforcing filler. Colloidal silicas are preferred because of their relatively high surface area, which is typically at least 50 square meters per gram. Fillers having surface areas of at least 200 square meters per gram are preferred for use in the present method. Colloidal silicas can be prepared by precipitation or a fume process. Both of these preferred types of silica are commercially available. The amount of finely divided silica used in the present compositions is at least in part determined by the physical properties desired in the cured elastomer. Liquid or pumpable polyorganosiloxane compositions typically contain from about 10 to 60 percent by weight of silica, based on the weight of polydiorganosiloxane. This value is preferably from 30 to 50 percent. Silica treating agents are typically low molecular weight organosilicon compounds containing silicon-bonded hydroxyl groups or groups that can be hydrolyzed to hydroxyl groups in the presence of water. Typical hydrolyzable groups include halogen atoms such as chlorine amino and other groups containing a silicon-bonded nitrogen atom. In accordance with the present invention, from 1 to 5.0 weight percent, preferably 1 to 4.6 weight percent of the organosilicon compounds used to treat the reinforcing silica filler are hexaorganodisilazanes containing at least two alkenyl radicals per molecule. The alkenyl radicals typically contain from 2 to 10 carbon atoms. Vinyl is a preferred alkenyl radical based on the availability of the intermediates used to prepare the disilazane. Most preferably, the remaining silicon-bonded hydrocarbon radicals are methyl and the silica treating agent is sym-tetramethyldivinyldisilazane. A preferred concentration range for the disilazane containing silicon-bonded alkenyl radicals is from 2 to 4 weight percent of the total silica treating agents. In addition to the ingredient A, optional ingredient A', curing agent, curing catalyst and treated silica filler the organosiloxane compositions of this invention can contain one or more additives that are conventionally present in curable compositions of this type. These materials are added to impart or enhance certain properties of the cured elastomer or facilitate processing of the curable composition. A small amount of water can be added together with the silica treating agent(s) as a processing aid. Typical additives include but are not limited to pigments, dyes, adhesion promoters, flame retardants, heat and/or ultraviolet light stabilizers and resinous organosiloxane copolymers to enhance the physical properties of the cured elastomer. Diatomaceous earth and calcium hydroxide are two preferred additives based on their ability to reduce the degradation in physical properties, particularly a decrease in tensile and tear strengths and an increase in compression set value, that occurs when the cured elastomer comes into contact with oil heated to temperatures of 150°C. In addition to improving the resistance of elastomers to property degradation during long term exposures, the presence of calcium hydroxide also reduces the compression set of the cured elastomer. The silica filler can be treated in the presence of at least a portion of the other ingredients of the present compositions by blending these ingredients together until the filler is completely treated and uniformly dispersed throughout the composition to form a homogeneous material. The ingredients that are present during treatment of the silica typically include the silica treating agents and at least a portion of the polydiorganosiloxanes referred to herein as ingredients A and optional ingredient A'. The organohydrogensiloxane and platinum-containing catalyst are typically added after treatment of the silica has been completed. Irrespective of the type of mixer used, blending of the silica, filler treating agent and ingredients A and A' is continued while the composition is heated at temperatures from about 100 to 250°C. under reduced pressure to remove volatile materials. The resultant product is then cooled prior to being blended with the organohydrogensiloxane (Ingredient B) and/or the platinum catalyst (Ingredient C), depending upon whether it is desired to prepare a one-part or two-part curable composition of this invention. The optional additives referred to hereinbefore can be added at this time or during blending of the silica with ingredients A and A'. In-situ treatment of the silica can require anywhere from 15 minutes to 2 hours, depending upon the amount of material being processed, the viscosity of the material and the shear rate to which the material is subjected during processing. Alternatively, treatment of the silica can occur before the silica is blended with other ingredients of the present compositions. Methods for treating finely divided silica fillers prior to incorporating the silica into a polyorganosiloxane composition are known in the art. To ensure adequate blending of all ingredients, the mixing equipment in which the present compositions are prepared should be capable of subjecting the composition to a high rate of shear. The advantage of using this type of a high intensity mixer to prepare silica filled polyorganosiloxane compositions is taught in U.S. Patent No. 3,690,804, which issued to Minuto on June 1, 1976. In accordance with the disclosure of this patent, the tip of the stirring device in the mixer is rotated at a speed of from 7.62 to 76.2 m/s (25 to about 250 feet per second), which would generate considerable shearing forces. The exemplified compositions are blended in a Henschel high intensity mixer wherein the rotor was operated at a speed of 3800 revolutions per minute, equivalent to a rotor tip speed of 47.85 m/s (157 feet per second). Dough type mixers equipped with sigma shape blades, are not as efficient as mixers wherein the mixing surfaces are of a relatively flat paddle configuration. Examples of the paddle type mixers include the Henschel mixer disclosed in the aforementioned Minuto patent and certain mixers manufactured by Neulinger A.G. The blade is preferably rotated at a speed of at least 100 revolutions per minute. Curable compositions prepared using the present method typically exhibit viscosities of about 0.5 up to about 1000 Pa·s at 25°C. To facilitate blending and transfer of the compositions and minimize entrapment of air during mixing, a viscosity of less than about 10 Pa·s at 25°C. is preferred for pumpable compositions. Mixtures of ingredients A and optional ingredient A' with the curing agent (ingredient B) and the platinum-containing catalyst may begin to cure under conditions encountered during storage of these composition, even in the presence of a catalyst inhibitor. To ensure long term storage stability it is sometimes necessary to separate the curing agent from the catalyst until it is desired to cure the composition. This is typically achieved by packaging the curing agent and curing catalyst in separate containers or by using one-part compositions containing a curing catalyst that is microencapsulated within one or more layers of a thermoplastic organic polymer or a thermoplastic polyorganosiloxane. Methods for microencapsulating platinum-containing hydrosilation catalysts are described in the art. For example, one part compositions curable by a platinum-catalyzed hydrosilation reaction and containing as the hydrosilation catalyst a liquid platinum compound that is microencapsulated within a layer of a thermoplastic organic polymer, together with methods for preparing the micro-encapsulated catalyst are described in U.S. Patent No. 4,766,176, which issued to Lee et al. on August 23, 1988. The present curable compositions can be formed into shaped articles by press molding, injection molding, extrusion or any of the other methods used to fabricate organosiloxane compositions. In the absence of one of the aforementioned catalyst inhibitors and/or an encapsulated catalyst, the compositions will cure at ambient temperature over a period of several hours or days or within several minutes when heated at temperatures of up to 250°C. Compositions containing one of these catalyst inhibitors are typically cured by heating them for several minutes at temperatures of from 50 to about 250°C. A preferred range is from 100 to 200°C. Compositions containing a microencapsulated catalyst should be heated to a temperature at least equal to the melting or softening temperature of the encapsulating polymer. Cured elastomerie articles prepared using the curable compositions of this invention comprising a tetraalkyldialkenyldisilazane, exhibit compression set values below 30 percent, preferably below 25 percent, without adversely affecting other desirable properties of the cured elastomer, such as durometer hardness or the extrudability of the composition from which it is formed. This unique combination of properties make the elastomers desirable for a number of end use applications, including gaskets and fabricated articles wherein at least a portion of the article is relatively thin and subjected to large amounts of stress. Articles of this type include diaphragms and bladders. The following examples describe preferred curable compositions of this invention and the desirable properties of elastomers, particularly low values of compression set and high durometer hardness values, prepared by curing these compositions. The examples are intended to illustrate the present invention and should not be interpreted as limiting the invention as defined in the accompanying claims. Unless indicated to the contrary, all parts and percentages are by weight and all viscosities were measured at 25°C. Example 1This example demonstrates the lower values of compression set achieved when a hexaorganodisilazane containing two vinyl radicals per molecule is used as a portion of the silica treating agent in place of a vinyl-containing hydroxyl-terminated polydiorganosiloxane. The organosiloxane compositions were prepared by blending to homogeneity in a dough type mixer the entire quantity (3800 parts) of a fume silica having a nominal surface area of 380 m2 per gram, 1689 parts of diatomaceous earth, 760 parts of hexamethyldisilazane as the first silica treating agent, 126.7 parts water and 8444 parts of a dimethylvinylsiloxy terminated polydimethylsiloxane having a viscosity of about 10 Pa·s at 25°C. (ingredient A). When all the filler had been blended into the resultant mixture, 22.8 parts of sym-tetramethyldivinyldisilazane were added as the second silica treating agent. Volatile materials were removed from the resultant mixture by circulating steam through the jacket of the mixer while maintaining the contents under reduced pressure. Following completion of the heating cycle, the resultant mixture (I) was blended to homogeneity with 3540.4 parts of ingredient A together with 84.4 parts of a silanol terminated polydimethylsiloxane having a viscosity of about 0.04 Pa·s at 25°C. and containing about 4 weight percent of silicon-bonded hydroxyl groups as the third silica treating agent and 5.07 parts of methylbutynol as a catalyst inhibitor. The silica treating agent of this invention, sym-tetramethyldivinyldisilazane, constituted 2.6 percent of the combined weight of the three silica treating agents. Curable compositions were prepared from the resultant mixture by combining 250 gram portions of this mixture with (1) the amount of an organohydrogensiloxane sufficient to provide one of the molar ratios of silicon-bonded hydrogen atoms to vinyl radicals present in ingredient A listed in the following Table 1 and (2) as the platinum-containing hydrosilation catalyst (ingredient C), a reaction product of hexachloroplatinic acid and sym-tetramethyldivinyldisiloxane that had been diluted with a liquid dimethylvinylsiloxy terminated polydimethylsiloxane in an amount sufficient to achieve a platinum content of 0.7 weight percent, based on the weight of both parts of the curable composition. The amount of catalyst was equivalent to 6.3 parts per million parts by weight of platinum, based on the weight of the complete curable composition. Three different organohydrogensiloxanes were evaluated. One of these (B1) contains 0.8 weight percent silicon-bonded hydrogen, exhibits a viscosity of 0.016 Pa·s and corresponds to the general formula (Me3SiO1/2)12.7 (Me2SiO)29.1 (MeHSiO)54.6 (MeSiO3/2)3.6. The second organohydrogensiloxane (B2), contains 1 weight percent of silicon-bonded hydrogen atoms, exhibits a viscosity of 0.024 Pa·s and can be represented by the general formula (SiO4/2)4.4(Me2HSiO1/2)8. The third organohydrogensiloxane (B3) was a trimethylsiloxy-terminated polydiorganosiloxane containing an average of five methylhydrogensiloxane units, three dimethylsiloxane units per molecule and about 0.8 weight percent of silicon-bonded hydrogen atoms. To demonstrate the unique ability of the present silica treating agents to reduce the compression set values of cured elastomers prepared from the curable compositions of this invention, a second set of curable compositions were prepared for comparative purposes using the same types and amounts of ingredients as the compositions describe in the preceding section of this example, with the exception that the 22.8 parts of sym-tetramethyldivinyldisilazane were replaced with 67.6 parts of a hydroxyl-terminated dimethylsiloxane/methylvinylsiloxane copolymer containing 10 weight percent vinyl radicals and 16 weight percent of hydroxyl groups. A second set of comparative compositions were prepared using a silica treating agent of the present invention and a molar ratio of SiH/vinyl that is above the present upper limit of 1.5. All of the curable compositions were cured in the form of sheets having a thickness of 1.9 mm. by confining the compositions in a chase that was then placed on the lower platen of a hydraulic press. The press was then closed and the compositions cured by heating them for 5 minutes at a temperature of 150°C. under a pressure of 140kN/m (800 psi). Test samples were then cut from each of the cured sheets to determine the physical properties of the cured elastomer. The American Society of Testing and Materials (ASTM) test procedures used to measure the properties evaluated included ASTM-395, method B for compression set values and ASTM-D2240, Shore A scale for durometer hardness values. Table 1 summarizes the type of silica treating agent and the parts by weight of curing agents B1, B2 or B3 added to the 250 gram mixtures of ingredient A, filler, filler treating agent and platinum catalyst inhibitor that were used to prepare the curable compositions and the resultant molar ratio of silicon-bonded hydrogen atoms (SiH) to vinyl radicals. The filler treating agent of this invention, sym-tetramethyldivinyl-disilazane, was present in samples 1-24C and the comparative filler treating agent was used to prepare comparative samples 25C-48C. The compression set and durometer hardness (Shore A scale) values of the samples are summarized in Table 2. Samples identified by the letter C in addition to a number are included for comparative purposes. Samples 24C to 48C were prepared using a silica treating agent outside the scope of the present invention. Samples 7C, 8C, 15C, 16C, 23C and 24C were prepared using a silica treating agent of this invention; however, the SiH/vinyl molar ratio was above the present upper limit of 2. The data in Table 2 demonstrate the compression set of below 25% and the desirably high Shore A durometer hardness values achieved by preferred composition using the silica treating agents of this invention and a molar ratio of SiH to vinyl within the present range of 0.8 to 2.0, preferably from 1 to 1.5. Example 2This example demonstrates the reduction in compression set values imparted to cured elastomers by one of the present silica treating agents in combination with two alkenyl-substituted polydiorganosiloxanes, one of which contains alkenyl radicals on non-terminal silicon atoms (optional ingredient A'). Organosiloxane compositions were prepared by blending to homogeneity in a dough type mixer the entire quantity (3800 parts) of a fume silica having a nominal surface area of 380 m2 per gram, 730.8 parts of diatomaceous earth, 760 parts of hexamethyldisilazane, 109.6 parts water and 4560 parts of a dimethylvinylsiloxy terminated polydimethylsiloxane having a viscosity of about 10 Pa·s at 25°C. (ingredient A). When all the filler had been blended into the resultant mixture 22.7 parts of sym-tetramethyldivinyldisilazane were added. Volatile materials were removed from the resultant mixture by circulating steam through the jacket of the mixer while maintaining the contents of the mixer under reduced pressure. Following completion of the heating cycle the resultant mixture (I) was blended to homogeneity with 2528.5 parts of ingredient A together with 219.2 parts of a dimethylvinylsiloxy-terminated dimethylsiloxane/methylvinylsiloxane copolymer containing 2 mol percent of methylvinylsiloxane units and exhibiting a viscosity of 0.3 Pa·s (optional ingredient A'), 84.0 parts of a silanol terminated polydimethylsiloxane having a viscosity of about 0.04 Pa·s at 25°C. and containing about 4 weight percent of silicon-bonded hydroxyl groups and 11.7 parts of methylbutynol as a catalyst inhibitor. Curable compositions were prepared from the resultant mixture by combining 250 gram portions of this mixture with (1) the amount of the organohydrogensiloxane identified as B1 in Example 1 sufficient to provide a molar ratio of silicon-bonded hydrogen atoms to vinyl radicals in the composition of 1.25 and 2) as the platinum-containing hydrosilation catalyst (ingredient C), a reaction product of hexachloroplatinic acid and sym-tetramethyldivinyldisiloxane that had been diluted with a liquid dimethylvinylsiloxy terminated polydimethylsiloxane in an amount sufficient to achieve a platinum content of 0.7 weight percent, based on the weight of both parts of the curable composition. The amount of catalyst, was equivalent to 6.3 parts per million parts by weight of platinum, based on the weight of the complete curable composition. The composition was cured and evaluated for compression set as described in Example 1. The compression set value was 21 percent. The reason for using the optional ingredient A' was to improve the tear strength of the cured elastomer.	An extrudable organosiloxane composition comprising the product obtained by mixing to homogeneity: (A) 100 parts by weight of a first diorganoalkenylsiloxy terminated polydiorganosiloxane in which the only alkenyl radicals present on the non-terminal silicon atoms thereof result from impurities present in the starting materials or due to rearrangements occuring during preparation, represented by the formula: YR1 2SiO(R2 2SiO)xSiR1 2Y in which Y represents an alkenyl radical containing from 2 to 10 carbon atoms, R1 and R2 are individually monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals containing from 1 to 20 carbon atoms, R1 and R2 are substantially free of ethylenic unsaturation and x represents a degree of polymerization equivalent to a viscosity of up to 20 Pa·s at 25°C; (B) an amount sufficient to cure said composition of an organohydrogensiloxane that is miscible with (A) and contains an average of more than two silicon-bonded hydrogen atoms per molecule, where the organic groups present in (A) and (B) are monovalent hydrocarbon or halogenated hydrocarbon radicals; (C) an hydrosilation catalyst consisting essentially of a platinum-group metal or a compound thereof, the concentration of said catalyst being sufficient to promote curing of said composition at a temperature of from ambient to 250°C, wherein in order to ensure sufficient miscibility the silicon-bonded hydrocarbon radicals that are present in the highest concentration in ingredients (A), (B) and (C) are selected from the same class, and (D) from 10 to 60 weight percent, based on the weight of said composition, of finely divided silica as the reinforcing filler which is treated with more than one organosilicon compounds, characterised in that a sym-tetraalkyldialkenyldisilazane in an amount which constitutes from 1 to 5.0 weight percent of the organosilicon compounds used to treat said filler is present and the molar ratio of silicon-bonded hydrogen atoms in said organohydrogensiloxane alkenyl radicals in all polydiorganosiloxanes present in said curable composition is from 0.8 to 2.0. An extrudable organosiloxane composition according to claim 1, characterised in that the sym-tetraalkyldialkenyldisilazane is present in an amount of from 1 to 4.6 weight percent of the organosilicon compounds used to treat said filler. A composition according to claim 1 where said composition contains from 0.5 to 30 percent based on the combined weight of alkenyl-substituted polydiorganosiloxanes, of a second diorganoalkenylsiloxy-terminated polydiorganosiloxane (A)' represented by formula: Y'R3 2SiO(R4 2SiO)y(Y'R4SiO)zSiR3 2Y' in which Y' represents an alkenyl radical containing from 2 to 10 carbon atoms; R3 and R4 are individually monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals and the degree of polymerization represented by the sum of y and z is equivalent to a viscosity of from 0.1 to 10 Pa·s and wherein said ingredient A' contains alkenyl radicals of from 1 to 5 mole percent of the non-terminal repeating siloxane units.	DOW CORNING; DOW CORNING CORPORATION	GRAY THOMAS EDWARD; JENSEN JARY DAVID; GRAY, THOMAS EDWARD; JENSEN, JARY DAVID
EP-0489521-B1	489,521	EP	B1	EN	19,960,313	1,992	20,100,220	new	G01S7	G01S13	G01S7, G01S13	G01S 7/26, G01S 13/93A	Displays and display systems	An aircraft display system has a display unit 4 with matrix array of LED's 40 mounted in the glareshield 5. Air traffic command signals received by a datalink processor 2 produce a visual indication on the display unit 4 which is visible to the pilot when looking through the window 50. A button 41 on the unit 4 is pressed by the pilot to acknowledge receipt of the instructions. Other important messages are displayed by the unit at different times. Radar altimeter height is displayed in one colour which changes when the aircraft descends below its flare height. When on the ground, the unit 4 displays the distance-to-go to the end of runway, and stripes that move horizontally along the display unit to indicate deviation from the runway centre line.	This invention relates to aircraft display systems including a processing unit, a visual display unit mounted in the region of the glareshield of the aircraft that receives the output of the processing unit, and a datalink receiver that receives air traffic command instructions from a source remote from the aircraft and provides an output to the processing unit to generate display driver signals in accordance therewith so that the display unit provides a visual display representation of the air traffic command instructions and the processing unit generates a response signal in response to acknowledgement of the air traffic command instructions. Aircraft have many displays presenting a variety of information to the pilot. When the pilot's attention needs to be drawn to information of particular importance, it can be difficult to ensure that he is able to distinguish this important information from other information. It has been proposed in GB 2226924A corresponding to EP-A-0370640 to mount a display in the glareshield of an aircraft to present information to the pilot from a TCAS collision avoidance system. The display is of a kind that produces changing symbols so that these are visible in the peripheral field-of-view of the pilot while he is looking forwardly through the aircraft window. There is, however, other information that it is desirable to present to the pilot, which does not necessarily have to be interpreted by the pilot when looking through the aircraft window. It has been found that it is very advantageous to present this information to the pilot on a display located in the region of the glareshield, because such a location is separate from the other aircraft instruments and is closest to the external field-of-view through the window. It is an object of the present invention to provide an improved aircraft display system. According to the present invention there is provided an aircraft display system of the above-specified kind, characterised in that the display driver signals generated by the processing unit provide a display of alphanumeric information of a variable value on the visual display unit, that the alphanumeric information is represented in one colour on a contrasting background when the value is in a predetermined range, and that the alphanumeric representation and or alternatively the background is changed in colour when the value falls outside the range so that the viewer's attention is drawn to the display unit. The visual display unit may be switchable to display one of the following instead of the air traffic command instructions: collision avoidance information, ground roll information and radar altimeter information. The system may include an aircraft attitude sensor that provides an output signal representative of aircraft attitude, the processing unit receiving the attitude output and providing a display driver signal that produces on the display unit a visual display representation of symbols moving horizontally along the display in a direction and at a rate dependent on the displacement of the aircraft from the runway centre line. The system may include a sensor that provides an output signal indicative of distance-to-go of the aircraft from a point on the runway, the processing unit providing display driver signals that generate on the display unit a numerical representation of the distance-to-go. The system may include a radar altimeter sensor, the variable alphanumeric information being radar altimeter information, and the colour change being produced when the height of the aircraft falls below a predetermined height. The processing means may be arranged to provide radar altimeter information on the visual display unit prior to touch down and then to provide information about displacement of the aircraft from the runway centre line. A multi-function aircraft display system in accordance with the present invention, will now be described, by way of example, with reference to the accompanying drawings, in which: Figure 1shows the system schematically; Figure 2shows a display provided by the system; and Figures 3a and 3bshow alternative displays. The display system includes a receiver 1 connected to a datalink processor 2, which also receives inputs from various other sources 3, and provides an output signal to drive a display unit 4 mounted in the aircraft glareshield 5 immediately below the forward window 50 of the aircraft. The receiver 1 receives radio transmissions via an aerial 12 and supplies an output to an input of the datalink processor 2. The datalink processor 2 provides a display driver signal on line 15 to the display unit 4 which causes the display unit to provide a visual display in alphanumeric form of the signals received by the receiver 1 from a transmitting station 6 on the ground. The transmitting station 6 transmits air traffic control commands to identified aircraft so as to control movement of aircraft, for example, in and around airports and when taxling on the ground. In the example shown, the air traffic control signal is for the aircraft to turn left to a heading of 250 degrees. This is displayed on the unit 4 by the legend TURN LEFT 250 . The display unit 4 has a matrix array of LED's 40 which may be of different colours so as to enable display representations to be in different colours. Typically, the usable size of the display unit 4 is about 20cm wide by 3cm high which is sufficient to enable short messages to be displayed with high visibility. The display unit 4 is not dedicated to display of air traffic control information but is used to display several different forms of important information of the kind having an immediate effect on the flight path of the aircraft. The use of the display unit 4 is confined to these important messages, other messages being displayed on the aircraft's MCDU (multi-function control display unit) 7 or on the EFIS/EICAS (electronic flight instrumentation system/engine indication and crew alerting system) 8. In this way, the pilot knows that, when a message appears on the display unit 4, it must be acted on with priority. The location of the display unit 4 in the glareshield 5 means that any change in the appearance of the unit is immediately apparent in the peripheral field of view of the pilot when he is looking forwardly through the aircraft window 50, or inside at the main instrument panels. The display unit 4 has an optional acknowledge button 41, or other manually-operable control, which the pilot presses when he has entered the new heading in the aircraft's autopilot 9. This causes a signal to be sent from the display unit 4 to the processor 2, and from there to the receiver 1 which transmit a message to the ground station 6, to acknowledge that the command signals have been acted on. Alternatively, the autopilot 9 may have a direct link 90 to the processor 2 so that the act of entering in a new heading to the autopilot automatically causes the acknowledge signal to be transmitted to the ground station 6. In additional to the air traffic command signals, the display unit 4 displays (at different times) the following information: TCAS, collison avoidance instruction; ground roll guidance with distance-to-go information; and radar altimeter with flare height information. The TCAS information is presented in the same manner as described in GB 2226924A. The ground roll guidance and distance-to-go information is presented in the format shown in Figure 2. The upper part of the display has a series of alternate bright and dark inclined stripes 42 that move left-to-right or right-to-left across the screen of the unit 4 according to the displacement of the aircraft relative to the centre line of the runaway after the aircraft has landed. If the aircraft is to the right of the centre line, the stripes 42 move the left; if the aircraft is to the left of the centre line, the stripes move the right. The rate of movement of the stripes is dependent on the amount of deviation. When central, the stripes are stationary. Similar forms of indicator have been previously provided using a rotating pole having a helical stripes that appears to move along the pole as it is rotated. Centrally in the lower part of the display screen, there is represented a box 43 within which appears the distance-to-go to end of runway. In the present example, this is between 2500 ft and 2600 ft. This format is displayed after landing, especially during low visibility, so that the pilot can maintain a central path along the runway without having to look directly at the display itself. The distance-to-go can be determined by glancing down to the display. The information needed to generate this display format is supplied to the datalink processor 2 from the group of sensors or sources 3 which include an ILS, instrument landing system that provides aircraft attitude information and information about the aircraft's distance-to-go to the end of the runway. The radar altimeter information is provided in the form shown in Figures 3A and 3B. The system is preset with the aircraft flare height that is, the height at which the aircraft should start to be flared from its descent to its landing pitch attitude. In this example, the flare height is 30ft. Above the flare height, the display unit 40 presents a legend such as RAD ALT 35 in bright letters against a dark background, as in Figure 3A, to indicate that the radar altimeter reads a height of 35ft. When the flare height of 30ft is reached, as detected by a radar altimeter sensor in the group of sources 3, the display format changes to dark letters against a bright background, as in the lower display RAD ALT 30 in Figure 3B. The pilot is, therefore, immediately made aware that the aircraft has gone below the flare height without having to look directly at the display, because the change in appearance is visible in the pilot's peripheral field of view. The display might typically represent the radar altimeter information until touch down and then switch automatically to the ground roll display. This might be followed by a representation of ground movement commands received from the source 6. Various other important information could be represented additionally or alternatively in the display unit 4.	An aircraft display system including a processing unit (2), a visual display unit (4) mounted in the region of the glareshield (5) of the aircraft that receives the output of the processing unit, and a datalink receiver (1) that receives air traffic command instructions from a source remote from the aircraft and provides an output to the processing unit (2) to generate display driver signals in accordance therewith so that the display unit (4) provides a visual display representation of the air traffic command instructions and the processing unit (2) generates a response signal in response to acknowledgement of the air traffic command instructions, characterised in that the display driver signals generated by the processing unit (2) provide a display of alphanumeric information of a variable value on the visual display unit, that the alphanumeric information is represented in one colour on a contrasting background when the value is in a predetermined range, and that the alphanumeric representation and or alternatively the background is changed in colour when the value falls outside the range so that the viewer's attention is drawn to the display unit (4). An aircraft display system according to Claim 1, characterised in that the visual display unit (4) is switchable to display one of the following instead of the air traffic command instructions: collision avoidance information, ground-roll information and radar altimeter information. An aircraft display system according to Claim 1 or 2, characterised in that the system includes an aircraft attitude sensor (3) that provides an output signal representative of aircraft attitude, that the processing unit (2) receives the attitude output and provides a display driver signal that produces on the display unit (4) a visual display representation of symbols (42) moving horizontally along the display in a direction and at a rate dependent on the displacement of the aircraft from the runway centre line. An aircraft display system according to Claim 3, characterised in that the system includes a sensor (3) that provides an output signal indicative of distance-to-go of the aircraft from a point on the runway, and that the processing unit (2) provides display driver signals that generate on the display unit a numerical representation of the distance-to-go An aircraft display system according to any one of the preceding claims, characterised in that the system includes a radar altimeter sensor (3), that the variable alphanumeric information is radar altimeter information, and that the colour change is produced when the height of the aircraft falls below a predetermined height. An aircraft display system according to Claim 5 and Claim 3 or 4, characterised in that the processing unit (2) provides radar altimeter information on the visual display unit (4) prior to touch down and then provides information about displacement of the aircraft from the runway centre line.	SMITHS INDUSTRIES PLC; SMITHS INDUSTRIES PUBLIC LIMITED COMPANY	DOUGAN KEITH GERALD; O'SULLIVAN PETER FRANCIS; DOUGAN, KEITH GERALD; O'SULLIVAN, PETER FRANCIS
EP-0489526-B1	489,526	EP	B1	EN	19,970,108	1,992	20,100,220	new	B65B51	null	B65B51, B29C65	B65B 51/14C, L29C65:18+A4, B29C 65/00H20, B29C 65/00M8D2B	Carton top sealing mechanism	A carton top sealing mechanism 10 for use in processing thermoplastic coated paperboard cartons 66 on a forming, filling and sealing machine. The top sealing mechanism 10 includes oppositely disposed fixed and movable sealing jaws 12 and 16, between which heated adjacent sealing fins 64 of a gable top carton 66 are positioned. A pneumatic bladder or membrane 20 is operatively connected to the movable sealing jaw 16 to move same upon being inflated to thereby squeeze the sealing fins 64 between the jaws 12 and 16 and seal same together.	This invention relates generally to carton top sealing mechanisms and, more particularly, to a carton top sealing mechanism utilizing a pneumatic membrane. Currently, plastic-coated paperboard gable top carton seals are created in the following manner. The plastic coating on the paperboard carton is heat-activated in any suitable manner, such as hot air, radiated head, or ultrasonic vibration, to a point at which the plastic is tacky. The carton panels are folded and guided together, and then squeezed between jaws and cooled, until the seal takes a set. Sufficient pressure must be applied during the sealing operation, to extrude the softened plastic, to fill the pockets and voids created by the folded and abutting multiple paperboard layers. Depending upon the number of cartons to be squeezed at one time, a few thousand to many thousands of newtons (several hundred to a few thousand pounds of force) must be transmitted to the jaws, to generate this pressure. The stroke requirement for the jaws is approximately 5/8 centimetre (1/4 inch). The force applied to the jaws to squeeze the cartons, is generated by either a straight push, or a leverage/linkage driven design. The straight push design requires large, relatively expensive pneumatic cylinders to push the sealing jaws. The leverage/linkage driven designs can utilize smaller pneumatic cylinders, or a cam, to actuate a linkage system, utilizing leverage ratios to generate the required force at the sealing jaws. However, the linkage components, pivot mounts, and lubrication requirements, are generally quite expensive for this method also. EP-A-0203572 discloses a portable sealing apparatus for the sealing of plastic-coated paperboard cartons, including a frame and a fixed jaw mounted thereto. A single movable jaw is utilized to seal top portions of the carton by fusing of a polyethylene coating thereon. A guide channel for the bottom of the carton enables manual placement of the carton with the sealable portions thereon disposed between the fixed and movable jaws. The top portions of the carton are guided between the jaws by guides formed at one end with laterally inwardly converging entrance surfaces. The jaws are generally spaced apart a distance of approximately 5/8 of a centimetre (approximately 1/4 of an inch). Proper selection of pressure, time and controlled heating of the jaws enables the carton to remain adjacent the fixed jaw before, during and after the sealing thereof, without subsequent remelting of the polyethylene coating and opening of the seal for a period of time. US-A-4,735,031 includes a pressing punch (Figures 13 and 14) which is pushed by a flexible hose or tube containing a medium under a definite pressure toward a pressing table to weld two folded-over layers of a container collar together. US-A-2,859,796 discloses two flexible tubes (Figures 3 and 4) which, when inflated, move heated resilient material into engagement with a workpiece, such as two plies of heat-sealable ends of a pouch, to seal the same. US-A-3,808,968 is typical of press devices wherein inflatable hoses are utilized in conjunction with platens to bind two superposed flat articles. US-A-4193341 discloses a platen for a press used to join, by way of a thin layer of uncured vulcanizable material, two sheets of rubber or rubber-like material. The platen comprises a housing having a recess therein, an inflatable tubular member being received in the recess. When the inflatable member is inflated, it acts as a pressure applying member on an elongate strip of flexible material, such as synthetic rubber, which itself acts directly on the workpiece. The strip and the tubular member are retained in position in the recess by means of a skirt secured to the housing. The housing is secured to a vertically movable ram. An oppositely disposed lower platen is fixed and includes an inverted-channel-form member containing an electrical heating element supported upon an insulating layer of fibrous lagging material itself supported upon a rigid layer of thermally insulating material, which directly supports the inverted-channel-form member. The press may be used for all types of pressing operations alternatively to vulcanization, for example as a brake-press for forming sheet metal. The press may be provided with one or two platens of the kind containing an inflatable member. According to the present invention, there is provided a sealing mechanism for sealing thermoplastic materials, said mechanism comprising a fixed sealing jaw, an oppositely disposed movable sealing jaw, driving means for displacing said movable sealing jaw towards said fixed sealing jaw when said materials are positioned intermediate the fixed and movable jaws, thereby to squeeze the materials between the jaws to seal the materials, and a pneumatic membrane operatively connected to said movable sealing jaw, said driving means serving to inflate said pneumatic membrane and thus displace said movable sealing jaw towards said fixed sealing jaw, characterized that said fixed sealing jaw comprises a plurality of separate, semi-rigidly arranged jaw segments for bearing against respective top sealing fins of respective thermoplastic-coated paperboard cartons. The separate, semi-rigid arrangement of the jaw segments permits non-defective cartons between the fixed and movable jaws to be sealed even in the event that a defective carton is present between the jaws. Moreover, owing to the invention, it is possible to provide an improved, efficient and simplified carton top sealing mechanism. The mechanism utilizes a pneumatic membrane, in lieu of mechanical drives or air cylinders, to actuate oppositely disposed sealer jaws. The membrane is operatively connected to a movable sealing jaw for urging the same into engagement with carton gable top sealing panels positioned between the movable jaw and a stationary jaw. In order that the invention may be clearly understood and readily carried into effect, reference will now be made, by way of example, to the accompanying drawings, in which:- Figure 1 is a fragmentary side elevational schematic view of a carton top sealing mechanism outside the scope of the present claim 1; Figure 2 is an exploded view of the carton top sealing mechanism of Figure 1; Figure 3 is a cross-sectional view of a pneumatic membrane component of the carton top sealing mechanism of Figure 1 in one operational condition; Figure 4 is a cross-sectional view of the pneumatic membrane component in another operational condition; Figure 5 is a side elevational view, similar to Figure 1, illustrating a carton top sealing mechanism which is within the scope of the present claim 1; Figure 6 is a top plan view of the Figure 5 embodiment; and Figure 6A is an enlarged view of a portion of Figure 6. Referring now to the drawings in greater detail, Figure 1 illustrates a carton top sealing mechanism 10 including a horizontally oriented stationary jaw 12 extending from a fixed support member 14. An oppositely disposed, horizontally oriented movable jaw 16 extends from a movable pressure plate 18. It is well-known that the oppositely disposed faces 19 of respective sealing jaws may be contoured to accommodate variable thicknesses therebetween. A pneumatic bladder or membrane 20 is mounted between the movable pressure plate 18 and a fixed pressure plate 22 secured to a support member 24. An inlet tube 26 extends from the pneumatic membrane 20 through aligned openings 28 and 30 formed in the pressure plate 22 and the support member 24, respectively. The inlet tube 26 is connected to a source of air under pressure, represented as 32. Figure 2 illustrates the above referenced elements 12, 16, 18, 20, 22, 24, 26, 26 and 30 in more detail, along with a pair of oppositely disposed side support members 34, a cover member 36, supporting legs 38, and two pairs of pinch blocks 40 positioned at opposite ends of the pneumatic membrane 20 between the movable and fixed pressure plates 18 and 22, respectively. For water cooled stationary and moving jaws 12 and 16, respectively, a coolant line 42, suitable fittings 44, and a return line 46 would be provided for each. In between the inlet tube 26 and the source 32 of air under pressure, various typical pneumatic connector and control components are utilized such as a nut 48, an elbow 50, a tube 52, a speed control unit 54, a pneumatic valve 56, a muffler 58, and a pressure regulator 60. Suitable converging closing rails 62 (Figure 2) may serve to bring the usual sealing fins 64 of a gable top carton 66 into close proximity to one another just before entering the space between the jaws 12 and 16, preventing any jam therewith. In operation, once the sealing fins 64 (Figure 1) of a typical gable top carton 66 are indexed into a position intermediate the spaced-apart stationary and movable sealing jaws 12 and 16, respectively, a suitable signal is transmitted to the pneumatic valve 56. The pressure regulator 60 supplies a predetermined pressure, e.g., 450 KPa (65 psi), via the tube 52, elbow 50, and inlet tube 26 to the interior of the membrane 20, to thereby cause the latter to expand from a condition represented in Figure 3 to that represented in Figure 4, resulting in approximately five-eights of a centimetre [1/4 inch] of horizontal stroke. This actuation forces the movable jaw 16 laterally to engage the container sealing fins 64 between the fixed and movable jaws 12 and 16, respectively. Inasmuch as, in the usual forming, filling and sealing machine, the sealing fins 64 of thermoplastic coated paperboard cartons 66 are heated prior to entering the sealing area, the resultant squeezing operation between the jaws 12 and 16 serves to create a liquid tight seal between the sealing fins. A predetermined plurality of aligned cartons 66 may be indexed by a conventional conveyor (not shown) into position between the oppositely disposed jaws 12 and 16, along the lengths thereof, prior to causing the expansion of the pneumatic membrane 20. Referring now to Figures 5, 6 and 6A, there is shown a mechanism constituting an embodiment of the invention: all elements comparable to elements of the Figures 1-4 mechanism bear the same reference numerals. In addition, it will be noted that the positions of the stationary and movable jaws 12 and 16, respectively, have been reversed. In this mechanism the membrane 20 expands to the right in Figure 5, moving a movable pressure plate 68 to the right, against the force of a spring support member 70 supporting the pressure plate 68, causing connector plates 74 to move the movable jaw 16 to the right to engage the sealing fins 64 between the oppositely disposed faces 19 to seal same. This action bows a second spring support member 72 serving to support the movable jaw 16. Once the membrane is deflated, the spring members 70 and 72 return the pressure plate 68 and the movable jaw 16 to their respective leftward positions. As shown in Figure 6, it is more apparent that from one to four cartons 66 may be aligned between and sealed by the action of the movable jaw 16, against the fixed jaw 12. The latter, in this mechanism, is formed to include four semi-rigidly fixed segments 12a, 12b, 12c and 12d, which are adapted to permit three cartons, for example, to be sealed in the event there is a fourth defective carton in place. As shown in Figure 6A, the ends of the membrane 20 are confined between the oppositely disposed pinch blocks 40. It should be apparent that there has been described with reference to the drawings an efficient and simplified carton top sealing mechanism for use with heat-activated thermoplastic-coated paperboard cartons processed on conventional forming, filling and sealing machines. More specifically, the geometric footprint or area of the pneumatic membrane is such that it is applied uniformly to the movable sealing jaw to thus permit more compact machine designs. Additionally, since the membrane does not include any frictional or rubbing components, smoother and more readily repeatable stroke acceleration characteristics are possible as compared to mechanical or air cylinder type drive arrangements. Furthermore, the membrane, being an unconstrained device, does not require critical mounting or alignment.	A sealing mechanism for sealing thermoplastic materials (64), said mechanism (10) comprising a fixed sealing jaw (12), an oppositely disposed movable sealing jaw (16), driving means (32) for displacing said movable sealing jaw (16) towards said fixed sealing jaw (12) when said materials (64) are positioned intermediate the fixed and movable jaws (12,16), thereby to squeeze the materials (64) between the jaws (12,16) to seal the materials (64), and a pneumatic membrane (20) operatively connected to said movable sealing jaw (16), said driving means (32) serving to inflate said pneumatic membrane (20) and thus displace said movable sealing jaw (16) towards said fixed sealing jaw (12), characterized in that said fixed sealing jaw (12) comprises a plurality of separate, semi-rigidly arranged jaw segments (12a-12d) for bearing against respective top sealing fins (64) of respective thermoplastic-coated paperboard cartons (66). A sealing mechanism according to claim 1, and further comprising a pair of fixed and movable pressure plates (22, 18) for confining said membrane (20) therebetween, said movable pressure plate (18) being operatively connected to said movable sealing jaw (16). A sealing mechanism according to claim 2 and further comprising a connector plate (74) interconnecting said movable pressure plate (18) and said movable sealing jaw (16). A sealing mechanism according to claim 2 or 3, and further comprising a pair of spring members (70,72) for supporting said movable pressure plate (68) and said movable sealing jaw (16), respectively, serving to return said movable pressure plate (68) and said movable sealing jaw (16) to their original positions when said membrane (20) is deflated. A sealing mechanism according to any preceding claim, wherein said plurality of segments (12a-12d) is four. A sealing mechanism according to any preceding claim, and further comprising converging rails (62) positioned so as to urge said sealing fins (64) into close proximity to one another in order to enter the space intermediate said fixed and movable jaws (12,16). A sealing mechanism according to any preceding claim, wherein said pneumatic membrane (20) is capable of expanding by of the order of five-eighths of a centimetre (one-fourth of an inch).	ELOPAK SYSTEMS; ELOPAK SYSTEMS AG	ESPER LEO JOSEPH; ESPER, LEO JOSEPH
EP-0489527-B1	489,527	EP	B1	EN	19,950,315	1,992	20,100,220	new	E21B17	null	E21B17	E21B 17/07	Downhole hydraulic shock absorber	A shock absorber apparatus for use in a tool string comprises outer (94,96,98) and inner (38) casings telescopically assembled with one casing having an uphole threaded joint member (12) and the other casing having a downhole threaded joint member (106). The concentric casings define spaced sealed voids (148,180) communicating through a metering sleeve clearance (200) that are filled with a compressible oil. Shock wave induced relative movement of the casings from either direction causes a shock absorbing displacement of oil from one void to the other via the metering clearance. Coil springs (182) may be disposed in the voids to aid in shock absorption.	This invention relates to hydraulic shock absorbers for downhole use, for example for insertion in a drill or tubing string to isolate downhole explosive apparatus. A number of shock absorber devices have been devised for isolating vibrations or explosive energy from more sensitive instruments in an oil well borehole. U.S. patent specification nos. 4,817,710 and 4,693,317 describe a borehole shock absorber that is used for guarding against both longitudinal and radial shock as it affects a gauge carrier or the like. U.S. patent specification no. 2,577,599 is an early teaching of a shock proof case providing wireline support of an instrument housing assembly through a series of resilient elastomeric isolation pads. U.S. patent specification no. 3,714,831 exemplifies the types of device that function to carry a measuring instrument suspended within such as a drill collar section that is designed to receive the instrument. Once again, an elastomeric body or series of annular bodies disposed between the instrument and the drill-collar frame provide reduced vibration suspension of the measuring instrument. This type of device also allows for central passage of drilling fluid through the drill collar simultaneously with sensing operations. U.S. patent specification no. 4,628,995 describes a carrier for supporting pressure gauges on a tool string while providing seating for one or more of the pressure gauges. This device utilizes a restricted flow passageway that impedes the flow of hydraulic well fluid under the effect of the pressure surge at detonation of a perforator, and subsequent expansion of the fluid pressure in an enlarged bore section damps the pressure surge to safely to isolate the pressure-sensitive component. GB-A-2025490 discloses a hydraulic shock absorber apparatus for absorbing shock vibration along a drilling tool string, comprising an outer casing having thread connector means on one end for securing into said tool string, and having a cap means on the other end that defines an axial opening; an inner casing slidably disposed through said axial opening with one end extending coaxially within the outer casing and defining an annular space adjacent thereto, and the other end having a threaded joint connector for securing into said tool string; metering means disposed around said inner casing and dividing said annular space into first and second cylindrical voids that are in communication through a restricted metering clearance; and oil filling the said voids and said clearance. The present invention is characterized in that the said metering means is a sleeve being maintained in position on the inner casing between an annular band on the inner casing and an annular locking ring axially spaced from the said band, the said sleeve and the outer casing forming therebetween a metering clearance of a predetermined value, which constitutes the sole communication between the said annular voice to provide a damping effect in both directions of relative longitudinal movement between the inner and outer casings, and in that said oil is an oil of predetermined compressibility. The arrangement disclosed in GB-A-2025490 provides for damping in one direction, whereas the apparatus of the present invention provides for bi-directional damping, enabling the apparatus to protect the drilling string against the effects of jet detonation travelling either upwardly or downwardly in the tool string. Additionally, this construction permits the metering clearance to be determined or changed simply by suitable dimensioning (or substitution) of the metering sleeve means. Preferably, the oil is a silicone oil of appropriate compressibility. It is also preferred to include first and second compression springs each aligned in a respective one of the first and second cylindrical voids. In order that the invention may be more fully understood, an embodiment thereof will now be described, by way of example only, with reference to the accompanying drawings, in which: Figure 1A is a view in vertical section of a top portion of the embodiment of shock absorber assembly; Figure 1B is a view in vertical section of the upper mid-portion of the shock absorber assembly; Figure 1C is a view in vertical section of the lower mid-portion of the assembly; and Figure 1D is a view in vertical section of the lower part of the shock absorber assembly. Figures 1A to 1D illustrate an embodiment of shock absorber assembly 10 in accordance with the invention. The upper end of assembly 10 (Figure 1A) consists of a box-type cylindrical joint 12 having female joining threads 14. the lower end of cylindrical joint 12 includes an axial, threaded bore 16 for receiving a threaded outer surface 18 of an adaptor sleeve 20 securely therein. A pair of elastomer sealing rings 22, 24 seated within annular grooves 26, 28 provide fluid-tight affixture of adaptor sleeve 20 and cylindrical joint 12. A plurality of longitudinal flats formed around the adaptor sleeve 20 to provide a wrench space for tightening connection. The lower end of sleeve adaptor 20 is formed with an axial bore 32 having threads 34 for receiving outer end threads 36 of a mandrel 38 (see Figure 1B). The mandrel 38 defines an internal flow way or bore 40 which aligns coaxially with bore 42 of the cylindrical joint 12. Elastomer O-ring seals 44 seated within respective annular grooves 46 provide sealing structure. An upset annular band 48 is formed around mandrel 38 about mid-length. Band 48 serves as a positioning member retaining one end of a metering sleeve 50. As shown in Figure 1C, the metering sleeve 50 is retained at the other end by means of a C-ring 52 and locking ring 54 as seated within an annular groove 56 formed in mandrel 38. Referring also to Figure 1D, the lower end of mandrel 38 is formed with external threads 58 for sealing engagement within internal bore threads 60 of a lower adaptor 62. Fluid-tight affixture of adaptor 62 is assured by the plurality of elastomer O-rings 64 seated within annular grooves 66. Adaptor 62 includes a coaxial bore 64 while the outer cylindrical surface is formed with a downwardly facing annular shoulder 70 to form into a reduced radius outer cylindrical surface 72, the bottom of which has external threads 74 formed thereon. A lower retaining cap 76 having threads 78 is then secured over the lower end of adaptor 62. The cap 76 includes axial opening 80 as an upper annular surface 82 provides abutment for a seal consisting of two elastomer O-rings 84, 86 retained between two square TEFLON® rings 88 and 90. Outer casing structure consists of an end cap 92, an upper sleeve 94, an adaptor 96, and a lower sleeve 98. Lower sleeve 98 (Figure 1D) includes internal threads 100 for receiving threads 102 of a collar 104 extending a pin-type joint structure 106 having male joining threads 108 and suitable sealing ring 110. The joint end 106 defines an axial bore 112 that is concentric with the remaining axial bores 40, 42 through the shock absorber apparatus 10 to allow fluid flow therethrough. The upper cap 92 includes an inner bore 114 that is slidingly received over adaptor sleeve 20. See Figure 1A. Cap 92 also extends a collar 116 having threads 118 for secure connection within internal threads 120 of upper sleeve 94. The inside cylindrical wall 122 of upper sleeve 94 extends a plurality of splines 124 radially inward from cylindrical wall 122, the splines 124 extending from a point adjacent the bottom annular surface 126 of sleeve 20 up to a point wherein a sealing space 128 is formed beneath the upper end cap 114. Thus, a square brass ring 130 is slidably received for abutment against the ends of splines 124. A standard type of seal consisting of square TEFLON® rings 132 and 134 on each side of a pair of elastomer O-rings 136 and 138 fills out the void 128 beneath upper cap 92. The lower portion of adaptor sleeve 20 (Figure 1B) includes a circumferential array of lands 140 each of which is disposed to slidably fit between respective ones in the circumferential series of splines 124. The lands 140 may be on the order of 19 mm (three-quarters inch) arcuate length with the splines 124 formed to be about 6.4 mm (one-quarter inch) radial dimension. The dimensions of lands 140 and splines 124 are not critical so long as the slidable engagement maintains axial alignment while allowing sufficient torque force exchange. In Figure 1B, a perforate annular ring 142 having a plurality of holes 144 therethrough is disposed adjacent the annular surface 126 of adaptor sleeve 20. The perforate ring 142 provides footing for a spring 146 disposed within a circular void 148. The other end of spring 146 is buttressed against a perforate ring 150 having a plurality of equi-spaced holes 152. The perforate ring 150 is supported against the annular surface 154 of adaptor 96 as internal threads 156 of upper sleeve 94 are engaged with adaptor external threads 158 of adaptor 96 as a pair of elastomer O-rings 160 are seated within grooves 162. Referring to Figure 1C, a lower collar 164 of adaptor 96 includes external threads 166 which serve for engagement with internal threads 168 of lower sleeve 98. A pair of sealing O-rings 170 seated within grooves 172 provide fluid-tight joinder of lower sleeve 98 to adaptor 96, and lower annular surface 174 of collar 164 provides a seating surface for yet another perforate ring 176 having holes 178. The perforate ring 176 defines a void space 180 in which is disposed a spring 182 as supported on the opposite end by a perforate ring 184 having feed-through holes 186. The perforate ring 184 is further supported by an annular shoulder 188 formed about the inner cylindrical wall 190 of the lower sleeve 98. The shock absorber apparatus 10 utilizes a suitably compressible oil in certain interior spaces as will be further described below. A particularly desirable oil is silicone oil which exhibits a compressibility between 6½% and 7% at about 68.9 MPa (10,000 psi) pressure. This compressibility quotient is in a range that facilitates operation of the present invention. The silicon oil is input to the assembled shock absorber assembly 10 through sealed screw plugs 190 (Figure 1A), 192 (Figure 1C), and 194 (Figure 1D). Filling of oil through these sealed screw plugs places oil in interior spaces such as clearance 196 within upper sleeve 94 and through splines 124, in communication with void 148 via ring holes 144. The flow space extends further through ring holes 152 and clearance space 198 to the metering clearance 200 adjacent the metering sleeve 50 (Figure 1B). The metering sleeve 50 is formed from a suitable high performance plastic such as RYTON™ and the metering clearance 200 can be adjusted by machining or replacement of sleeves 50 thereby to adjust the rate of oil displacement within the void spaces, depending upon the exigencies of the particular application. Further flow communication from metering clearance 200 communicates via ring holes 178 through void space 180 and ring holes 186 to a lower sleeve clearance 202 which terminates at the seal combination made up of TEFLON® rings 88, 90 and O-ring seals 84, 86. In a present design, the springs 146 and 182 are rated to be 24.6 cm (9.69 inches) free length with a 3.8 cm (1.5 inch) preload compression while accounting for a 10.2 cm (4 inch) travel during shock absorption. There is a 305 kg (672 pound) installation load on the springs in quiescent state and they are compressible at a 203 kg (448 pounds) per 2.54 cm (inch) rate, thus requiring 813 kg (1790 pounds) per 10.2 cm (4 inch) travel during shock absorption compression. The volume of void space in spring voids 148 and 180 is 1.04 dm³ (63.44 cubic inches) and the volume of silicone oil in quiescent state contained with the springs 146, 182 is 0.62 dm³ (37.93 cubic inches) including the various clearance spaces. In operation, the shock absorber apparatus 10 is assembled with a metering sleeve 50 that provides the desired metering clearance positioned adjacent adaptor 96 as other components are assembled to make-up the tool. The interior reservoir spaces are then filled with silicone oil of selected compressibility through the respective sealable screw plugs 190, 192 and 194. In some cases, where lesser violent shock may be encountered, the assembly 10 may be utilized without inclusion of the heavy steel springs 146 and 182. In their place, additional volume of silicone oil is included since the oil compressibility provides sufficiently rapid reaction to absorb up-going or down-going shock. The tool string may include an absorber assembly 10 at various points along the string, and perforating jets may be located either above or below during detonation. Thus, the jarring effect as transmitted to the tubing may be either up-going or down-going as it creates a tremendous shock wave which sensitive gauges and recorders must endure. Any metering system that is built to handle the instantaneous loads of the shock absorber assembly 10 must be able to meter fast in order to reduce the loading, otherwise the shock absorber will effectively become a rigid member of the tubing string. The metering system of assembly 10 is formed between the clearances of the outside diameter of mandrel 38 and the inside diameter of the outer sleeve and adaptor components, and metering tolerance can be adjusted by inter-changeability of mandrel parts, particularly the metering sleeve 50. The shock force generated by the jets' detonation peaks within .045 seconds of initiation. Thus, the action of the shock absorber must be very fast in order to be effective. In a first case, with springs 146 and 182 eliminated, the compressibility of the silicone oil load within the reservoir spaces will provide sufficiently fast reaction to absorb the requisite shock. As the shock force affects the shock absorbing apparatus 10, the outer sleeve components tend toward the movement as indicated by major arrow 210 (Figure 1A) as opposite reaction of the inner or mandrel components moves in the direction of major arrow 212 (Figure 1D). For an up-going force, the outer sleeve structure including adaptor 96 and upper and lower sleeves 94 and 98 are urged upward in the direction of major arrow 210 and this tends to compress the oil contained within void 180 as released oil is metered through metering clearance 200 into the void 148 thereabove. Thus, the up-going force is effectively cushioned by the compressible oil which then rapidly decompresses to equalize pressures throughout the interior void spaces of shock absorber apparatus 10. The apparatus 10 would function in equal but opposite manner in response to down-going forces in the direction of major arrow 212. Thus, downward relative movement of inner mandrel 38 and associated components would force silicone oil from the upper void space 148 in metered amounts through metering clearance 200 to the lower void space 180 whereupon the components would then assume initial position as the oil pressures equalize. Inclusion of the springs 146 and 182 within the respective upper and lower void spaces 148 and 180 would tend to provide additional cushioning of initial force so that greater forces can be absorbed by the apparatus 10 with little or no adverse effect to sensitive components along the tool string. The foregoing discloses a novel form of shock absorber for inclusion in the tool string to isolate intense vibration and shock from sensitive components. The device can be readily assembled with interchangeable components that enable adjustment of spring and spring recovery forces so that the apparatus can be adapted for use in any of a great number of shock absorption situations. In addition, the shock absorber apparatus has the capability of being reactive to shock forces that approach from either end of the apparatus while providing equal isolation.	A hydraulic shock absorber apparatus for absorbing shock vibration along a drilling tool string, comprising an outer casing (94,96,98) having thread connector means (100) on one end for securing into said tool string, and having a cap means (92) on the other end that defines an axial opening (114); an inner casing (38) slidably disposed through said axial opening with one end extending coaxially within the outer casing and defining an annular space (148,180) adjacent thereto, and the other end having a threaded joint connector (12) for securing into said tool string; metering means (50) disposed around said inner casing and dividing said annular space into first (148) and second (180) cylindrical voids that are in communication through a restricted metering clearance (200); and oil filling said first and second cylindrical voids and said metering clearance characterized in that the said metering means (50) is a sleeve being maintained in position on the inner casing between an annular band (48) on the inner casing and an annular locking ring (54) axially spaced from the said band, the said sleeve (50) and the outer casing (96) forming therebetween a metering clearance (200) of a predetermined value, which constitutes the sole communication between the said annular voids (148,180) to provide a damping effect in both directions of relative longitudinal movement between the inner and outer casings, and in that said oil is an oil of predetermined compressibility. Apparatus according to claim 1, wherein said oil is silicone oil having a preselected compressibility. Apparatus according to claim 1 or 2, which further includes: first (146) and second (182) compression springs each aligned in a respective one of the first (148) and second (180) cylindrical voids. Apparatus according to claim 1,2 or 3, which further includes a plurality of lands (140) formed to extend longitudinally along a portion of the inner casing (38); and a plurality of splines (124) formed to extend longitudinally along a portion of the outer casing (94), said splines being slidably retained between respective pairs of lands. Apparatus according to claim 1,2,3 or 4, wherein said outer casing includes upper (94) and lower (98) sleeves sealingly joined by a threaded adaptor sleeve (96) that defines a cylindrical inner wall for disposition adjacent said metering sleeve means (50). Apparatus according to claim 1,2,3 or 4, wherein said outer casing comprises an adaptor (96) located centrally having first and second ends and having a cylindrical inner wall; an upper sleeve (94) having upper and lower ends with the lower end sealingly secured to the adaptor first end; said cap means (92) is sealingly secured to the upper sleeve upper end and defining a central bore (114) through which the inner casing (38) is closely received; a lower sleeve (98) having upper and lower ends with the upper end sealingly secured to the adaptor second end; and tool joint connector means (106) threadedly connected to said lower sleeve lower end. Apparatus according to any of claims 1 to 6, wherein said threaded joint connector (12) has a threaded lower collar; and said inner casing further comprises: an adaptor sleeve (20) having upper and lower ends with the upper end sealingly secured in the joint connector lower collar, and the lower end closely received through said cap means axial opening (114) of said outer casing; a mandrel (38) defining an axial bore (40) and having upper and lower ends with the upper end sealingly secured in said adaptor sleeve lower end, and lower cap means (76) threadedly received over the mandrel lower end with the cap means periphery closely slidable with the outer casing proximate the thread connector at one end. Apparatus according to claim 7, wherein said mandrel (38) defines said first (148) and second (180) cylindrical voids relative to the outer casing (94,98). A downhole tool string which includes a hydraulic shock absorber apparatus as claimed in any of claims 1 to 8.	HALLIBURTON CO; HALLIBURTON COMPANY	BARRINGTON BURCHUS Q; BARRINGTON, BURCHUS Q.
EP-0489528-B1	489,528	EP	B1	EN	19,960,221	1,992	20,100,220	new	H01C7	H01C1, H01C10	H01C13, H01C10, H01C7, H01C1	H01C 1/14B, H01C 7/02	Resistor device for blower motor	A resistor device for blower motor comprising one plate (A) of PTC element having two side surfaces and a plurality of electrodes (1, 2, 3) disposed on at least one of the two side surfaces. A plurality of different resistance values can be obtained from the one plate of PTC element, which makes it possible to realize a small and compact structure for the resistor device.	The present invention relates to a resistor device for controlling the rotational speed of a blower motor used in an air conditioning system for instance, one installed in an automobile. Resistor devices such as mentioned above are disposed around an outlet of a blower of an air conditioning system of an automobile so that the resistor device is cooled by the wind from the blower. A resistor device of this type is disclosed in Japanese Patent Publications (KOKOKU) No.57-45041 and No.57-32482 in which a semiconductor element of positive temperature coefficient (referred to as PTC element hereinafter) is used as the resistor element of the device. The PTC element has such a characteristic, as widely known, that the resistance thereof rises abruptly and greatly when the ambient temperature exceeds a predetermined value (Curie temperature). As a result, when the PTC element is not appropriately cooled when the current is applied thereto or when an excessive current over an allowable extent is applied to the PTC element, the temperature of the PTC element is raised gradually first and when the temperature reaches Curie temperature, the resistance of the element increases suddenly very large so that the current is controlled and the temperature is maintained below the Curie temperature. Accordingly, the PTC element is very useful for proper operation of the motor and avoiding fires in the automobile. However, according to the above mentioned Japanese patent publications (57-45041 and 57-32462) aiming at the safety structure for the motor and vehicle, the resistor device is arranged in such a manner that a plurality of ring-shaped PTC element plates and a plurality of terminal plates having a center hole are disposed alternately and combined together by bolt inserted through the center holes of the plates and secured together by a nut screwed on the bolt. In this structure, it is necessary to dispose an insulation spacer between the bolt and the terminal plates to avoid contact and short circuit between the bolt and the terminal plates. As a result, the structure becomes complicated and proper adjustment of the torque for fastening the nut is necessitated, which makes the assembling work troublesome and the cost of the device becomes high. An example of a resistor unit showing a more compact structure is given in document US-A-3 691 503; in which the resistor unit disclosed therein comprises a sheet of PTC material and a plurality of electrodes disposed on both surfaces of said sheet. The present invention was made considering the above mentioned problems of the related art. It is therefore an aim of the present invention to provide a resistor device for blower motor wherein the number of parts is reduced and the resistance against the draught from the blower is decreased, which makes it possible to simplify the structure and raise the reliability of the device. Another aim of the present invention is to provide a resistor device for blower motor wherein the productivity of the device is raised and the maintenance of the device can be conveniently carried out. Also, it is required that the structure of the resistor device be compact so as to reduce the airflow loss of the blower as much as possible. Still another aim of the present invention is to provide a resistor device for a blower motor which satisfies the requirements mentioned above. According to the present invention there is provided a resistor device for a blower motor comprising: a plate-like PTC element having two side surfaces; a plurality of electrodes disposed on at least one of said two side surfaces; and at least one terminal plate comprising at least one electrode member disposed opposite to said electrodes of the PTC element plate, the or each of said electrode members being electrically separated from the other members and having a lead terminal portion, said terminal plate means abuting said PTC element so that said electrodes of said PTC element contact said electrode members in such a manner that, by selecting any two terminals, various resistance values can be obtained between the two terminals. In another embodiment of resistor device for blower motor according to the present invention, it is desirable that a terminal plate unit comprising a plurality of electrode members be disposed to face to the electrodes of the PTC element plate, each of the electrode members being electrically separated from the other members and having a lead terminal portion. In an embodiment of the resistor device for blower motor according to the present invention, it is desirable that each of the electrode members of the terminal plate unit be formed corresponding to each of the electrodes of the PTC element plate. In still another embodiment of the resistor device for blower motor according to the present invention, it is desirable that the terminal plate unit include an electrode member spanning between a plurality of the electrodes of the PTC element plate. In a further embodiment of the resistor device for blower motor according to the present invention, it is desirable that only one electrode be disposed on the other side surface of said PTC element plate covering almost entire area of the other side surface. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that a plurality of electrodes be also disposed on the other side surface of the PTC element plate. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that electrodes be disposed in only one of the side surfaces of the PTC element plate. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that the PTC element plate and the terminal plate unit be held and secured together with the use of an elastic clip means. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that the electrode member of the terminal plate unit have a lead terminal portion protruding therefrom. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that the PTC element plate and the terminal plate unit be installed in a base holder unit in a state being combined together and pressed against each other by inserting the protruding lead terminal portions into through-holes formed in the base holder unit. In a still further embodiment of the resistor device for blower motor according to the present invention, it is desirable that a small projection for engagement be formed on a lateral side of each protruding lead terminal portion to prevent the lead terminal portion from slipping out from the through-hole. In the arrangement of the present invention mentioned above, the resistor device is constructed in such a manner that on at least one of the side surfaces of one PTC plate, a plurality of electrodes, each having a desired electric resistance, are formed and that a plurality of electrode members of terminal plates are pressingly abutted against the electrodes of the PTC plate. Therefore, only one PTC plate is needed to form the resistor device wherein the PTC plate is sandwiched by terminal plates from the both sides thereof, which makes it possible to realize a resistor device having a regular thickness irrespective of the number of electrodes of the PTC element. Therefore, it is an advantage of the present invention that the structure becomes compact as a whole so that the airflow loss is reduced and the current capacity is increased according as the cooling effect is promoted. Also, it is another advantage of the present invention that the structure of the base holder for assembling the sandwiched structure of the PTC element can be also simplified so that the number of the parts can be reduced and the device can be assembled easily and reliably. Also, the number of the resistance value obtained from the resistor device is the total number of combination from any two of the terminals. For example, if there are four electrode terminals, six kinds of resistance can be obtained from the resistor device. Thus, so many different resistance values can be obtained from one simple structure of the device of the present invention, which raises the industrial applicability of the resistor device. It is to be noted that the term terminal plate used in the present invention includes not only the plate which itself is made from a conductive member such as metal constituting an electrode itself but also a structure comprising an electric insulation plate having metal electrodes formed thereon as well. The present invention will be further described hereinafter with reference to the following description of exemplary embodiments of the invention and the accompanying drawings, in which: Fig. 1a is an exploded perspective view of the resistor device in accordance with an embodiment of the present invention; Fig.1b is a perspective view of the PTC element of the device of Fig.1a seen from the back side of the element; Fig.2 is a perspective view of an assembly of the resistor device in accordance with the present invention; Fig.3a is an exploded perspective view of the resistor device in accordance with another embodiment of the present invention; Fig.3b is a perspective view of the PTC element of the device of Fig.3a seen from the back side of the element; Fig.4 is a sectional view of the center portion of the resistor device of Fig.3; Fig.5 is a sectional view of the center portion of still another embodiment of the resistor device in accordance with the present invention; and Fig.6 is a sectional view of the center portion of further embodiment of the resistor device in accordance with the present invention. Figs.1 and 2 illustrate an embodiment of the resistor device in accordance with the present invention wherein electrodes are disposed and attached to both sides of one plate of a PTC element. Reference A in the drawings designates a plate of a PTC element having two side surfaces (front side and back side). On one of the side surfaces, which is the front side surface in this particular drawing, a plurality of electrodes 1,2 and 3 are disposed. Each electrode has a size corresponding to a desired resistance value. On the other side of the PTC plate A (back side surface), one electrode 4 is disposed, as illustrated in Fig.1b. The PTC element is made from a ceramic member composed of BaTiO₃ or compound comprising BaTiO₃ or the component elements of the compound or the compound of the same group or series of BaTiO₃ or other ceramic or plastic members. Reference B in Fig.1a designates a terminal plate comprising an electric insulation plate 50 having terminal portions 5, 6 and 7 protruding from the lower edge thereof and electrode members 8, 9 and 10 disposed on one side surface of the insulation plate 50. The electrode members 8, 9 and 10 have sizes corresponding to the sizes of the electrodes 1, 2 and 3 of the PTC element, respectively. The electrodes 8, 9 and 10 extend into the protruding terminal portions 5, 6 and 7 of the plate 50, respectively. A small projection 11 for engagement is formed on each lateral side of each of the terminal portions 5, 6 and 7. Reference C in Fig.1a designates a terminal plate comprising an electric insulation plate 51 having a terminal portion 12 protruding from the lower edge thereof and an electrode member 13 disposed on one side surface of the insulation plate 51. The electrode member 13 has a size corresponding to the size of the electrode 4 of the PTC element A (Fig.1b). The electrode 13 is formed extending into the protruding terminal portion 12 of the insulation plate 51. The terminal protrusion 12 has a small projection 11 on each of lateral sides thereof. In accordance with the present invention, the PTC element A is sandwiched between the terminal plates B and C in such a way that the electrode members 8, 9 and 10 of the terminal plate B abut against the electrodes 1, 2 and 3 of the PTC element A, respectively and that the electrode 13 of the terminal plate C abuts against the terminal 4 of the PTC element A. The sandwich structure is held and secured by a elastic clip 14 and installed in a base holder 15. The base holder 15 has a guide groove 17 into which the sandwich structure of the PTC element A interposed between the insulation plates B and C is inserted. In the bottom of the groove 17, through-holes 16 are formed at positions corresponding to the protruding terminals 5, 6, 7 and 12 of the terminal plates B and C, respectively. Only one through-hole 16 for the terminal 12 of the plate C is illustrated in Fig.1a. The terminal protrusions 5, 6, 7 and 12 are inserted to the corresponding through-holes 16 and penetrate through the base holder 15 and project below the base holder 15. The holder 15 has a connector housing 18 formed underside thereof to surround the terminals 5, 6, 7 and 12 projecting below the base holder 15. The sandwich structure is installed in the base holder 15 and secured thereto by pressingly inserting the protruding terminals into the through-holes 16 of the guide groove 17 whereby the small projections 11 of each terminal intrude into the inner surface of the through-hole to prevent the terminal protrusions from slipping out from the through-holes and avoid separation of the plates from the holder 15, thus making an assembled structure of the resistor device as illustrated in Fig.2. Figs.3 and 4 illustrate another embodiment of the resistor device in accordance with the present invention. One plate of PTC element A has a plurality of electrodes 1, 2 and 3 formed on one side surface (front surface in this particular example), as illustrated in Fig.3a. Each electrode has a size corresponding to a desired resistance value. Also, the PTC plate A has a plurality of electrodes 21, 22 and 23, each having a size corresponding to a desired resistance value, on the other side surface (back side surface) of the plate A, as illustrated in Fig.3b. Numerals 24 and 25 designate terminal plates, each constituting an electrode by itself and having a terminal 26, 27 projecting from the lower edge thereof. The terminal plate 24 is pressed against the electrode 1 of the PTC plate A. The terminal plate 25 spans over and between the electrodes 2 and 3 of the PTC plate A. The terminal plate 25 is pressed against the electrodes 2 and 3. The numerals 28 and 29 designate terminal plates, each constituting an electrode by itself and having a terminal 30, 31 projecting from the lower edge thereof. The terminal plate 28 is pressed against the two adjacent electrodes 21 and 22 formed on the backside of the PTC element A. Also, the terminal plate 29 is pressed against the electrode 23 formed on the backside of the PTC element A. The terminal plates are pressed against the electrodes of the PTC element by any appropriate means. For example, insulation plates 32 and 33 are disposed in the outside of the terminal plates from both sides of the PTC plate A, as illustrated in Fig.3a, and the vertical layered sandwich structure is held and combined together by the same elastic clip 14 as used in the first embodiment mentioned above. The sandwich structure secured by the clip is installed in the base holder 15 in a same manner as the above mentioned first embodiment, that is, by inserting the protruding terminals 26, 27, 30 and 31 into the through-holes 34 of the base holder 15. To avoid separation of the terminal plate from the base holder, small projections (not shown) may be formed on the lateral sides of the protruding terminal, as in the case of the first embodiment mentioned above. Or other appropriate means may be adopted to prevent the terminals from slipping out from the through-holes 34. Fig.4 illustrates a horizontal section of a central portion of the resistor device of Fig.3, showing the contact relation between the PTC element A, electrodes of the element and the terminal plates. The terminal plate 24 disposed in the left end of the front side of the PTC plate A and the terminal plate 29 disposed in the right end of the back side of the PTC plate A are connected in series through the PTC plate and the other terminal plates, that is, from terminal 24 through electrode 1, PTC A, electrode 21, terminal 28, electrode 22, PTC A, electrode 2, terminal 25, electrode 3, PTC A and electrode 23 to the terminal 29. By selecting any two terminals, various resistance values can be obtained between the two terminals. Fig.5 illustrates a horizontal section of a central portion of still another embodiment of the resistor device in accordance with the present invention. In this embodiment, three electrodes 1, 2 and 3 are disposed on the front surface of the PTC plate A and three electrodes 21, 22 and 23 are also disposed on the back surface of the PTC plate A. The six electrodes of the PTC plate A are pressingly covered by six terminal plates 35 to 40, respectively. Fig.6 illustrates a horizontal section of a central portion of still another embodiment of the resistor device in accordance with the present invention. In this embodiment, four electrodes 1, 2, 3 and 41 are disposed on one side surface of a PTC element plate A. One terminal plate 43 is disposed spanning between the electrodes 2 and 3 and abuts against the two electrodes 2 and 3. Also, terminal plates 42 and 44 are disposed corresponding to the electrodes 1 and 41 and abut against the electrodes, respectively. In the embodiment of Fig.6, the terminal plate 43 covers the adjacent two electrodes 2 and 3. However, any two electrodes may be covered by one terminal plate. The two electrodes may not necessarily be adjacent to each other. Also, one terminal plate may cover three electrodes or more. Further, the number of the terminal plates is not limited to three which is the case of the particular embodiment of Fig.6. It is also to be noted that the number of the electrodes of the PTC plate is not limited to that of the first embodiment or the second embodiment wherein three electrodes are disposed in the front surface and one electrode is disposed in the back surface of the PTC plate in accordance with the first embodiment and three electrodes are disposed in each of the two surfaces of the PTC plate in accordance with the second embodiment. Also, a plurality of electrodes may be arranged in only one side surface of the PTC plate and a terminal plate is disposed corresponding to each of the electrodes so that any two terminal plates are selected to obtain desired resistance values between the two terminal plates. Further, heat radiation fins may be arranged on the outer surface of the insulation plates or the terminal plates to enhance the cooling effect. It is also to be noted that the shape of the PTC element is not limited to the rectangular shape. Any desired shape may be adopted according to the design condition, the characteristic to be obtained or spatial condition of the place to mount the device.	A resistor device for a blower motor comprising: a plate-like PTC element (A) having two side surfaces; a plurality of electrodes (1, 2, 3) disposed on at least one of said two side surfaces, said device being characterized in that it comprises at least one terminal plate (B, C) comprising at least one electrode member (8, 9, 10) disposed opposite to said electrodes of the PTC element plate, the or each of said electrode members being electrically separated from the other members and having a lead terminal portion (5, 6, 7), said terminal plate abuting said PTC element so that said electrodes of said PTC element contact said electrode members, in such a manner that, by selecting any two terminals, various resistance values can be obtained between the two terminals. A resistor device according to claim 1, wherein each of said electrode members corresponds to one of said electrodes of said PTC element plate. A resistor device according to claim 1, wherein at least one electrode member spans between a plurality of said electrodes of said PTC element plate. A resistor device according to claim 1, 2 or 3, wherein a single electrode (4) is disposed on the other side surface of said PTC element plate covering substantially the entire area of the other side surface. A resistor device according to claim 1, 2 or 3, wherein a plurality of electrodes are disposed on the other side surface of said PTC element plate. A resistor device according to claim 1, 2 or 3, wherein electrodes are disposed on only one of the side surfaces of said PTC element plate. A resistor device according to any one of claims 1 to 6, wherein said PTC element plate and said terminal plate are held and secured together with the use of an elastic clip means (14). A resistor device according to any one of claims 1 to 7, wherein said lead terminal portion of said electrode member protrudes therefrom. A resistor device according to claim 8, wherein said PTC element plate and said terminal plate are installed in a base holder means (18) in a state being combined together and pressed against each other by inserting said protruding lead terminal portions into through-holes (16) formed in said base holder means. A resistor device according to claim 9, wherein a small projection (11) for engagement is formed on a lateral side of each protruding lead terminal portion to prevent said lead terminal portion from slipping out from said through-hole. A resistor device according to any one of the preceding claims, wherein there are a plurality of terminal plate each bearing a single electrode member. A resistor device according to any one of claims 1 to 10, wherein the or each terminal plate bears a plurality of electrode members.	PACIFIC ENG; PACIFIC ENGINEERING CO, LTD.	MURAKAMI IWAO; MURAKAMI, IWAO
EP-0489529-B1	489,529	EP	B1	EN	19,980,715	1,992	20,100,220	new	H01C7	H01C10	H01C7, H01C1	H01C 1/16, H01C 7/02	Resistor device for blower motor	A resistor device for blower motor comprising a plurality of PTC element plates (5, 6, 7) having both side surfaces and disposed side by side substantially in a same plane. Each PTC element has an electrode formed on each of said both side surfaces thereof. The device comprises a plurality of terminal plates (46-53) sandwiching the PTC element (5, 6, 7) plates from the both side surfaces thereof.	The present invention relates to a control circuit including a resistor device for controlling the rotational speed of a blower motor used in an air conditioning system, for instance one installed in an automobile.Resistor devices such as mentioned above are disposed around an outlet of a blower of an air conditioning system of an automobile so that the resistor device is cooled by the wind from the blower.A resistor device of this type is disclosed in Japanese Patent Publication No. 57-45041 (Kokoku)/55-155454 (Kokai) and in Publication No. 57-32482 (Kokoku)/50-102859 (Kokai) in which a semiconductor element of positive temperature coefficient (referred to as PCT element hereinafter) is used as the resistor element of the device. The PTC element has such a characteristic, as widely known, that the resistance thereof rises abruptly and greatly when the ambient temperature exceeds a predetermined value (Curie temperature). As a result, when the PTC element is not appropriately cooled when the current is applied thereto or when an excessive current over an allowable extent is applied to the PTC element, the temperature of the PTC element is raised gradually first and when the temperature reaches the Curie temperature, the resistance of the element increases suddenly very largely so that the current is controlled and the temperature is maintained below the Curie temperature. Accordingly, the PTC element is very useful for proper operation of the motor and avoiding fires in the automobile.However, according to the above mentioned Japanese patent publications (57-45041 and 57-32482) aiming at the safety structure for the motor and vehicle, the resistor device is arranged in such a manner that a plurality of ring-shaped PTC element plates and a plurality of terminal plates having a center hole are disposed alternately and combined together by bolt inserted through the center holes of the plates and secured together by a nut screwed on the bolt. In this structure, it is necessary to dispose an insulation spacer between the bolt and the terminal plates to avoid contact and short circuit between the bolt and the terminal plates. As a result, the structure is complicated and proper adjustment of the torque for fastening the nut is necessitated, which makes the assembling work troublesome and the cost of the device high.The present invention was made considering the above mentioned problems of the related art.It is therefore an aim of the present invention to provide a resistor device for a blower motor wherein the number of parts is reduced and the resistance against the draught from the blower is decreased, which makes it possible to simplify the structure, and in particular reduce the thickness of the device and raise its reliability.Another aim of the present invention is to provide a resistor device for blower motor wherein the productivity of the device is raised and the maintenance of the device can be conveniently carried out.Also, it is required that the structure of the resistor device be compact so as to reduce the airflow loss of the blower as much as possible. Still another aim of the present invention is to provide a resistor device for blower motor which satisfies the requirements mentioned above.According to the present invention there is provided a blower motor control circuit including a resistor device to be placed in the air flow from the blower, the resistor device comprising: a plurality of PTC element plates having two side surfaces and being disposed side by side substantially in the same plane, each element plate having an electrode formed on each of said side surfaces thereof; anda plurality of terminal plates sandwiching said PTC element plates on both side surfaces thereof. In a preferred embodiment of the present invention, the plurality of terminal plates include a plate comprising an electrode disposed spanning between a plurality of PTC element plates.In another preferred embodiment of the present invention, the plurality of PTC element plates are connected sequentially in series through the terminal plates disposed in both side surfaces of the PTC element plates. In a further preferred embodiment of the present invention, the terminal plate has one or more electrode terminal portions projecting therefrom.In a still further preferred embodiment of the present invention, the PTC element plates sandwiched by the terminal plates are attached to a base holder in such a way that the projecting terminal portions of the terminal plates are inserted into through-holes formed in the base holder corresponding to the terminal portions.In a still further preferred embodiment of the present invention, the PTC element plates and terminal plates are held and clamped by an elastic clip unit. In a still further preferred embodiment of the present invention, the PTC element plates and terminal plates are held and clamped by a rivet means. In a still further preferred embodiment of the present invention, the PTC element plates and terminal plates are held and clamped by a rectangular frame unit. In the arrangement of the present invention mentioned above, a plurality of PTC elements can be held without using screws or an insulation bush by such a way that the PTC elements are disposed side by side in one plane and sandwiched by a pair of terminal plates, which makes it possible to realise a resistor device having a regular thickness irrespective of the number of PTC elements. Also, in some embodiments of device of the present invention, a pair of terminal plates and the PTC element can be combined together in such a way that an end electrode of one of the terminal plate is connected in series to the other end electrode of the other terminal plate through the other electrodes of the terminal plates and the PTC elements sandwiched between the terminal plates. With such an arrangement, the number of resistance values obtained from the resistor device becomes the total combination number of any two electrode terminals.Therefore, it is an advantage that a lot of different resistance values can be easily obtained from the resistor device.Another advantage of the present invention is that the structure becomes compact as a whole, which reduces the airflow loss of the blower and raises the current capacity of the blower motor according as the cooling effect is increased.Further advantages are that the base holder structure can also be simplified, that the number of parts can be reduced, and that the device can be easily and reliably assembled, as a result of which the industrial applicability of the device can be raised. It is to be noted that the term terminal plate used in the present invention includes not only a plate made from a conductive member such as metal which forms an electrode but also a structure comprising an electrical insulating plate having metal electrodes formed thereon.The present invention will be further described hereinafter with reference to the following description of exemplary embodiments and the accompanying drawings, in which:- Figure 1 is an exploded view of an embodiment of the resistor device in accordance with the present invention;Fig.2 is a perspective view of an assembled state of the resistor device of Fig.1;Fig.3 is a sectional view of another embodiment of the present invention wherein the arrangement of the PTC elements with respect to the terminal plates is different from that of the embodiment of Fig.1;Fig.4 is an exploded view of still another embodiment of the resistor device in accordance with the present invention;Fig.5 is a perspective view of an assembled state of the resistor device of Fig.4;Fig.6 is a partial perspective view of rivet means for combining and securing the terminal plates and the PTC elements;Fig.7 is a partial perspective view of frame means as another example for combining and securing the terminal plates and the PTC elements;Fig.8 is an exploded view of still another embodiment of the resistor device in accordance with the present invention; andFig.9 is a sectional view of a further embodiment of the present invention wherein the arrangement of the PTC elements with respect to the terminal plates is different from those of the other embodiments.Fig.1 illustrates an embodiment of the present invention in an exploded view. A PTC element group C comprises a plurality of PTC elements 5, 6 and 7, each element having a desired resistance value and current capacity depending on the requirement for use. The PTC elements have a regular thickness, respectively. Also, on each side surface of the PTC elements 5, 6 and 7 is formed an ohmic electrode 5a, 6a, 7a, made from silver paste, for instance.The PTC element is made from a ceramic member composed of BaTiO3 or compound comprising BaTiO3 or the component elements of the compound or the compound of the same group or series of BaTiO3 or other ceramic or plastic members.The PTC element hereinafter refers to the PTC plate having the electrodes formed on both sides thereof.The PTC elements 5, 6 and 7 are disposed side by side in one plane. A terminal plate group A comprising two terminal plates 1 and 2 is disposed on one side of the PTC elements 5, 6 and 7. Also, another terminal plate group B comprising two terminal plates 3 and 4 is disposed on the other side of the PTC elements 5, 6 and 7. Each of the terminal plates 1 to 4 has a terminal 10, 11, 12, 13 formed at the lower edge projecting downward therefrom. The PTC element 5 is sandwiched by the terminal plates 1 and 3. The PTC element 6 is sandwiched by the terminal plates 2 and 3. And the PTC element 7 is sandwiched by the terminal plates 2 and 4.An electric insulation film 14 is disposed in the outside of the terminal plate group A. Similarly, an insulation film 15 is disposed in the outside of the terminal plate group B. The vertically layered structure of the PTC elements, terminal plates and insulation films is sandwiched by covers 16 and 17 which are made from aluminum, for instance, which is heat radiative. The covers 16 and 17 are combined and secured together by ears 18 and 19 which clamp the covers from outside thereof, as illustrated in Fig.2, so that the PTC elements are held in a state being pressed by the terminal plates from both sides thereof. An elastic clip means may be used to clamp the covers together instead of the ears 18 and 19.The combined structure constituted from the PTC elements, terminal plates and insulation films sandwiched between the covers 16 and 17 is installed in a base holder 20 in such a way that each of the projecting terminals 10 to 13 of the terminal plates 1 to 4 is inserted into a through-hole 21 which is formed in a guide groove 22 of the base holder 20 at a position corresponding to each terminal.The base holder 20 is made from synthetic resin which is heat resistant and electric insulating. The base holder 20 has the guide groove 22 formed along the center line thereof, as illustrated in Fig.1. Through-holes 21 are formed in the groove 22 corresponding to the terminals 10 to 13 of the terminal plates 1 to 4, respectively. A connector housing 23 is formed in the lower side of the base holder 20 surrounding the through-holes 21 as a whole.Each of the terminals 10 to 13 has a small projection 24 for engagement formed on each of lateral edges thereof so as to intrude into the inner surface of the through-hole wall to prevent each terminal from being slipped out from the through-hole.As mentioned above, the PTC elements 5, 6 and 7 are disposed side by side in a same plane and interposed between a pair of terminal plate groups A and B which are sandwiched between the covers 16 and 17 through the insulation films 14 and 15 disposed in the outside of each terminal group. In this state, the covers 16 and 17 are combined and secured together by the ears 18 and 19 which are folded to clamp the covers together, as illustrated in Fig.2. The sandwiched structure of the PTC elements covered by the covers 16 and 17 is attached to the base holder 20 in such a way that the terminals of the terminal plates are inserted into the through-holes 21 of the base holder 20 whereby the small projections 24 of each terminal engage and intrude into the inner wall of the through-hole so that the terminal is prevented from slipping out from the through-hole. Thus, the sandwiched structure is reliably assembled with the base holder.In accordance with the embodiment of the present invention mentioned above, six different resistance values can be obtained from the combination of any two of four terminals 10 to 13.The above mentioned embodiment refers to the arrangement wherein three PTC elements 5, 6 and 7 are sandwiched between two terminal plate groups A and B. However, the number of the PTC elements is not limited to three. Any number of the PTC elements can be interposed between the terminal plates.Fig.3 illustrates another embodiment of the present invention wherein five PTC elements 5, 6, 6, 6 and 7 are sandwiched between six terminal plates, disposing three plates 1, 3 and 3 on one side of the PTC elements and disposing the other three plates 2, 2 and 4 on the other side of the PTC elements. In this arrangement, the terminal plate 1 disposed at an end of one of the sides of the PTC elements is connected to the terminal plate 4 disposed at the other end to the other side of the PTC elements in series through the PTC element 5, the terminal plate 2, the PTC element 6, the terminal plate 3, the PTC element 6, the terminal plate 2, the PTC element 6, the terminal plate 3 and the PTC element 7. In accordance with the arrangement mentioned above, fifteen different resistance values can be obtained from the combination number of any two of six terminals.It is to be noted that the projecting terminal is not necessarily formed to every terminal plate but it may be formed only to necessary plates. Also, the shape of the terminal is not limited to that illustrated in the drawings.Fig.4 illustrates another embodiment of the present invention. Reference F designates a group of PTC elements 5, 6 and 7, each having a size corresponding to a required resistance value and current capacity as in the case of the embodiment of Fig.1.Numeral 30 designates an electric insulation plate made from alumina and having protruding terminal portions 32 and 33 formed at the lower edge thereof extending downward therefrom. On one of the side surfaces of the insulation plate, electrode members 36 and 37 are coated by printing conductive ink, for instance, extending continuously into the terminal protrusions 32 and 33, respectively. The electrode members 36 and 37 are electrically separated from each other. The insulation plate 30 and the electrodes 36 and 37 constitute a terminal plate designated by reference D as a whole. In this particular embodiment, the electrode member 36 occupies about one third of the plate 30 in the left side thereof while the other electrode member 37 occupies about two thirds of the plate 30 in the right side thereof.Numeral 31 designates an electric insulation plate made from the same material as the plate 30 mentioned above and having also protruding portions 34 and 35 for terminal extending from the lower edge thereof. Also, electrode members 38 and 39 are similarly formed on the surface of the plate 31 facing to the electrodes of the plate 30. The electrodes 38 and 39 are electrically independent from each other and extend into the protrusions 34 and 35, respectively. The insulation plate 31 and the electrode members 38 and 39 constitute a terminal plate designated by reference E as a whole. The electrode member 38, in this particular embodiment, occupies about two thirds of the plate 31 in the left side thereof seen from the back side thereof while the electrode member 39 occupies about one third of the plate 31 in the right side thereof.The terminal plates D and E are disposed in such a way that the electrode members thereof face to each other and that the PTC elements 5, 6 and 7 are interposed between the plates D and E in a state of being arranged side by side in a same plane. The PTC element 5 is disposed between the electrodes 36 and 38. The PTC element 6 is disposed between the electrodes 37 and 38. And the PTC element 7 is disposed between the electrodes 37 and 39. In this state, the terminal plates D and E are combined and secured together by an elastic clip 40 as illustrated in Fig.5.It is to be noted that the two terminal plates D and E may be combined and secured together by a rivet 41 at each corner thereof, as illustrated in Fig.6, instead of the clip 40 mentioned above. Or otherwise, a rectangular frame 42 may be used to combine and secure the two terminal plates D and E, by inserting the plates into the frame 42, as illustrated in Fig.7.In the above mentioned state where the three PTC elements 5, 6 and 7 are sandwiched and pressed by four electrode members 36 to 39, the combined structure is installed into the base holder 20 in such a way that the terminal protrusions 32 to 35 projecting from the lower edges of the plates D and E are inserted into through-holes 21 formed in the base holder 20 corresponding to the protrusions 32 to 35, respectively. The base holder is formed substantially in the same shape as that of the embodiment of Fig.1.It is to be noted that numeral 43 is a small projection for engagement formed on each lateral side edge of the terminal protrusion in order to engage and intrude into the inner wall of the through-hole 21 to prevent the protrusion from being slipped out from the through-hole 21.As mentioned above, the PTC elements 5, 6 and 7 are disposed side by side in a same plane and sandwiched between a pair of terminal plates D and E which have electrode members 36, 37, 38 and 39 in the inner side thereof, respectively. In this state, the PTC elements are held and pressed from both outer side thereof by the plates D and E with the use of any appropriate means, such as clip means, for instance, as in the case of Fig.5. The sandwich structure is installed into the base holder 20 by inserting the protruding terminal portions 32 to 35 into the through-holes 21 formed in the base holder 20 so that the sandwich structure is reliably assembled with the base holder by the function of the small projections formed on the terminal portion, as mentioned above.It is to be noted that in the above mentioned embodiment of the present invention, as in the case of the preceding embodiments, the number of PTC elements and/or electrode members are not limited to that illustrated. Also, the electrode members may be formed by affixing sheet-like electrodes to the plate by an appropriate bonding means, instead of printing the electrodes with the use of conductive ink.Fig.8 illustrates a still further embodiment of the resistor device in accordance with the present invention in an exploded view thereof. A PTC element group I is constituted from three PTC elements 5, 6 and 7, in this particular embodiment, each element having a size corresponding to a required resistance and current capacity, as in the case of embodiment of Fig.1.Numerals 44, 45 and 46 designate terminal plates constituting a terminal plate group G which is disposed facing to the front side of the PTC elements 5, 6 and 7. Each of the terminal plates has a terminal portion 47, 48, 49 protruding from the lower edge thereof. Numerals 50, 51 and 52 designate terminal plates similarly constituting a group H of terminal plates disposed facing to the rear side of the PTC elements 5, 6 and 7. The terminal plates 50 to 52 also have protruding terminal portions 53, 54 and 55, respectively, formed at the lower edges thereof.In this embodiment, the device structure is essentially arranged in such a way that each of the plurality of PTC elements which are disposed side by side in a same plane is sandwiched by a pair of terminal plates arranged individually for each element. Electric insulation plates 56 and 57 are disposed in the outer sides of the terminal plates, respectively. The plates 56 and 57 are combined and secured together sandwiching the PTC elements and terminal plates therebetween by an appropriate clamping means such as clip means 40 of Fig.5, rivet means 41 of Fig.6 or rectangular frame means 42 of Fig.7. And in the state where the group I of PTC elements is sandwiched and pressed by the pair of terminal plate groups G and H, the terminal protrusions 47 to 49 and 53 to 55 formed at the lower edges of the terminal plates are inserted into through-holes 21 formed in the base holder 20 corresponding to the protrusions. The sandwich structure is held and secured to the base holder by an appropriate means to form an assembly of the resistor device.Fig.9 illustrates a still further embodiment of the resistor device in accordance with the present invention along a cross section thereof. A PTC element group L is constituted from five PTC elements 5, 6, 7, 58 and 59, disposed side by side in a same plane, each of which elements has a size corresponding to a required resistance and current capacity, as in the case of the embodiment of Fig.1. In this embodiment of Fig.9, the arrangement of terminal plates is featured in that the plates press and sandwich the PTC elements from both sides thereof in such a way that the PTC element 5 is held by terminal plates 60 and 61 which are independent from the other terminal plates, that the PTC element 6 is held by an independent terminal plate 62 disposed in one side thereof and a terminal plate 63 disposed in the opposite side thereof covering also the adjacent PTC element 7, that the element 7 is held by the plate 63 and a terminal plate 64 disposed in the opposite side of the plate 63 which plate 64 spans between the elements 7 and 58, that the PTC element 58 is held by the terminal plate 64 and an independent terminal plate 65, and that the PTC element 59 is held by independent terminal plates 66 and 67 from both sides thereof.In accordance with the embodiment of Fig.9 mentioned above, from the combination of five PTC elements and eight terminal plates, it becomes possible to obtain various different resistance values in a manner different from those of the preceding embodiments mentioned before.It is to be noted that in the illustrated embodiments mentioned above, the PTC elements have a same thickness for every embodiment. However, the thickness and size of the PTC elements are not necessarily the same in the same group of the elements. If a PTC element of different thickness is included in a group of PTC elements, the thickness of the insulation plate disposed in the outside of the terminal plates is adjusted to compensate for the unevenness of thickness so as to obtain a flat outer plane of the resistor device.It is also to be noted that the shape of the PTC element is not limited to the circular shape or rectangular shape as illustrated in the drawings.	A blower motor control circuit including a resistor device to be placed in the air flow from the blower, the resistor device comprising: a plurality of PTC element plates (5,6,7) having two side surfaces and being disposed side by side substantially in the same plane, each element plate having an electrode (5a,6a,7a) formed on each of said side surfaces thereof; anda plurality of terminal plates (1 to 4) sandwiching said PTC element plates on both side surfaces thereof.A control circuit according to claim 1, wherein said plurality of terminal plates includes a plate (2,3) forming an electrode disposed so as to span between a plurality of PTC element plates.A control circuit according to claim 1 or 2, wherein said plurality of PTC element plates are connected in series through said terminal plates disposed against both side surfaces of the PTC element plates.A control circuit according to claim 1, 2 or 3, wherein each terminal plate has one or more terminal portions (10,11,12,13) projecting therefrom.A control circuit according to claim 4, wherein said PTC element plates sandwiched by said terminal plates are attached to a base holder (20) in such a way that said projecting terminal portions of said terminal plates are inserted into corresponding through-holes (21) formed in said base holder. A control circuit according to claim 5, wherein said PTC element plates and terminal plates are held and clamped by an elastic clip means (18,19,40).A control circuit according to claim 5, wherein said PTC element plates and terminal plates are held and clamped by a rivet means (41).A control circuit according to claim 5, wherein said PTC element plates and terminal plates are held and clamped by a rectangular frame means (42).A control circuit according to any one of the preceding claims wherein there are two terminal plates (30,31), each comprising an electrically insulating plate having conductive electrodes (36 to 39) thereon.	PACIFIC ENG; PACIFIC ENGINEERING CO, LTD.	MURAKAMI IWAO; MURAKAMI, IWAO
EP-0489531-B1	489,531	EP	B1	EN	19,951,004	1,992	20,100,220	new	H01Q1	H01Q1, B64G1	H01Q1, B64G1	B64G 1/54, H01Q 1/00C, H01Q 1/42C	Antenna sunshield membrane	An RF-transparent sunshield membrane (324) covers an antenna reflector such as a parabolic dish. The blanket includes a single dielectric sheet (310) of polyimide film 1/2-mil thick. The surface of the film facing away from the reflector is coated with a transparent electrically conductive coating (316) such as vapor-deposited indium-tin oxide. The surface of the film facing the reflector is reinforced by an adhesively attached polyester or glass mesh (312), which in turn is coated with a white paint (314). In a particular embodiment of the invention, polyurethane paint is used. In another embodiment of the invention, a layer of paint primer is applied to the mesh under a silicone paint, and the silicone paint is cured after application for several days at room temperature to enhance adhesion to the primer.	This invention relates to RF-transparent electrically conductive thermal membranes or blankets for protection of antennas against thermal effects from sources of radiation such as the sun. An antenna including a parabolic reflector can, if pointed at a source of radiation such as the sun, focus the energy from the sun onto the reflector's feed structure, possibly destroying the feed. Also, the reflector may be heated in such a manner that mechanical distortion or warping occurs, which may adversely affect proper operation. When the antenna is mounted on a satellite as illustrated in FIGURE 1, a fluence of charged particles may cause electrostatic potentials across portions of the antenna made from dielectric materials. If the potentials are sufficiently large, electrostatic discharges (ESD) may occur, resulting in damage to sensitive equipments. A sunshield adapted for use across the aperture of a reflector antenna should significantly attenuate passage of infrared, visible and ultraviolet components of sunlight to the reflector, should have a conductive outer surface to dissipate electrical charge buildup which might result in electrostatic discharge (ESD), and should be transparent to radio-frequency signals, (RF) which for this purpose includes signals in the range between the UHF band (30 to 300 MHz) and Ku band (26 to 40 GHz), inclusive. Prior art multilayer sunshields which include plural layers of aluminized polyimide film such as Kapton film cannot be used, because they are opaque to RF at the above-mentioned frequencies. An RF-transparent multilayer blanket is described in a copending application entitled RF-TRANSPARENT SPACECRAFT THERMAL CONTROL BARRIER , filed concurrently herewith in the names of Munro, III et al. A multilayer blanket may be disadvantageous because absorbed heat can become trapped among the several layers. The temperature of the layers rises, and they produce infrared radiation which can impinge on the reflector, thereby causing the reflector to overheat. U.S. Patent 4,479,131, issued October 23, 1984 to Rogers et al., describes a thermal protective shield for a reflector using a layer of germanium semiconductor on the outer surface of a sheet of Kapton, with a partially aluminized inner surface, arranged in a grid pattern which is a compromise between RF transmittance and solar transmittance. To the extent that this arrangement allows solar transmittance, the shield and/or the reflector may heat. Such heating may not be controllable because the reflectivity of the aluminized sheet may reflect infrared from the reflector back toward the reflector, and also because both the germanium and aluminization have low emissivity. FIGURE 2 illustrates a cross-section of another RF-transparent prior art sunshield, which consists of one layer of structure. The one layer of structure includes a two-mil (0.002 inch) black Kapton film 210, reinforced with adhesively-affixed Dacron polyester mesh 212 on the side facing the reflector, and with the space-facing side painted to a thickness of about four mils with a white polyurethane paint 214 such as Chemglaze Z202, manufactured by Lord Corporation of 2000 West Grandview Boulevard, Erie, Pennsylvania 16512. The surface of the paint is vapor coated with an electrically conductive layer 216 such as 75 ± 25Å of indium-tin oxide (ITO). Such a sunshield, immediately after manufacture, has solar absorptivity α, averaged over the visible spectrum, between 2.5 and 25 microns, of about 0.3, an emissivity (ε) of about 0.8, and a surface resistivity in the range about 10⁶ to 10⁸ ohms per square. It has two-way RF insertion loss of 0.24 dB. It has been discovered that exposure of the above described single-layer sunshield to a fluence of charged particles and solar ultraviolet radiation causes a gradual degradation. The on-orbit data, together with simulation data, suggest that in the course of a 10-year mission, α increases from about 0.3 to about 0.85, and surface resistivity increases to about 10⁹ ohms per square. Such an increase in absorptivity may cause the single-layer sunscreen to produce infrared radiation, which may cause the antenna reflector to overheat. The increase in surface resistivity may result in ESD. New generations of satellites are intended to have mission durations much exceeding ten years, so the prior art sunscreen cannot be used. An improved sunscreen is desired. Summary Of The InventionA thermal membrane according to the invention is defined in claim 1. In a particular embodiment of the invention, the white paint is a cured polyurethane paint, which may be degraded in the presence of a fluence of charged particles and ultraviolet radiation. In this particular embodiment, the dielectric film is transparent Kapton polyimide film about 1/2-mil (0.0005 inch) thick, which absorbs ultraviolet light, and which prevents the charged particles from reaching the paint, whereby the paint does not degrade excessively over time. In a further embodiment of the invention, the single layer comprises a reinforcing mesh of Dacron polyester fiber adhesively affixed to the inner surface of the Kapton film, with the polyurethane paint applied over the mesh. In a further embodiment of the invention, the polyurethane paint is Chemglaze Z202, cured at room temperature (air cured) for seven days. Description Of The DrawingFIGURE 1 is a perspective or isometric view of a reflector antenna mounted on a spacecraft, with a sunscreen illustrated as being exploded away from the reflector to show details; FIGURE 2 is a cross-sectional view of a single structured layer sunscreen according to the prior art, which may be used as the sunscreen in FIGURE 1 but which may not have a sufficiently long life span for some missions; and FIGURE 3 is a cross-sectional view of a single structured layer sunscreen according to the invention, which may be used as a sunscreen in FIGURE 1 and which is expected to have a longer mission life than the sunscreen of FIGURE 2. Description Of The InventionIn FIGURE 1, a spacecraft designated generally as 10 includes a body 12 having a wall 14. First and second solar panels 18a and 18b, respectively, are supported by body 12. A reflector antenna 20 including a feed cable 21 provides communications for satellite 10. Feed cable 21 terminates in a reflector feed 23 at the focal point of reflector 20. As mentioned above, if reflector 20 is directed toward a source of radiation such as the sun, the radiation may be absorbed by the structure of the reflector, raising its temperature and possibly warping or destroying its structure. Even if the reflector is not affected, it may concentrate energy on, and destroy, feed 23. A known scheme for reducing the problems described above is to cover the open radiating aperture of reflector 20 with a sunscreen or thermal barrier membrane (blanket), illustrated as sheet 24 in FIGURE 1, exploded away from reflector 20. Sunscreen 24 may be attached to the rim of reflector 20 by means (not illustrated) such as adhesive, or it may be held by fasteners, such as Velcro tape. FIGURE 2 illustrates in cross-sectional view a prior-art sunscreen which may be used with reflector 20 of FIGURE 1. Sunscreen 24 of FIGURE 2 is a single sheet-like structure, termed a single layer, to distinguish it from multilayer blankets which are also used in the art. A multilayer blanket may be similar to that described in the above-mentioned Munro, III et al. application, and includes plural, separated layers of dielectric, some of which may be coated. As mentioned above, such multilayer structures allow heat to build up among the layers, which rise in temperature and generate infrared radiation. The infrared radiation can heat the reflector, possibly causing warping or damage. Such multilayer blankets may be advantageous by virtue of decreasing the temperature rise of the inner layers when a source of radiation heats the outer layer, but the several layers interpose more mass between the antenna and free space than a single-layer blanket, and this additional mass may occasion more loss or attenuation for RF signals passing therethrough than a single-layer blanket. This attenuation may be particularly troublesome when RF signal must pass through the blanket twice, as may occur when the reflector feed must radiate through the blanket to the reflector, and back from the reflector through the blanket to space. Single-layer blanket 24 of FIGURE 2 includes a sheet 210 of black polyimide film about two mils (0.002 inch) thick. A layer 212 of polyester fiber mesh, such as Dacron polyester fiber or glass fiber mesh, is affixed to the reflector-facing side of polyimide sheet 210 by a hot-melt moisture-cure polyurethane adhesive (not illustrated). The space-facing side of polyimide film 210 is coated to a thickness of about four mils (0.004 inch) with a layer 214 of polyurethane paint such as Chemglaze Z202. An electrically conductive coating 216 such as vapor-deposited indium-tin oxide is deposited over the space-facing side of paint layer 214. In the presence of charged particles and solar ultraviolet radiation, the paint tends to turn brown, which is a visible indication of the degradation of its properties. As mentioned, the absorptivity α tends to rise from 0.3 toward 0.85, thereby tending to absorb more energy in the form of visible light and infrared, which therefore tends to raise the temperature of the sunscreen. The emissivity remains substantially constant, which means that the increased energy which the sunscreen absorbs tends to be reradiated as heat both toward space and toward the reflector. Also, the resistivity of the ITO coating tends to increase, thereby increasing the danger of ESD. FIGURE 3 illustrates a cross-section of a sunscreen 324 according to the invention, which may be used as sunscreen or membrane 24 of FIGURE 1. The single structure of FIGURE 3 includes a sheet 310 of transparent polyimide film about 1/2-mil thick (0.0005 inch). A suitable material is Kapton, manufactured by E.I. Du Pont de Nemours Company. A reinforcing web 312 of Dacron polyester fiber mesh or glass fiber mesh is affixed to the reflector-facing side of polyimide sheet 310 by a hot-melt moisture-cure polyurethane adhesive (not separately illustrated). A coating 316 of transparent indium-tin oxide is deposited on the space-facing side of polyimide sheet 310. Satisfactory performance has been achieved by a coating with a thickness of about 75±25Å, applied by a vapor deposition process by Sheldahl, whose address is 1150 Sheldahl Road, Northfield, Minnesota 55057-0170. Such ITO coatings have a resistivity in the range of 10⁶ to 10⁸ ohms per square. In accordance with an aspect of the invention, a layer 314 of white polyurethane paint is applied to the reflector-facing side of polyimide film 310, over reinforcing mesh 312 if a mesh is used. The aforementioned Chemglaze type Z202 may be used, or type S13-G/LO silicone paint, manufactured by Illinois Institute of Technology Research Institute, whose address is 10 West 35th Street, Chicago, Illinois. Adhesion of the silicone paint is promoted by applying an adhesive primer (not separately illustrated) before applying the silicone paint. A suitable primer is made from A-1100, manufactured by Union Carbide Chemicals and Plastics Company, Inc., whose address is 318-24 4th Avenue, P.O. Box 38002, South Charleston, West Virginia. The primer is transparent, so the white silicone paint is visible from the space-facing side of sunscreen 324, through transparent ITO layer 316, transparent Kapton film layer 310, transparent or translucent mesh 312 and its adhesive, and through the transparent primer. Sunscreen 324 of FIGURE 3 has absorptivity α = 0.291, and an emissivity ε = 0.91 looking at the space-facing side. The paint is protected from charged particles by the Kapton film, and the film also absorbs a significant amount of solar ultraviolet light. Thus, polyurethane paint layer 314 receives less ultraviolet light than layer 214 of FIGURE 2. A sunscreen according to the invention was tested by exposure to a simulated space environment. The tests included exposure to ultraviolet light for 3525 equivalent sun hours (ESH), 400 thermal cycles from -150°C to +150°C, and an exposure for 1024 ESH to the combined effects of electron fluence of 3x10¹⁵ #/cm², a proton fluence of 4X10¹⁴ #/cm², and UV light. The 3525 ESH UV test is equivalent to about 1 1/2 years in orbit. The tests showed a change of α from 0.30 to 0.32 for the S13-G/LO paint, and from 0.41 to 0.42 for the Z202 paint, which is within the accuracy of the measurement. The emissivity was unchanged at 0.90 by the test, and the resistivity remained at 10⁷ ohms per square. It has been observed that seven-hour oven-curing of the polyurethane paint may produce conditions under which the reinforcement mesh tends to delaminate from the Kapton film. It is believed that this occurs because the solvents distilled from the paint are also solvents for the hot-melt moisture-cure polyurethane. A similar problem occurs with silicone paint. In both cases, the problem is avoided by the use of room temperature cure (air cure). The single-structure or single-layer sunscreen may be manufactured by the following steps, in the order listed. (a) attach reinforcing mesh to 1/2-mil Kapton film. The mesh may be polyester or glass fiber. (b) deposit ITO coating on non-reinforced side. (c) mask ITO-coated side to prevent painting thereof, by attaching TEXWIPE material, manufactured by TEXWIPE Company, whose address is P.O. Box 308, Upper Saddle River, New Jersey 07458, or 1/2-mil Mylar film, with Kapton adhesive tape along the perimeter of the sample. (d) paint reinforced side with primer; allow to dry. (e) paint reinforced side with S13-G/LO. (f) cure paint at room temperature (no higher than 30°C) for seven days. (g) remove masking material by cutting off the edges of the TEXWIPE or 1/2-mil Mylar. If Chemglaze Z202 is used in step (e) above, step (d) is deleted, as no primer is needed. Other embodiments of the invention will be apparent to those skilled in the art. For example, while the sunscreen has been described as a cover for a reflector antenna, it may be applied as a blanket around a portion of the spacecraft, as illustrated by sunscreen 26 of FIGURE 1, illustrated exploded away from wall or face 14 of spacecraft body 12. As illustrated in FIGURE 1, an antenna 22 is flush-mounted in wall 14, and may radiate through sunscreen 26 when in place. Also, the reflector feed may be within the reflector, so that the feed is also protected against thermal effects by a membrane according to the invention placed over the mouth or opening of the reflector.	A thermal membrane for at least a portion of a spacecraft comprising: a sheet (310) of transparent dielectric film located between said portion and space, to thereby define inner and outer surfaces of said dielectric film facing said portion and space, respectively; a layer (316) of transparent, electrically conductive material affixed to said outer surface of said sheet of dielectric film; and a layer (314) of white paint affixed to said inner surface of said sheet of dielectric film. A membrane according to claim 1, further comprising a reinforcing mesh (312) interposed between said layer of white paint and said inner surface of said film. A membrane according to claim 2 wherein said reinforcing mesh is a polyester fiber mesh or a glass fiber mesh. A membrane according to claim 2 further comprising adhesive means in contact with said inner surface of said film and with said reinforcing mesh for affixing said mesh to said film. A membrane according to claim 1 wherein said dielectric film absorbs significant amounts of ultraviolet radiation. A membrane according to claim 1 wherein said dielectric film is a polyimide film. A membrane according to claim 6 wherein said film has a thickness of about 0.0005 inch. A membrane according to claim 1 further comprising a primer interposed adjacent to said layer of white paint. A membrane according to claim 1 or 8 wherein said paint is a polyurethane or a room-temperature-cured silicone paint. A membrane according to claim 1 wherein said layer of electrically conductive material comprises a vacuum-deposited layer less than 100Å thick of indium-tin oxide.	GEN ELECTRIC; GENERAL ELECTRIC COMPANY	BOGORAD ALEXANDER NMN; BOWMAN CHARLES KENNETH JR; MEDER MARTIN GERHARDT; BOGORAD, ALEXANDER (NMN); BOWMAN, CHARLES KENNETH, JR.; MEDER, MARTIN GERHARDT
EP-0489532-B1	489,532	EP	B1	EN	19,950,201	1,992	20,100,220	new	H05B41	H01J65	H05B41, H01J65, H01J61, F21S2	H05B 41/24, H01J 65/04A, H01J 61/54C, H01J 65/04A3	Electrodeless discharge lamp	This electrodeless high intensity discharge lamp comprises a light-transmissive arc tube having spaced wall portions of dielectric material and a first gaseous fill within the arc tube. An excitation coil about the arc tube is energizable with RF current effective to develop a toroidal arc discharge in the first gaseous fill upon a dielectric breakdown of the fill. A starting container is joined to the arc tube and has an end wall constituted by one of said arc-tube wall portions. a second gaseous fill within the starting container has a dielectric strength lower than that of the first gaseous fill. For initiating said toroidal arc discharge, we provide means for producing a dielectric breakdown of the gaseous fill within the starting container that develops into an electric discharge that changes the potential at said end wall in such a manner as to cause a dielectric breakdown of said first gaseous fill.	FIELD OF THE INVENTIONThe present invention relates generally to high intensity discharge (HID) lamps. More particularly, the present invention relates to an improved starting aid for an electrodeless HID lamp. BACKGROUND OF THE INVENTIONIn a high intensity discharge (HID) lamp, a medium to high pressure ionizable gas, such as mercury or sodium vapor, emits visible radiation upon excitation typically caused by passage of current through the gas via an arc discharge. One class of HID lamps comprises inductively coupled electrodeless lamps which develop and maintain an arc discharge by generating a solenoidal electric field in a high-pressure gaseous lamp fill. In such a lamp, the high pressure fill within an arc tube is initially broken down by an electric discharge, and the resulting discharge plasma is excited by radio frequency (RF) current in an excitation coil surrounding the arc tube. The arc tube and excitation coil assembly act essentially as a transformer which couples RF energy to the plasma. That is, the excitation coil acts as a primary coil, and the plasma functions as a single-turn secondary coil inductively coupled to the primary coil. RF current in the excitation coil produces a time-varying magnetic field, in turn creating an electric field in the plasma which substantially closes upon itself, i.e., a solenoidal electric field. Current flows as a result of this electric field, resulting in a toroidal arc discharge in the plasma within the arc tube. The toroidal discharge in an inductively coupled HID arc tube is generally more difficult to start than the discharge in a conventional arc tube having electrodes serving as terminals for the discharge. There are several reasons for this. First, the absence of electrodes eliminates the beneficial role which electrodes often play in starting electroded arc tubes. For example, without the electrodes, there is no opportunity for electric field concentrations at the electrode tip and no opportunity for generating initial electrons by physical processes at the surface of the cathode electrode such as by thermionic emission, field emission, or ion bombardment. Second, it is very difficult to inductively generate the very high electric fields required for breakdown of the relatively high-pressure fill gas within the arc tube. Third, we utilize as the buffer gas in our arc-tube fill a high pressure inert gas, rather than mercury. For example, in one embodiment of our invention, we utilize as the buffer gas within our arc-tube fill krypton or xenon having a room-temperature pressure of 250 torr or more. This inert-gas pressure is approximately ten times higher than the inert-gas pressure which is desirable for initial starting breakdown. There have been a number of approaches tried or suggested for initiating the arc discharge in the high pressure inert gas arc-tube fill of an electrodeless lamp. One early approach involves lowering the gas pressure of the fill, for example, by first immersing the arc tube in liquid nitrogen so that the gas temperature is decreased to a very low value and then allowing the gas temperature to increase. As the temperature rises, an optimum gas density is momentarily reached for ionization, or breakdown, of the fill to occur so that an arc discharge is initiated. However, the liquid nitrogen method of initiating an arc discharge is not practical for widespread commercial use. More recent approaches have involved the use of a variety of metallic starting aids , which typically serve to increase the electric field for starting. These metallic starting aids are usually located outside the arc-tube envelope but in some cases have been starting electrodes which enter the arc-tube envelope through seals. Examples of such metallic starting aids are shown in U.S. Patents 4,894,589, 4,894,590, 4,902,937, 5,047,693 published September 10, 1991, 4,982,140 published Januar 01,1991, 5,059,868 published Oktober 22, 1991 (EP-A-0 458 546 publ. 27.11.91) and 5,084,654 published Januar 28, 1992 (EP-A-0 458 544 publ. 27.11.91). There are some disadvantages in using a metallic starting aid. For example, if the metallic starting aid is of such a character that it remains in place during lamp operation, it may serve as a vehicle for a life-limiting mechanism such as sodium loss, degradation of the arc-tube envelope wall, or seal failure. On the other hand, if a metallic starting aid is of such a character that it is removed or withdrawn after starting, then the complications and expense involved in controlling such moving part are introduced into the lamp design. Furthermore, a movable starting aid tends to change the impedance matching requirements of the energizing circuit for the excitation coil. SUMMARY In carrying out the invention in one form, we provide an electrodeless HID lamp comprising a light-transmissive arc tube having spaced wall portions of dielectric material and a first gaseous fill within the arc tube. Disposed about the arc tube is an excitation coil energizable with radio frequency current that is effective to develop a toroidal arc discharge in the first gaseous fill upon a dielectric breakdown of this fill. A starting container of tubular configuration and primarily of dielectric material is joined to the arc tube and has an end wall that is constituted by one of said arc-tube wall portions. Within the starting container there is a second gaseous fill that has a dielectric strength substantially lower than that of the first fill under normal conditions prevailing immediately prior to start up of the lamp. The toroidal arc discharge within the arc tube is initiated by means producing a dielectric breakdown of the gaseous fill within the starting container, which breakdown develops into a discharge that extends along the length of said starting container and changes the potential at said end wall in such a manner as to increase the voltage present between said arc-tube wall portions sufficiently to trigger a dielectric breakdown of said first gaseous fill. BRIEF DESCRIPTION OF FIGURESFor a better understanding of the invention, reference may be made to the following detailed description taken in connection with the accompanying drawings, wherein: Fig. 1 is a partially schematic and partially sectional view of an electrodeless lamp embodying one form of our invention. Fig. 1 depicts the lamp in its run , or operating, mode. Fig. 2 is a view similar to that of Fig. 1 except showing the lamp during an initial breakdown stage early in a startup operation. Fig. 3 is a view similar to that of Fig. 1 except showing the lamp in a transfer stage that occurs immediately following the stage depicted in Fig. 2 but immediately prior to the start of the operating mode depicted in Fig. 1. Fig. 4 is an enlarged sectional view of a portion of a lamp embodying a modified form of our invention. Fig. 5 is a view similar to that of Fig. 1 showing a modified electrodeless lamp embodying another form of our invention. DETAILED DESCRIPTION OF EMBODIMENTReferring first to Fig. 1, the electrodeless lamp 10 shown therein comprises an arc tube 14 having its walls formed, preferably, of a high temperature glass, such as fused quartz, or an optically transparent or translucent ceramic, such as polycrystalline alumina. An excitation coil 16 surrounds the arc tube and is coupled to a radio frequency (RF) ballast 18 for exciting a toroidal arc discharge 20 in the arc tube. By way of example, arc tube 14 is shown as having a substantially ellipsoidal shape. However, arc tubes of other suitable shapes may sometimes be desirable, depending upon the application, and are comprehended by our invention. For example, the arc tube may be substantially spherical or may have the shape of a short cylinder, or pillbox , having rounded edges. An arc tube of the latter configuration is shown and described in U.S. Patent 4,810,938, Johnson et al, referred to in more detail in the next paragraph hereof. Arc tube 14 contains a fill in which the above-mentioned arc discharge having a substantially toroidal shape is excited during lamp operation. A suitable fill is described in U.S. Patent No. 4,810,938 of P. D. Johnson, J. T. Dakin and J. M. Anderson, issued on March 7, 1989, and assigned to the instant assignee. The fill of the Johnson et al patent comprises a sodium halide, a cerium halide and xenon combined in weight proportions to generate visible radiation and exhibiting high efficacy and good color rendering capability at white color temperatures. For example, such a fill according to the Johnson et al patent may comprise sodium iodide and cerium chloride, in equal weight proportions, in combination with xenon at a room temperature partial pressure of about 500 torr. Another suitable fill is described in U.S. patent 4,972,120 (Witting). The fill of this patent comprises a combination of a lanthanum halide, a sodium halide, and xenon or krypton as a buffer gas. A specific example of a fill according to US-A-4972120 (Witting) comprises a combination of lanthanum iodide, sodium iodide, cerium iodide and 250 torr partial pressure of xenon at room temperature. Another suitable fill is one comprising a combination of sodium iodide, cerium iodide and 250 torr partial pressure of krypton at room temperature. As illustrated in Figure 1, RF power is applied to the HID lamp by RF ballast 18 via excitation coil 16 coupled thereto. Excitation coil 16 is illustrated as comprising a two-turn coil having a configuration such as that described in the commonly assigned U.S. Patent 5,039,903 published August 13, 1991. Such a coil configuration results in very high efficiency and causes only minimal light blockage from the lamp. The excitation coil of the Farrall application comprises one or more turns connected in series. The shape of each turn is generally formed by rotating a bilaterally symmetric trapezoid about a coil center line situated in the same plane as the trapezoid, but which line does not intersect the trapezoid, and providing a cross-over means for connecting the turns. However, other suitable coil configurations may be used with the starting aid of the present invention, such as that described in commonly assigned U.S. Patent No. 4,812,702 of J. M. Anderson issued March 14, 1989. In particular, the Anderson patent describes a coil having six turns which are arranged to give the coil a substantially V-shaped cross section on each side of the coil center line. Still another suitable excitation coil may be of solenoidal shape, for example. In operation, RF current in coil 16 results in a time-varying magnetic field which produces within arc tube 14 an electric field that substantially closes upon itself. Once the lamp is started, as will soon be described, current flows through the fill within arc tube 14 as a result of this solenoidal electric field, producing the toroidal arc discharge 20 in the fill. Suitable operating frequencies for RF ballast 18 are in the range from 0.1 to 300 megahertz (MHz), an exemplary operating frequency being 13.56 MHz. A suitable ballast 18 is described in commonly assigned U.S. Patent 5,047,692 of J. C. Borowiec and S. A. El-Hamamsy published September 10, 1991. The lamp ballast of the cited patent application is a high-efficiency ballast comprising a Class-D power amplifier and a tuned network. The tuned network includes an integrated tuning capacitor network and heat sink. In particular, two capacitors, the first in series combination and the second in parallel combination with the excitation coil, are integrated by sharing a common capacitor plate. Furthermore, the metal plates of the parallel tuning capacitor comprise heat conducting plates of a heat sink used to remove excess heat from the excitation coil of the lamp. The arc tube 14 of Fig. 1 is enclosed within an outer envelope 22, preferably of quartz, that serves to reduce heat loss from the arc tube, absorb ultraviolet radiation from the toroidal arc discharge within the arc tube, and protect the arc tube walls from harmful surface contamination. The arc tube is also supported from the outer envelope 22 by means of a hollow stem 24 of elongated tubular configuration. In a preferred form of the invention, the arc tube wall is of quartz and the stem 24 is of quartz tubing butt-joined through fusion to the outer surface of the quartz arc tube wall. In the localized region 27 where the quartz tubing is joined to the quartz arc-tube wall, the portion 52 of the arc-tube wall is substantially flat on both its outer surface and on its inner surface. In a location 29, spaced along the stem 24 from the region 27, the stem 24 extends through an opening in the top wall 30 of the outer envelope 22 and is fused about the outer periphery to the top wall to form a vacuum-tight seal. The space 32 between the outer envelope 22 and the arc tube 14 is evacuated so as to provide thermal insulation for reducing heat loss from the arc tube. The upper end of the stem 24 is sealed off so that within the stem there is a closed chamber 35. This chamber is filled with a gas that has a substantially lower dielectric strength than that of the gaseous fill located within the arc tube 14, considered under the normal conditions prevailing just prior to start-up of the lamp 10. This gas that fills chamber 35 can be the same gas as present in the arc tube 14 but at a lower pressure than the gas present in the arc tube, e.g., at a pressure of about 1/10 of that of the arc tube. Alternatively, the gas in chamber 35 may be a different gas which can be broken down by an easily-developed and handled high voltage. Examples of specific gases usable in the chamber 35 are krypton, xenon, neon, argon, helium, and mixtures thereof. In each case the pressure of this fill should be low enough to impart a dielectric strength to the gas below that of the gas within arc tube 14. In our specific embodiment, we use for the fill in chamber 35 pure krypton at a room-temperature pressure of 20 torr. A specific example of a gas mixture that is advantageously usable is a Penning mixture consisting of a mixture of neon and argon. The stem, or container, 24 and the gas within its chamber 35 may be thought of as being part of a starting aid for assisting in the development of the toroidal arc discharge 20 in arc tube 14. As will soon appear more clearly, a significant feature of our lamp is that the starting container, or stem, 24 has one end wall (its lower end wall) which is constituted by a part of the wall portion 52 of the arc tube 14. Our starting aid further comprises means for developing and applying a high voltage to initiate breakdown in hollow stem 24 and subsequently in chamber 14. This means schematically illustrated in Fig. 1, comprises the parallel combination of an inductor 38 and a capacitor 40 connected between a ground potential point on the upper turn of excitation coil 16 and the upper end of the starting container 24 via conductors schematically shown at 39 and 41. A suitable switch 42 connected in series with the parallel combination can be closed to connect the parallel combination across the source through the stray capacitance of the lamp and can be opened to interrupt the circuit that connects the parallel combination across the source. Additional details of the voltage developing and applying means 38 - 42 are disclosed in commonly-assigned U.S. Patent 5,103,140 published April 07, 1992 - Cocoma et al and US Patent 5,057,750 published Oktober 15, 1991 - Farrall et al. The L-C circuit 38, 40 is tuned so that it is in a condition of approximate resonance when energized by the 13.56 MHz RF current of ballast 18. When a high voltage is developed across the L-C circuit 38, 40 by the RF current from ballast 18, a corresponding high voltage is applied across the length of starting container 24 and also across the length of the column of gas in chamber 35 of the starting container. This high voltage is sufficient to produce a dielectric breakdown across this length of gas in chamber 35; and this breakdown develops into a discharge that extends along the entire length of the chamber 35. This discharge, through which capacitive current flows, is shown at 45 in Fig. 2, where the lamp is shown in a condition that we refer to as the initial breakdown stage. The discharge 45 of Fig. 2, like the toroidal arc 20 of Fig. 1, is an electrodeless arc. But a basic difference between these two arcs is that the arc 45 is capacitively coupled to its power source 18, 38-42, whereas the toroidal arc 20 is inductively coupled to its power source 18, 16. Just prior to the initial breakdown stage depicted in Fig. 2, and while the excitation coil 16 is energized, the upper wall portion 52 of the arc tube and the equatorial wall portion 50 of the arc tube are at relatively low potentials determined primarily by the average potential of the excitation coil 16, the upper turn of which is at ground potential. Any potential difference present between these two wall portions 50 and 52 at such time is relatively small and not great enough to cause a dielectric breakdown between these wall portions since they are separated by the relatively high-dielectric-strength fill gas in arc tube 14. Just prior to the initial breakdown stage depicted in Fig. 2, a relatively high voltage with respect to ground is developed across the L-C circuit 38, 40. This voltage is an RF voltage appearing at the top of the starting container 24, whereas the bottom of the starting container 24 is then at substantially ground potential. When the above-described dielectric breakdown occurs in the chamber 35 and develops into the discharge 45, the potential that is applied to the starting container 24 is connected through discharge 45 (which acts as a low impedance conductor) to the wall portion 52 of the arc tube at the bottom terminal of the discharge. The result is that the potential of this wall portion 52 quickly increases to a high level near that of the applied voltage thereby increasing the voltage present between arc-tube wall portions 52 and 50 by a large amount. Immediately thereafter, as shown in Fig. 3, filamentary discharges 60 appear within the arc tube 14, emanating from the wall portion 52. These filamentary discharges 60 represent a dielectric breakdown of the gaseous fill within the arc tube 14. This dielectric breakdown allows the electric and magnetic fields then being generated by RF current through the excitation coil 16 to develop a toroidal arc discharge of the form shown at 20 in Fig. 1. Thereafter, these electric and magnetic fields are capable of maintaining the toroidal arc discharge without assistance from the starting discharge 45. Accordingly, the starting discharge is then extinguished in a suitable manner, e.g., by opening the switch 42 to interrupt the circuit 43 and thereby disconnect the discharge 45 from its power source. It will be apparent from the above that because the lower end wall of the starting container 24 is constituted by a portion 52 of the arc tube, the same potential will be present at the lower end wall of the starting container and at the wall portion 52 of the arc tube. Accordingly, when discharge 45 is developed as above described, it transfers to the arc tube wall portion 52 the same potential as it tansfers to the end wall of the starting container. As pointed out hereinabove, the inner surface of the arc tube in the region 52 where the filamentary discharges 60 emanate is substantially flat. This feature has proven to be significant because if the construction in this region is such that the stem 24 protrudes into the arc tube, it has been found that the protruding tip of the stem is subject to overheating and resultant failure. On the other hand, designs which result in local cavities in this region are problematic because these cavities serve as condensation sites for halides in the gaseous fill. Another significant feature of our lamp is that the relevant portion of its starting container, or stem, 24 is smaller in transverse cross-section than is the relevant portion of the arc tube. The relevant portion of the arc tube is the hollow portion thereof that extends about the outer periphery of the toroidal discharge 20, and this hollow portion has an average cross-sectional area which is large in comparison to the transverse cross-sectional area of the starting container in its relevant region, i.e., the region of the starting container immediately adjacent its end wall. Keeping the cross-sectional area of the starting container relatively small in this region is important because it prevents an inductively coupled, or toroidal, discharge from developing in the starting container 24 under the influence of the magnetic and electric fields present therein (as a result of RF current through excitation coil 16). The lamp can sustain only one inductively coupled, or toroidal, arc discharge at any one time, and if such an inductively coupled discharge develops in the starting container or anywhere else in the lamp outside the arc tube, its presence will prevent such an inductively-coupled discharge from developing within the arc tube 14, where it is intended. While we have shown in our drawings a tubular starting container 24 that is of a simple straight-line configuration, it is to be understood that our invention in its broader aspects comprehends other configurations, such as a tubular member of curved form or a tubular member with a bend in it. It is also to be understood that our invention in its broader aspects may include additional means for initiating a breakdown in the starting container, or stem, 24. Other suitable means may be used for this purpose. For example, an electrode (such as shown at 62 in Fig. 4) may be incorporated into the top end of the starting container 24 and high voltage applied to this electrode to initiate a breakdown of the gaseous fill in the starting container. In the Fig. 4 embodiment the electrode 62 is shown connected to the conductor 41 of Figs. 1-3 to enable it to receive energizing voltage from means 38-42 of Figs. 1-3. A conventional foil type seal 61 is provided where the electrode passes through the quartz tubing. Of course, other suitable high voltage sources instead of that shown may be used for applying a starting high voltage to electrode 62. Even though an electrode such as 62 is present in the starting container of Fig. 4, the lamp itself is still considered to be an electrodeless lamp inasmuch as there would still be no electrode for the main arc, i.e., the toroidal arc within arc tube 14. A related application on starting means of the general type described in this paragraph is commonly-assigned, concurrently-filed U.S. Patent 5,095,249 published March 10, 1992. It is also to be understood that our invention in its broader aspect is not limited to the specific means shown at 38-42 for supplying voltage to the starting container or stem 24. For example, another way of initiating a breakdown is to utilize for this purpose the induced electric field from a suitably configured secondary coil, which in combination with the main excitation coil forms a transformer. When this transformer is energized by the above-described radio frequency current, the resulting electric field establishes a relatively high potential at the upper end of the stem 24 and a sufficiently high electric field within the gas inside the stem to cause a discharge between the two ends of the stem. A device relying upon this approach is shown in Fig. 5, which uses the same reference numerals as appear in Fig. 1 to designate corresponding components. The above-noted secondary coil is shown at 70. This secondary coil 70 is wound around a tube 72 of vitreous material, such as quartz or Pyrex glass, which surrounds the portion of the lamp above the main excitation coil 16. The secondary coil is electrically connected at its lower end to the upper turn of the main excitation coil 16 and at its upper end is connected through conductor 41 to the upper end of the starting container 24. This secondary coil 70 in combination with the main excitation coil 16 forms an autotransformer which, when energized by suitable RF current through coil 16, acts as above described to cause a discharge in the starting container. The vitreous tube 72 spaces the secondary coil a relatively large distance from the arc tube 14. It will be apparent from the above description that our starting means does not rely upon metal electrodes, metal probes, or similar metal parts positioned near or within the arc tube. This enables us to eliminate most of the life-limiting problems associated with metallic starting aids and also enables us to eliminate the need for any mechanism for withdrawing such metal parts after starting. While our starting means, like a metallic starting aid, does initiate arcing within the arc tube by increasing or concentrating the electric field therein, this is done not by positioning metal parts adjacent or within the arc tube but by using an electric discharge for transferring high potential from a remote point to a portion of the arc tube wall. Any metal parts that we utilize to assist in starting are located not adjacent to the arc tube but rather adjacent to a secondary chamber that contains a fill that is isolated from the fill in the arc tube and more easily broken down than the fill within the arc tube.	An electrodeless high intensity discharge lamp (10) comprising: (a) a light-transmissive arc tube (14) having spaced wall portions of dielectric material and a first gaseous fill within said arc tube, (b) an excitation coil (16) disposed about said arc tube (14) and energizable with radio frequency current effective to develop a toroidal arc discharge (20) in said first gaseous fill upon a dielectric breakdown of said first gaseous fill, characterized by further comprising: (c) a starting container (24) primarily of dielectric material joined to said arc tube (14) and having an end wall (52) that is constituted by one of said arc-tube wall portions of dielectric material, (d) a second gaseous fill within said starting container (24) having a dielectric strength lower than that of said first fill under normal conditions prevailing immediately prior to start-up of said lamp, and (e) means for initiating said toroidal arc discharge (20) in said arc tube (14) comprising means for producing a dielectric breakdown of the gaseous fill within said starting container (24) that develops into a discharge (45) within said starting container that changes the potential at said end wall (52) by an amount to increase the voltage present between said arc-tube wall portions sufficiently to trigger a dielectric breakdown of said first gaseous fill. The lamp of claim 1 in which: (a) the portion of said arc tube (14) that extends about the outer periphery of said toroidal arc discharge (20) has a predetermined cross-sectional area, and (b) said starting container (24) is tubular and has a transverse cross-sectional area adjacent said end wall (52) thereof that is smaller than said predetermined cross-sectional area of the arc tube. The lamp of claim 1 or 2, in which said arc tube (14) has a substantially flat internal surface on its wall in the region where said starting container (24) is joined to the arc tube. The lamp of claim 1 in which said second gaseous fill has a lower pressure than said first gaseous fill under conditions normally prevailing immediately before start-up of said lamp (10). The lamp of claim 1 in which the means for producing a dielectric breakdown of the gaseous fill within said starting container (24) comprises voltage-applying means (38-42) located outside said starting container for applying a high voltage across a portion of said second fill, and in which the electric discharge (45) developed by said latter voltage is an electrodeless arc capacitively coupled to said voltage-applying means. The lamp of claim 1 in which: (a) said means for producing a dielectric breakdown of the gaseous fill within said starting container (24) establishes at a point remote from said end wall a potential that if applied to said end wall is sufficient to cause a dielectric breakdown within said arc tube, and (b) said electric discharge (45) in said starting container electrically connects said predetermined point to said end wall (52). The lamp of claim 1 or 6 in which: (a) energization of said excitation coil (16) by said radio frequency current causes said spaced wall portions of said arc tube (14) to have potentials relative to each other insufficient to cause a dielectric breakdown of said first gaseous fill, assuming there is then no dielectric breakdown of said second gaseous fill, and (b) development of said discharge (45) in said starting container (24) causes the potential of said one arc-tube wall portion relative to the other of said arc-tube wall portions to change by an amount sufficient to initiate a dielectric breakdown in said first gaseous fill. The lamp of claim 1 in which said starting container (24) includes a chamber (35) in which said electrical discharge (45) is developed, said chamber having a transverse cross-section that is so small as to preclude the development therein of a toroidal arc discharge. The lamp of claim 1 in which there is provided in said starting chamber (35) an electrode (62) to which a high voltage is applied to initiate said dielectric breakdown of the gaseous fill within said starting container (24). The lamp of claim 1 in which said means for producing a dielectric breakdown of the gaseous fill within said starting container (24) comprises a second coil (70) connected between a point on said excitation coil and a point on said starting container to form in combination with said excitation coil (16) a transformer for developing a voltage across said second gaseous fill that is effective to break down said second gaseous fill upon energization of said transformer prior to initiation of said toroidal discharge (20) in said arc tube (14). The lamp of claim 10 in which a tube of vitreous material (72) is provided about a portion of said lamp and said second coil (70) is wound about said tube. The lamp of claim 10 in which said excitation coil acts as the primary winding and said second coil acts as the secondary winding of said transformer.	GEN ELECTRIC; GENERAL ELECTRIC COMPANY	DAKIN JAMES THOMAS; DUFFY MARK ELTON; HEINDL RAYMOND ALBERT; DAKIN, JAMES THOMAS; DUFFY, MARK ELTON; HEINDL, RAYMOND ALBERT
EP-0489533-B1	489,533	EP	B1	EN	19,961,030	1,992	20,100,220	new	G03G5	null	C08L75, G03G5	G03G 5/05C6	Photosensitive material for electrophotography	A photosensitive material for electrophotography, comprising a support and, provided thereon, an organic photoconductive layer of single-layer structure comprising a mixture of a metal-free phthalocyanine and a binder organic compound; said binder organic compound being comprised of an isocyanate in which the isocyanate terminal has been blocked with a blocking agent. The present photosensitive material can achieve good sensitivity and charge characteristics and is suited for the positive charge system.	This invention relates to a photosensitive material for electrophotography, suited for a positive charge system, carried out by a process comprising static charging, exposure and developing. Photosensitive compounds hitherto used for photosensitive materials for electrophotography include inorganic photoconductive substances and organic photoconductive substances. The former has problems in thermal stability, safety, etc. On the other hand, the latter has excellent safety and economic advantages, and are in recent years being prevalent in photosensitive materials for electrophotography. In the present invention also, the latter organic photoconductive substances are used. Photosensitive materials or photoconductors for electrophotography (hereinafter often OPCs ) making use of such organic photoconductive substances are usually used in double-layer structure comprised of a charge-generating layer (hereinafter CG layer ) that absorbs light to generate carriers and a charge transport layer (hereinafter CT layer ) that transports the carriers generated, and it is attempted to make them more highly sensitive. In general, in the double-layer structure, the CT layer is formed on the surface side on account of strength, run length, etc., and hence the photosensitive materials are used in a negative charge system. In such a negative charge system, however, there have been the problems that (1) deterioration due to ozone may occur because of the negative charge used for electrification, (2) the charge may be imperfect and (3) the photosensitive material tends to be affected by the properties of a drum surface. In order to solve such problems, development is energetically being made on OPCs that employ a positive charge system. In order to accomplish the positive charge system photosensitive material, studies have been made on (1) OPCs of reverse double-layer structure in which the layer structure for the CG layer and CT layer is made reverse to the case of the negative charge system (herein OPCs-1 ), and (2) OPCs of single-layer structure in which a charge-generating agent (herein CG agent ) and a charge-transporting layer (herein CT agent ) are contained together in a single layer (herein OPCs-2 ). In the OPCs-1, however, since the CG layer, which is essentially required to be made thin, is provided on the surface side of the photosensitive material, a decrease in run length and a deterioration of lifetime characteristics are questioned. There are also the problems in the complicated production process and separation of layers that may arise from the double-layer structure. Thus this photosensitive material has not been put into practical use. The single-layer type OPCs-2 are inferior to the OPCs-1 in respect of sensitivity and charge characteristics (repetition deterioration). In the case of the single-layer type as in OPCs-2, however, there is the advantage that wear in the photosensitive material does not immediately result in a lowering of run length so long as the agents are uniformly dispersed. In other words, wear in the photosensitive material is considered to have less influence on its photosensitivity characteristics. The single-layer type OPCs-2 are also advantageous in that they do not require as complicated a production process as the double-layer type OPCs-1. Under the above circumstances, an object of the present invention is to provide a single-layer type photosensitive material for electrophotography, having good sensitivity and charge characteristics and suited for the positive charge system. To achieve the above object, the present inventors made studies from various approaches. They took note of a single-layer type OPC comprising a mixture obtained by mixing a metal-free phthalocyanine as the CG agent and a binder organic compound (an organic compound for a binder), and further continued to study the latter binder organic compound. As a result, they found that use of an isocyanate whose isocyanate terminal has been blocked can achieve a superior single-layer type OPC, and thus have accomplished the present invention. That is to say, the photosensitive material for electrophotography according to the present invention comprises a support and, provided thereon, an organic photoconductive layer of single-layer structure comprising a mixture of a metal-free phthalocyanine comprising an X-type metal-free phthalocyanine and a binder organic compound; said binder organic compound consisting essentially of an isocyanate in which the isocyanate terminal has been blocked with a blocking agent, and wherein at least a part of the X-type metal-free phthalocyanine has been changed so that, in the X-ray diffraction pattern of the phthalocyanine, the ratio of the diffracted beam intensity at 2 of about 7.5° to the diffracted beam intensity at 2 of about 9.1° is from 1:1 to 1:10. The present invention also provides the use of a photosensitive material according to the invention in producing a visible image by electrophotography. The isocyanate in which the isocyanate terminal has been blocked (hereinafter blocked isocyanate ) may include compounds wherein a polyisocyanate terminal has been blocked with a blocking agent of an oxime, lactam or ester type (i.e., a polyisocyanate terminal has been reacted with a blocking agent). Compounds of an oxime, lactam or ester type are suitable for the blocking agent. Those of a phenol type or acid type tends to bring about an in sufficient charge potential. The oxime type blocked isocyanate can be exemplified by Colonate 2507 (trade name), available from Nippon Polyurethane Industry Co., Ltd. The lactam type blocked isocyanate can be exemplified by Colonate 2515 (trade name), available from Nippon Polyurethane Industry Co., Ltd. The ester type blocked isocyanate can be exemplified by Colonate 2513 (trade name), available from Nippon Polyurethane Industry Co., Ltd. The phenol type blocked isocyanate can be exemplified by Colonate AP Stable (trade name), available from Nippon Polyurethane Industry Co., Ltd., and the acid type blocked isocyanate can be exemplified by Milionate MS-50 (trade name), available from Nippon Polyurethane Industry Co., Ltd. The binder organic compound may further comprise a polyol containing a fluorine atom (hereinafter fluorine-containing polyol ). This can bring about an improvement in charge characteristics. The fluorine-containing polyol may include hydroxyl group-containing fluoroolefin copolymers whose main chains have been protected with fluorine. The weight ratio (as solid content) of the metal-free phthalocyanine to the binder organic compound is typically from 1:1.2 to 1:4.5. Use of the binder in an excessively small proportion makes it difficult to obtain a sufficient charge potential. Use of the binder in an excessively large proportion makes it difficult to obtain a sufficient sensitivity. In the case when the blocked isocyanate and the fluorine-containing polyol are used in combination, the weight ratio (as solid content) of isocyanate to said polyol is typically from 1:1 to 9:1. Use of the fluorine-containing polyol in an excessively large proportion makes it difficult to ensure a sufficient quantity of blocked isocyanate and also makes it difficult to control the change of charge potential to a sufficiently low rate. In the photosensitive materials for electrophotography, it is conventional to use a methacrylate together with the isocyanate and polyol (or polymers of these) as in Colonate L (trade name; available from Nippon Polyurethane Industry Co., Ltd). This is for the purpose of improving the repetition stability. The isocyanate used has a disadvantage in storage stability. In usual instances, in combination with the binder organic compound, a solvent in which the binder organic compound is soluble is used to make a mixture. A suitable solvent may include nitrobenzene, chlorobenzene, dichlorobenzene, dichloromethane, trichloroethylene, chloronaphthalene, methylnaphthalene, benzene, toluene, xylene, tertrhydrofuran, cyclohexanone, 1,4-dioxane, N-methylpyrrolidone, carbon tetrachloride, bromobutane, ethylene glycol, sulforan, ethylene glycol monobutyl ether, aceotoxyethane and pyridine. Any of these solvents may be used alone, or, without limitation thereto, may also be used in combination. Thus, a mixture obtained by adding and well mixing the metal-free phthalocyanine, blocked isocyanate, fluorine-containing polyol, solvent and so forth is coated on the surface of a substrate such as a drum or belt by means of a bar coater, a calender coater, a spin coater, a blade coater, a dip coater or a gravure coater, followed by heat treatment to effect curing. The heat-cured film thus completed is the main component of the photosensitive material for electrophotography. In the OPC of the present invention, use of an X-type metal-free phthalocyanine as the CG agent brings about a particularly good result. Typically, the metal-free phthalocyanine comprises a particulately dispersed X-type phthalocyanine and a molecularly dispersed phthalocyanine. Phthalocyanines can be grouped into metal phthalocyanines which have a metal atom in their center and metal-free phthalocyanines which contain no metal atom. The latter metal-free phthalocyanines (hereinafter H2-Pc ) are hitherto known to typically include two kinds of phthalocyanine, an α-type and a β-type. In this regard, Xerox Corporation has developed an X-type H2-Pc having a superior electrophotographic performance, and has conducted research into synthesis methods, the relationship between crystal forms and electrophotographic performance, and made structural analyses (see USP3,357,989). The X-type H2-Pc can be produced by converting a β-type H2-Pc synthesized by a conventional method, to the α-type by subjecting it to a sulfuric acid treatment, followed by ball milling for a long period of time. Its crystal structure is clearly different from the conventional α-types and β-types. The X-ray diffraction pattern of the X-type H2-Pc shows that its diffracted beams appear at 2 = 7.4, 9.0, 15.1, 16.5, 17.2, 20.1, 20.6, 20.7, 21.4, 22.2, 23.8, 27.2, 28.5 and 30.3 (unit: °). The diffracted beam with the highest intensity is the diffracted beam in the vicinity of 7.5° (corresponding to the spacing d = 11.8 Å). Assuming its intensity as 1, the diffracted beam intensity in the vicinity of 9.1° (corresponding to the spacing d = 9.8 Å) is 0.66. The X-type H2-Pc and the binder organic compound are added to the solvent, and then mixed with stirring (or kneaded) to effect dispersion. As a result of thorough mixing with stirring, the X-type H2-Pc is brought into fine particles and, at the same time, part thereof is solubilized (considered to have been solubilized on account of the fact that the viscosity has increased). The molecularly dispersed H2-Pc, which is different from the particulately dispersed X-type H2-Pc, is produced in the resulting mixture. It can be presumed that the presence of the molecularly dispersed H2-Pc carries out the function of charge transport. In the case when part of the X-type H2-Pc is solubilized as described above, the X-ray diffraction pattern is clearly different from the diffraction pattern of the X-type H2-Pc used alone, and is clearly different also from the diffraction patterns of the α-type and β-type H2-Pc's. More specifically, in its X-ray diffraction pattern, the diffracted beams with 2 of 21.4° or more tend to disappear and the diffracted beam in the vicinity of 16.5° tend to increase, compared with the X-ray diffraction pattern of the X-type H2-Pc. A most distinctive change is that, among the most characteristic diffracted beams of the X-type H2-Pc, (i.e., the two diffracted beams in the vicinity of 7.5° (d = 11.8 Å) and in the vicinity of 9.1° (d = 9.8 Å), only the diffracted beam in the vicinity of 7.5° has selectively disappeared. From these facts, it can be presumed that at least part of the X-type H2-Pc has changed to something new. Degree of the mixing with stirring (usually, stirring for a day or more is necessary), time, temperature, etc. may vary depending on the solvent, etc. to be used. A suitable degree of treatment can be found on the basis of the ratio (I11.8/I9.8) of the diffracted beam intensity in the vicinity of 7.5° and the diffracted beam intensity in the vicinity of 9.1° of the X-ray diffraction pattern described above. This ratio may preferably be from 1 to 0.1. As described above, the H2-Pc, blocked isocyanate alone, or together with fluorine-containing polyol, and solvent are put together and mixed by a ball mill, an attritor, a sand mill or a sand grinder, followed by coating and then heating to form a heat-cured film. In the course of the mixing treatment, the phthalocyanine is partially solubilized and at the same time formed into fine particles with progress of the treatment, and brought into an appropriately dispersed state. Furthermore, its viscosity is further increased and the absorbance of the film formed becomes better with progress of the treatment. Although the reason why the absorbance becomes better is not clear, it is presumed that mutual action takes place between the X-type phthalocyanine solubilized during the mixing treatment and the binder organic compound. The photosensitive material for electrophotography according to the present invention can be used in recording machinery such as copying machines, printers and facsimile apparatus. It may also be used for other purposes. The structure of the OPC of the present invention is not limited to that exemplified above. The OPC may further comprise a surface protective layer formed of an insulating resin laminated to the heat-cured film, or a blocking layer between the photosensitive layer and the substrate. In the photosensitive material for electrophotography according to the present invention, an isocyanate type organic compound is used as a binder, and hence it can achieve good charge characteristics and sensitivity characteristics. Since this isocyanate type organic compound is a blocked isocyanate, a satisfactory stability can be achieved, e.g., the rate of change in charge potential can be small after charging has been repeatedly operated. The photosensitive material for electrophotography according to the present invention is of a single-layer type, and hence it has the advantages that the complicated production process can be avoided and the run length can be superior. Moreover, since the positive charge system can be applied, the difficulties such as ozone deterioration occurring in the case of the negative charge system can be eliminated. Since also the CT agent, having a weakness to heat, can be omitted when the metal-free X-type phthalocyanine is used, the present invention can bring about an improvement in heat stability. EXAMPLEExamples of the photosensitive material for electrophotography of the present invention will be described below, starting from the stage of production. Needless to say, the present invention is by no means limited to the following Examples. Example 1 An X-type metal-free phthalocyanine (Fastogen Blue 8120B, trade name; available from Dainippon Ink & Chemicals, Incorporated) and a blocked isocyanate (Colonate 2507, trade name; available from Nippon Polyurethane Industry Co., Ltd.) were used in a weight ratio of 1:3.5 (solid content). Tetrahydrofuran was used as a solvent. First, at room temperature, the solvent and blocked isocyanate were put in a ball mill container in a proportion of 2:3. Thereafter the space portion of the container was substituted with dry air, and then the container was closed. After stirring for about 2 hours, Fastogen Blue was added, and the space portion was similarly substituted with dry air, followed by stirring for 24 hours. Then the resulting solution was coated on an aluminum substrate by means of a bar coater, followed by heat treatment (drying) at 150°C for 3 hours to give a single-layer type OPC. Example 2A single-layer type OPC was obtained in the same manner as in Example 1 except that Colonate 2513 was used as the blocked isocyanate. Example 3 A single-layer type OPC was obtained in the same manner as in Example 1 except that Colonate 2515 was used as the blocked isocyanate and the heat treatment was carried out at 160°C for 4 hours. Comparative Example 1A single-layer type OPC was obtained in the same manner as in Example 1 except that the blocked isocyanate was replaced with a usual toluene diisocyanate, 2,4-tolylene diisocyanate (Colonate T-65, trade name; available from Nippon Polyurethane Industry Co., Ltd.) and the heat treatment was carried out at 120°C for 3 hours. Comparative Example 2A single-layer type OPC was obtained in the same manner as in Example 1 except that the blocked isocyanate was replaced with diphenylmethane-4,4′-diisocyanate (Milionate MT, trade name; available from Nippon Polyurethane Industry Co., Ltd.) and the heat treatment was carried out at 120°C for 3 hours. Comparative Example 3A single-layer type OPC was obtained in the same manner as in Example 1 except that the blocked isocyanate was replaced with polymethylene-polyphenyl-polyisocyanate (Milionate MR, trade name; available from Nippon Polyurethane Industry Co., Ltd.) and the heat treatment was carried out at 120°C for 3 hours. Comparative Example 4A single-layer type OPC was obtained in the same manner as in Example 1 except that the blocked isocyanate was replaced with a modified isocyanate, a reacton product of trimethylol propane with 2,4-tolylene diisocyanate (Colonate L, trade name; available from Nippon Polyurethane Industry Co., Ltd.) and the heat treatment was carried out at 120°C for 3 hours. Photosensitivity characteristics of the OPCs obtained in Examples 1 to 3 and and Comparative Examples 1 to 4 were examined. For the measurement, a paper analyzer EPA-8100 Type, manufactured by Kawaguchi Denki K.K. was used. Each OPC brought into a positively charged state was irradiated with white light using a tungsten lamp, and the rate of change in charge potential with respect to the initial charge potential was determined after charging operation was repeated 1,000 times. Results obtained are shown in Table 1. Rate of charge potential change Example 1:7 % Example 2:11 % Example 3:6 % Comparative Example 1:40 % Comparative Example 2:38 % Comparative Example 3:33 % Comparative Example 4:28 % It is well understood from the results shown in Table 1 that use of the blocked isocyanate can bring about a remarkable improvement of repetition performance. Example 4A single-layer type OPC was obtained in the same manner as in Example 1 except that Fastogen Blue and Colonate 2507 were used in a weight ratio of 1:1.2 and the heat treatment was carried out at 140°C for 4 hours. Example 5A single-layer type OPC was obtained in the same manner as in Example 1 except that Fastogen Blue and Colonate 2507 were used in a weight ratio of 1:3.0 and the heat treatment was carried out at 140°C for 4 hours. Example 6A single-layer type OPC was obtained in the same manner as in Example 1 except that Fastogen Blue and Colonate 2507 were used in a weight ratio of 1:4.5 and the heat treatment was carried out at 140°C for 4 hours. Photosensitivity characteristics of the OPCs obtained in Examples 4 to 6 were examined. For the measurement, a paper analyzer EPA-8100 Type, manufactured by Kawaguchi Denki K.K. was used. Each OPC brought into a positively charged state was irradiated with white light using a tungsten lamp, and the charge potential and photosensitivity were determined. The photosensitivity was measured as half decay exposure, E1/2. Results obtained are shown in Table 1. Charge potential Photosensitivity (V) (lux·sec) Example 4:7301.6 Example 5:7802.0 Example 6:8003.1 It is well understood from Table 2 that good charge potential and photosensitivity characteristics can be obtained when the metal-free phthalocyanine and the blocked isocyanate are used in a weight ratio of from 1:1.2 to 1:4.2. Meanwhile, it was also confirmed that their use in a weight ratio less than 1:1.2 (for example, 1:0.8) tended to bring about an insufficient charge potential and their use in a weight ratio more than 1:45 (for example, 1:55) tended to bring about an insufficient photosensitivity. These tendencies were similarly seen when Colonate 2513 or 2515 was used. Example 7Fastogen Blue and binders, Colonate 2515 and Fluonate K-700 (trade name; a fluorine-containing polyol, hydroxyl group-containing fluorine resin, available from Dainippon Ink & Chemicals, Incorporated) were used in a weight ratio of 1:3 (solid content). Colonate 2515 and Fluonate K-700 were in a weight ratio of 5:5. Tetrahydrofuran was used as a solvent. First, in a glass container with a stirrer, the solvent and binders were put to hold the whole quantity. After stirring for about 3 hours, Fastogen Blue was added, followed by stirring for 24 hours. Then the resulting solution was coated on an aluminum substrate by dip coating, followed by heat treatment (drying) at 140°C for 4 hours to give a single-layer type OPC. Example 8A single-layer type OPC was obtained in the same manner as in Example 7 except that Colonate 2515 and Fluonate K-700 were used in a weight ratio of 7:4. Example 9A single-layer type OPC was obtained in the same manner as in Example 7 except that Colonate 2515 and Fluonate K-700 were used in a weight ratio of 9:1. Example 10A single-layer type OPC was obtained in the same manner as in Example 7 except that Colonate 2515 was used to hold the whole quantity (i.e., no Fluonate K-700 was used). Example 11A single-layer type OPC was obtained in the same manner as in Example 7 except that Colonate 2515 and Fluonate K-700 were used in a weight ratio of 4:6. The rate of change in charge potential was determined in the same manner as in Example 7 except that charging operation was repeated 2,000 times. Results obtained are shown in Table 3. Rate of charge potential change Example 7:7 % Example 8:8 % Example 9:8 % Example 10:10 % Example 11:18 % It is well understood from Table 3 that use of the fluorine-containing polyol in appropriate combination can be effective for improving the rate of change in charge potential. An increase in the amount of the fluorine-containing polyol result in a loss of the effect of improving the rate of change in charge potential (Example 11). The photosensitivity and charge potential were also measured to obtain good results. As having been described above, the single-layer type photosensitive material for electrophotography is comprised of the metal-free phthalocyanine and the organic compound capable of acting as a suitable binder, and hence can have good sensitivity and charge characteristics, can be produced through a not so complicated process, can be superior in run length, and also can be applied to the positive charge system, bringing about a very high practical utility.	A photosensitive material for electrophotography, comprising a support and, provided thereon, an organic photoconductive layer of single-layer structure comprising a mixture of a metal-free phthalocyanine comprising an X-type metal-free phthalocyanine and a binder organic compound; said binder organic compound consisting essentially of an isocyanate in which the isocyanate terminal has been blocked with a blocking agent, and wherein at least a part of the X-type metal-free phthalocyanine has been changed so that, in the X-ray diffraction pattern of the phthalocyanine, the ratio of the diffracted beam intensity at 2 of about 7.5° to the diffracted beam intensity at 2 of about 9.1° is from 1:1 to 1:10. A photosensitive material according to claim 1, wherein said blocking agent is an oxime, a lactam or an ester. A photosensitive material according to claim 1 or 2, wherein the weight ratio of metal-free phthalocyanine to binder is from 1:1.2 to 1:4.5. A photosensitive material according to any one of the preceding claims wherein said binder organic compound further comprises a fluorine-containing polyol. A photosensitive material according to claim 4, wherein the weight ratio of isocyanate to said polyol is from 1:1 to 9:1. A photosensitive material according to any one of the preceding claims wherein said metal-free phthalocyanine comprises an X-type metal-free phthalocyanine at least a part of which has been changed so that, in the X-ray diffraction pattern of the phthalocyanine, the diffracted beams with 2 of about 21.4° or more disappear and the diffracted beam at 2 of about 16.5° is increased. A photosensitive material according to any one of the preceding claims wherein the metal-free phthalocyanine comprises a particulately dispersed X-type phthalocyanine and a molecularly dispersed phthalocyanine. A photosensitive material according to any one of the preceding claims which further comprises a surface protective layer formed of an insulating resin, or a blocking layer between the photosensitive layer and the substrate. Use of a photosensitive material as claimed in any one of the preceding claims in producing a visible image by electrophotography.	MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.	ITO YOSHIMASA; MURAKAMI MATSUAKI; OMOTE ATSUSHI; TSUCHIYA SOHJI; ITO, YOSHIMASA; MURAKAMI, MATSUAKI; OMOTE, ATSUSHI; TSUCHIYA, SOHJI
EP-0489534-B1	489,534	EP	B1	EN	19,960,508	1,992	20,100,220	new	B29C47	B29C47	B29C47, B29K61, B29L23, B29K101	B29C 47/24, L29C261:04, B29C 47/00B	Extrusion method and extruder for obtaining phenolic resin pipe	An extrusion method for obtaining a long phenolic resin pipe (7) having excellent heat resistance by using an extruder comprising a screw (4), a cylinder (2), a die (5) and a mandrel (6), the mandrel being inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis, the die satisfying the following formulas R₁/R₂ = 0.25 ∼ 1.0 S₁/S₂ = 0.1 ∼ 2.5 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet, and the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 35° to the axis of the screw, and by shaping and extruding a phenolic resin material in a state that the material after extrusion is cured so as to be able to retain its own shape, by controlling the temperature of the heating zone of the cylinder communicating with the die inlet at 120-145°C and the temperature of the die at 150-200°C; an extruder used for effecting said method; and an extruded article obtained by using said method and said extruder.	Field of the InventionThe present invention relates to an extrusion method used for obtaining a phenolic resin pipe and an extruder used in effecting said method. Description of the Prior ArtAs the method for molding a thermosetting resin, there are known compression molding, transfer molding, injection molding and extrusion. Various apparatuses suitable for respective methods are in use. With respect to the extrusion as one of the methods for molding a thermosetting resin, plunger extrusion is generally used. For example, Japanese Patent Application Laid-Open No. 83155/1973 and Plastics Vol. 25, No. 3, p. 47 describe the production by plunger extrusion, of long shaped articles of simple configuration such as round bar, pipe and the like. Plunger extrusion, however, makes it difficult to produce an extrudate of homogeneous quality and gives low productivity because it employs a high extrusion pressure in the mold cavity of the plunger extruder used and is conducted intermittently. From the above reasons, extrusion using a so-called screw type equipment is disclosed in, for example, Japanese Patent Application Laid-Open No. 23661/1979 or Japanese Patent Application Laid-Open No. 18949/1974. Such extrusion uses an extruder wherein a thermosetting resin is kneaded and melt in an extrusion unit and the molten resin is extruded from the unit and introduced into a die unit through an adapter or the like in a time as short as possible to prevent the progress of thermosetting reaction and shaped into a final form. With such an extruder, however, continuous and stable extrusion has been difficult because the resin makes complex flow and, as a result, slight fluctuation in temperature and/or pressure causes rapid progress of thermosetting reaction, or appearance of flow stagnation gives rise to localized curing reaction. That is, in the extrusion disclosed in, for example, Japanese Patent Application Laid-Open No. 23661/1979, the resin heated and melt in a cylinder is introduced into a die through an adapter and shaped into a final form. In this procedure, the resin is squeezed and then expanded around a mandrel fixed by a spider; thus, the resin makes complex flow. Consequently, stagnation of flow takes place easily, giving rise to localized curing reaction, or slight fluctuation in pressure and/or temperature causes rapid appearance of curing reaction. In order to extrude a resin while overcoming the resistance caused by complex flow and preventing the resulting flow stagnation, a very large extrusion pressure is required and a special extruder capable of generating such a pressure is needed. Further with the above extruder, it has been unable to prevent quality problems such as (a) spider marks caused by a spider used for supporting a mandrel and (b) welds generated owing to the presence of the spider. In order to solve these problems, extrusion by a screw extruder employing a screw having a smooth zone at the front end is proposed in, for example, U.S. Patent No. 4797242, and is currently used for production of phenolic resin pipe. In this extruder, however, the smooth zone at the front end of the screw corresponds to the inside diameter of a pipe to be produced and accordingly, in view of the wall thickness of the pipe, it is impossible to produce a pipe having an outside diameter smaller than 20 mm because of the restriction of the mechanical strength of the screw. Further, since the screw and the cylinder have also a role of a die, production of a pipe of new size requires designing of a new screw and a new cylinder, providing an economical disadvantage particularly in production of a variety of products in small amounts. U.K. Patent No. 2089717 discloses an extruder which corresponds to the extruder of Japanese Patent Application Laid-Open No. 23661/1979 minus the adapter and the spider and which comprises a screw, a cylinder, a die and a mandrel, wherein the mandrel is provided on the extension of the screw axis. This extruder was proposed for production of thermoplastic resin pipe. This extruder relates to an extrusion technique for obtaining a pipe of balanced strengths by utilizing the property of molten thermoplastic polymer that their molecules, when flowing through a small path at a high speed, are orientated to the flow direction and by orientating the polymer molecules to different directions at the inner and outer layers of the pipe. In order to achieve the orientation to different directions, there was proposed the use of an extruder having an torpedo on the extension of a screw. This extruder was proposed for application to thermoplastic resins, as mentioned above. When the extruder was applied to extrusion of phenolic resin, i.e. thermosetting resin, extrusion became impossible in a short time after the start of pipe delivery from the die, making it impossible to obtain a satisfactory shaped article. The progress of partial curing at the die inlet was presumed to be a reason for inviting failure in extrusion. Thus, no fully satisfactory extrusion technique is developed for obtaining thermosetting resin shaped articles. Objects and Summary of the InventionAn object of the present invention is to provide an extrusion method and an extruder used for obtaining a phenolic resin pipe at excellent productivity. Other object of the present invention is to provide an extrusion method capable of producing a shaped article having no quality problems such as (a) spider marks and (b) welds generated owing to the presence of spider. Other object of the present invention is to provide an extrusion method capable of producing a pipe having an outside diameter smaller than 20 mm. Other object of the present invention is to provide an extrusion method capable of producing a shaped article having no quality problem caused by the partial curing at the die inlet when a torpedo is used. Still other object of the present invention is to provide a phenolic resin pipe having excellent homogeneity. The above object of the present invention can be achieved by providing an extrusion method for obtaining a phenolic resin pipe by using an extruder comprising a screw, a cylinder, a die and a mandrel, the mandrel being inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis (so as to be able to move forward and backward and being fitted to the screw so as to be able to freely rotate independently from the screw or the mandrel being firmly fitted to the front end of the screw so as to be able to rotate synchronously with the screw), the die satisfying the following formulas R1/R2 = 0.25 ∼ 1.0 S1/S2 = 0.1 ∼ 2.5 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet, and the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 35° to the axis of the screw, which method comprises shaping and extruding a phenolic resin material in a state that the material after extrusion is cured so as to be able to retain its own shape, by controlling the temperature of the heating zone of the cylinder communicating with the die inlet at 120-145°C and the temperature of the die at 150-200°C. The other objects of the present invention can be achieved by providing an extruder for obtaining a phenolic resin pipe, comprising a screw consisting of a feed zone, a compression zone and a metering zone, a cylinder having heating means corresponding to the feed zone, the compression zone and the metering zone, a die fitted to the front end of the cylinder, having a heating means, and a mandrel inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis, (so as to be able to move forward and backward and being fitted to the screw so as to be able to freely rotate independently from the screw or firmly fitted to the front end of the screw), the die satisfying the following formulas R1/R2 = 0.25 ∼ 1.0 S1/S2 = 0.1 ∼ 2.5 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet, and the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 35° to the axis of the screw. According to the present invention, there can be produced easily and stably at high productivity a long phenolic resin pipe having high resistances to heat and flame, without causing resin stagnation or localized curing which has been seen in the conventional extruder owing to the complex resin flow path. Brief Description of the DrawingsFig. 1 illustrates a preferred extruder used in the extrusion method of the present invention. Fig. 2 is an enlarged view showing the inlet of the die in the extruder of Fig. 1. Fig. 3 is an example of a detachable mandrel. Detailed Description of the InventionThe present inventors made study based on the technique which one of the present inventors disclosed in U.S Patent No. 4797242. As a result, there has been found an extrusion method for obtaining a phenolic resin pipe, which method uses an extruder comprising a screw consisting of a feed zone, a compression zone and a metering zone, a cylinder having heating means corresponding to the feed zone, the compression zone and the metering zone, a die fitted to the front end of the cylinder, having a heating means, and a mandrel inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis, or firmly fitted to the front end of the screw, and which method comprises shaping and extruding a phenolic resin material in the die in a state that the material before extrusion is cured to a certain extent and the material after extrusion can retain its own shape. This extrusion method has made it possible to produce a pipe having an outside diameter smaller than 20 mm which had been impossible to produce by the technique disclosed in U.S. Patent No. 4797242, and further can produce many different pipes in small amounts advantageously by using different dies and different mandrels. The extruder used in the present invention can be any of a single-screw extruder, a twin-screw extruder and a multi-screw extruder. However, the double-screw extruder and the multi-screw extruder must be those in which the screw front is integrated into a monoaxial state. The extruder used in the present invention may have a gas vent and/or a special kneading means between the feed zone and the metering zone. The extruder may further have, at the front end of the die, a unit having a cross section very slightly smaller than the die outlet so as to be able to control the back pressure applied to the resin being shaped and extruded. The screw is a type generally used in the extrusion of synthetic resin. It may be full-flighted or may have a torpedo shape having a smooth zone at the front end. The front end shape of the screw may be columnar or conical. The extrusion method for phenolic resin material is described with reference to Fig. 1. In Fig. 1, a phenolic resin material fed from a hopper 1 is heated and melt in a cylinder 2 having heaters 3, sent forward by the rotation of a screw 4, and introduced into a die 5 in a molten state. The material at the die inlet is in a molten and homogeneous state so as to be adapted to the change of the flow path, by controlling the temperature of the heating zone of the cylinder communicating with the die inlet at 120-145°C, preferably 125-140°C. When the temperature of said heating zone is lower than 120°C, the material at the die inlet may not be in a molten and homogeneous state. When the temperature is higher than 145°C, the material may cause partial curing and may find the smooth change of the flow path difficult. Thereafter, the material is heated in the die to 150-200°C, preferably 150-185°C, whereby the curing of the material is promoted and the material is shaped and extruded as a shaped article in a state that the material after extrusion is cured so as to be able to retain its own shape. The heating temperature in the die is appropriately controlled depending upon the pipe thickness and extrusion speed employed. When the heating temperature is lower than 150°C, the curing reaction of the material does not proceed sufficiently. Meanwhile, the heating to higher than 200°C is unnecessary because the phenolic resin is sufficiently cured at temperatures up to 200°C. As shown in Fig. 2, the cross section of the resin inlet 10 of the die is the same as the cross section formed by the cylinder and the screw front, and the cross section of the resin outlet 11 is the same as that of desired product. The resin flow path in the die is made so as to allow for smooth change from the inlet to the outlet. That is, as to the cross section of the die outlet 11, the outer diameter can be appropriately selected in a range of 0.25-1.0 time that of the die inlet 10 (i.e. R₁/R₂ = 0.25 ∼ 1.0), preferably 0.3-0.9 time, and the cross-sectional area of the flow path at the die outlet 11 can be appropriately selected in a range of 0.1-2.5 times that of the die inlet 10 (i.e. S₁/S₂ = 0.1 ∼ 2.5), preferably 0.15-2.0 times. When the outer diameter of the cross section of the die outlet deviates from 0.25-1.0 time that of the die inlet, or when the cross-sectional area of the flow path at the die outlet deviates from 0.1-2.5 times that of the die inlet, the change of the resin flow path is not smooth and the flow of the resin is not smooth, which invites partial stagnation of resin, excessive curing and difficult extrusion. The inclination of the outer periphery of the flow path portion 8′ from the die inlet 10 to the starting point of the uniform flow path portion having the same cross section as the die outlet 11 is not larger than 35°, preferably not larger than 30° to the axis of the screw. When the inclination is larger than 35°, the change in flow path in the portion 8′ is rapid, making the resin flow non-smooth. As shown in, for example, Fig. 3, the mandrel 6 is, at one end, inserted into a through-hole 9 in the screw along the screw axis and, at other end, protruding into the die along the screw axis. Accordingly, no spider as used for supporting a mandrel in ordinary dies is necessary, whereby the flow of material resin is not hindered at all. The resin introduced into the die is sent forward through the constantly changing flow path portion in a molten state; in the uniform flow path portion having the same cross section as the die outlet, is shaped and cured; and is extruded as a shaped article 7. Here, the length of the uniform flow path portion having the same cross section as the die outlet must be determined depending upon the combination of wall thickness of article, viscosity and curing rate of material used, other extrusion conditions, etc., but can be appropriately selected in a range of usually 1D to 30D (D is the inside diameter of die), preferably 5D to 25D, more preferably 5D to 20D. When the length of said uniform flow path portion is smaller than 1D, no sufficient curing is likely to occur and it is difficult to obtain a satisfactory shaped article. When the length is larger than 30D, the back pressure is too large and extrusion tends to be difficult. In the extrusion method of the present invention, there is substantially no rapid change in resin flow path from the screw front end of the extruder to the die outlet; therefore, there is no resin stagnation and there is invited neither localized curing reaction nor sudden curing reaction caused by the change in pressure and/or temperature. The shaped article obtained by the extrusion method of the present invention retains its own shape already right after extrusion and, by controlling the extrusion conditions, can be sufficiently shaped and cured to such an extent that it undergoes no easy deformation by an external force. Therefore, it causes no warpage, bending, swelling, etc. when put into actual usages. As necessary, a post-curing treatment may be conducted. The treatment can increase the thermal deformation temperature of shaped article and allows the use of the resulting article at temperatures of, for example, 200°C or more. The phenolic resin material used in the present invention may comprise, as necessary, additives generally used in molding of phenolic resin, such as filler, releasing agent, thickener, coloring agent, dispersing agent, foaming agent, curing accelerator and the like. The phenolic resin material may further comprise other polymers and organic or inorganic fibrous substances such as glass and the like. With respect to the flow properties of the phenolic resin material used in the present invention, the material preferably gives a flow amount of 0.05-25 g when subjected to the flow test by extrusion method according to JIS K 6911. The test is conducted under conditions of test mold temperature = 140°C and extrusion pressure = 150 kgf/cm². When the flow amount is smaller than 0.05 g, the uniform melting in the cylinder tends to be sacrificed; when the flow amount is larger than 25 g, the melting in the cylinder is easy but the curing in the die tends to be slow. The present invention is hereinafter described more specifically by way of Examples. However, the present invention is by no means restricted to the following Examples. Example 1An extruder having a cylinder diameter of 30 mm and an L/D ratio of 12 was used. The cylinder contained a full-flight screw having a feed zone 7D, a compression zone 1D, a metering zone 4D and a compression ratio of 1.5. A mandrel having an outer diameter of 5 mm was inserted into the screw along the screw axis. To the front end of the cylinder was fitted a die having a diameter of 9 mm, a length of 200 mm and a flow path construction as shown in Table 1. Using this extruder, extrusion was effected. There was used a phenolic resin material giving a flow amount of 5 g when subjected to the flow test by extrusion method according to JIS K 6911 under the conditions of test mold temperature = 140°C and extrusion pressure = 150 kgf/cm² (the flow amount obtained by the above test is hereinafter referred to simply as flow amount). The temperatures of the cylinder zones and the die were set as follows. CylinderC₁ (0 to 2D): water-cooled C₂ (3D to 6D): 80°C C₃ (7D to 10D): 105°C C₄ (11D to 12D): 130°C Die: 165°CThe screw rotation was set at 8 rpm. A pipe having an outside diameter of 9 mm and a wall thickness of 2 mm could be obtained continuously by extrusion. The properties of the pipe are shown in Table 1. Example 2Extrusion was effected in the same manner as in Example 1 except that the outside diameter of the mandrel was changed to 8 mm, the diameter and length of the die were changed to 12 mm and 300 mm, respectively, and the rotation of the screw was changed to 12 rpm. The construction of the die flow path and the properties of the pipe obtained are shown in Table 1. Example 3Extrusion was effected in the same manner as in Example 1 except that there was used a phenolic resin material giving a flow amount of 0.2 g in the flow test, the outside diameter of the mandrel was changed to 11 mm, the diameter and length of the die were changed to 16 mm and 300 mm, respectively, and the rotation of the screw was changed to 15 rpm. The construction of the die flow path and the properties of the pipe obtained are shown in Table 1. Example 4Extrusion was effected in the same manner as in Example 1 except that there was used a phenolic resin material giving a flow amount of 18 g in the flow test, the outside diameter of the mandrel was changed to 18 mm, the diameter and length of the die were changed to 24 mm and 400 mm, respectively, and the rotation of the screw was changed to 20 rpm. The construction of the die flow path and the properties of the pipe obtained are shown in Table 1. Example 5A phenolic resin material giving a flow amount of 4 g in the flow test was used. An extruder having a cylinder diameter of 50 mm and an L/D ratio of 12 was used. The cylinder contained a full-flight screw having a feed zone 7D, a compression zone 1D, a metering zone 4D and a compression ratio of 1.5. A mandrel having an outer diameter of 22 mm was inserted into the screw along the screw axis. To the front end of the cylinder was fitted a die having a diameter of 39 mm, a length of 508 mm and a flow path construction as shown in Table 1. Using the above resin material and extruder, extrusion was effected. The temperatures of the cylinder zones and the die were set as follows. Cylinder C₁ (0 to 2D): water-cooled C₂ (3D to 5D): 80°C C₃ (6D to 8D): 90°C C₄ (9D to 10D): 100°C C₅ (11D to 12D): 130°C Die: 170°CThe screw rotation was set at 10 rpm. A pipe having an outside diameter of 39 mm and a wall thickness of 8.5 mm could be obtained continuously by extrusion. The properties of the pipe are shown in Table 1. Example 6Extrusion was effected in the same manner as in Example 5 except that the outside diameter of the mandrel was changed to 32 mm. The properties of the pipe obtained are shown in Table 1. Comparative Example 1Extrusion was effected in the same manner as in Example 1 except that the outside diameter of the mandrel was changed to 2 mm, the diameter and length of the die were changed to 6 mm and 300 mm, respectively, and the rotation of the screw was changed to 6 rpm. Extrusion load increased suddenly in about 5 minutes from the start of extrusion, and the continuation of extrusion became impossible. The construction of the die flow path is shown in Table 1. Comparative Example 2Extrusion was effected in the same manner as in Example 1 except that the outside diameter of the mandrel was changed to 37 mm, the diameter and length of the die were changed to 45 mm and 508 mm, respectively, the rotation of the screw was changed to 25 rpm, and the temperatures of the cylinder C₄ zone and the die were changed to 135°C and 175°C, respectively. Extrusion load increased suddenly in about 4 minutes from the start of extrusion, and the continuation of extrusion became impossible. The construction of the die flow path is shown in Table 1. Comparative Example 3Extrusion was effected in the same manner as in Example 3 except that the outside diameter of the mandrel was changed to 6 mm, the diameter and length of the die were changed to 8 mm and 300 mm, respectively, the rotation of the screw was changed to 6 rpm, and the temperatures of the cylinder C₄ zone and the die were changed to 125°C and 175°C. Extrusion load increased in about 5 minutes from the start of extrusion, and the continuation of extrusion became impossible. The construction of the die flow path is shown in Table 1. Comparative Example 4Extrusion was effected in the same manner as in Example 5 except that the outside diameter of the mandrel was changed to 1 mm, the diameter and length of the die were changed to 45 mm and 508 mm, respectively, the rotation of the screw was changed to 20 rpm, the temperatures of the cylinder C₅ zone and the die were changed to 140°C and 160°C and a phenolic resin material giving a flow amount of 5 g was used. Extrusion load increased suddenly in about 5 minutes from the start of extrusion, and the continuation of extrusion became impossible. The construction of the die flow path is shown in Table 1. Comparative Example 5Extrusion was effected in the same manner as in Example 1 except that the inclination angle of the flow path-changing portion of the die was changed as shown in Table 1. Extrusion load was not stable and it was impossible to obtain a pipe of homogeneous quality. Comparative Example 6Extrusion was effected in the same manner as in Example 1 except that a phenolic resin material giving a flow amount of 35 g was used. The properties of the pipe obtained are shown in Table 1. Continuous extrusion was possible but the pipe surface had no gloss and was rough. Comparative Example 7Extrusion was effected in the same manner as in Example 1 except that the temperature of the cylinder C₄ zone was changed to 110°C. Extrusion load fluctuated largely and soon became high, which made extrusion impossible. Comparative Example 8Extrusion was effected in the same manner as in Example 1 except that the temperature of the cylinder C₄ zone was changed to 155°C and the temperature of the die was changed to 175°C. Extrusion load increased suddenly in about 15 minutes from the start of extrusion and the continuation of extrusion became impossible. Comparative Example 9Extrusion was effected in the same manner as in Example 1 except that the temperature of the cylinder C₄ zone was changed to 125°C and the temperature of the die was changed to 140°C. The properties of the pipe obtained are shown in Table 1. The pipe had insufficient curing and, when heated to, for example, 135°C, was deformed even by a small force. Comparative Example 10It was tried to produce a pipe of 16 mm in outside diameter and 2.5 mm in wall thickness by extrusion according to the technique disclosed in U.S. Patent No. 4797242. The same phenolic resin material as in Example 1 was used. Screw breakage occurred when the extruder front end began to deliver a glossy pipe, and the continuation of extrusion became impossible.	An extrusion method for obtaining a phenolic resin pipe by using an extruder comprising a screw, a cylinder, a die and a mandrel, the mandrel being inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis, the die satisfying the following formulas R1/R2 = 0.25 ∼ 1.0 S1/S2 = 0.1 ∼ 2.5 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet, and the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 35° to the axis of the screw, which method comprises shaping and extruding a phenolic resin material in a state that the material after extrusion is cured so as to be able to retain its own shape, by controlling the temperature of the heating zone of the cylinder communicating with the die inlet at 120-145°C and the temperature of the die at 150-200°C. The extrusion method of Claim 1, wherein the flow amount of the phenolic resin material, when subjected to the flow test by extrusion method according to JIS K 6911, is 0.05-25 g. The extrusion method of Claim 1, wherein the temperature of the heating zone of the cylinder at the back of the die inlet is controlled at 125-140°C and the temperature of the die is controlled at 150-185°C. The extrusion method of Claim 1, wherein the die satisfies the following formulas R1/R2 = 0.3 ∼ 0.9 S1/S2 = 0.15 ∼ 2.0 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet. The extrusion method of Claim 1, wherein the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 30° to the axis of the screw. The extrusion method of Claim 1, wherein the length of the uniform flow path portion of the die having the same cross section as the die outlet is 1D to 30D where D is the inside diameter of the die. The extrusion method of Claim 6, wherein the length of the uniform flow path portion of the die having the same cross section as the die outlet is 5D to 20D. An extruder for obtaining a phenolic resin pipe, comprising a screw consisting of a feed zone, a compression zone and a metering zone, a cylinder having heating means corresponding to the feed zone, the compression zone and the metering zone, a die fitted to the front end of the cylinder, having a heating means, and a mandrel inserted into a through-hole formed in the screw along the screw axis and protruding into the die along the screw axis, the die satisfying the following formulas R1/R2 = 0.25 ∼ 1.0 S1/S2 = 0.1 ∼ 2.5 where R₁ is an outside diameter of the die flow path at the die outlet, S₁ is a cross-sectional area of the die flow path at the die outlet, R₂ is an outside diameter of the die flow path at the die inlet, and S₂ is a cross-sectional area of the die flow path at the die inlet, and the inclination of the outer periphery of the die flow path portion from the die inlet to the starting point of the uniform flow path portion having the same cross section as the die outlet is not larger than 35° to the axis of the screw.	MITSUI TOATSU CHEMICALS; MITSUI TOATSU CHEMICALS, INC.	HANAUE KUNIO; MIYASAKA TAKESHI; HANAUE, KUNIO; MIYASAKA, TAKESHI
EP-0489537-B1	489,537	EP	B1	EN	19,940,810	1,992	20,100,220	new	B60J10	B60S1, B60J10, E06B7	B60J10, E06B7, B60S1	B60S 1/04F, B60J 10/00D5C, B60J 10/00D7B, E06B 7/215, B60J 10/04B	Sealing arrangements	A sealing arrangement for a window pane 10 in a vehicle door which can be raised and lowered is shown. The body panel 14 on the outside of the door is connected to a metal channel 38 by a spring steel metal strip 40 which enables the channel 38 to pivot about a pivot point 41 and biases it in a clockwise direction therearound. Channel 38 carries a sealing strip 20 having a lip 36. When the window pane 10 is fully raised, as shown, a cam 46 carried by the pane 10 holds channel 38 in the attitude shown and presses the lip 36 sealingly against the window pane. When the pane is lowered, cam 46 moves out of engagement with the channel 38 which moves clockwise around the pivot 41, disengaging lip 36 from the window pane. The inside body panel 12 of the door may carry a similar strip or a conventional strip.	The invention relates to a sealing and wiping arrangement for sealing and wiping against a slidable window glass, comprising a flexible element mounted adjacent to the window glass, and control means for moving the element between first and second positions in which it is respectively in and out of sealing contact with the window glass and for controlling the force with which the flexible element contacts the window glass. Such an arrangement is known from US-A-3 452 384. This known arrangement is for wiping the upwardly and downwardly slidable tailgate window glass of a vehicle body. A flexible wiping element extends longitudinally of the tailgate window glass and is mounted adjacent to it so as to be pivotable about an axis parallel to the glass surface. A roller in contact with the window glass pivots the wiping element away from the window glass as it is lowered. When the window glass is raised, the same roller pivots the wiper blade into contact with the window glass. This movement of the wiper blade into contact with the window glass is transmitted through a slip clutch arrangement which is arranged to slip when the wiper blade has contacted the window glass so as to prevent over-pressure between the blade and the glass. The slip clutch can be adjusted to provide the optimum wiping pressure. With this arrangement, therefore, the wiper blade is either completely out of contact with the window glass or is contacting the window glass with a fixed and predetermined pressure. Such an arrangement does therefore not permit the wiper blade to be selectively in contact with the window glass with respectively different and predetermined pressures. The invention aims to overcome this problem. Accordingly, the known arrangement is characterised in that the control means includes means selectively operable to move the flexible element into a third position in which it contacts the glass with a greater force than in the second position, whereby to wipe the glass as the latter slides. In this way, therefore, the flexible element can act simply as a sealing element or it can be forced into greater contact with the window glass so as to act as a wiping element. Sealing and wiping arrangements embodying the invention and for sealing against slidable window glass in a motor vehicle body will now be described, by way of example only, with reference to the accompanying diagrammatic drawings in which: Figure 1 is a cross-section through an arrangement, in a sealing configuration; Figure 2 corresponds to Figure 1 but shows the arrangement of Figure 1 in a non-sealing configuration; and Figure 3 corresponds to Figure 1 but shows the arrangement in a wiping configuration. The arrangements to be described are for sealing against the window pane (10) which can be raised and lowered, such as a window pane in a vehicle body which can be lowered into and raised from the lower part of the door. The Figures show a cross-section through part of the door to an enlarged scale. The lower part of the door is hollow and is the space between an inner body panel 12 and an outer body panel 14. The window pane 10 can be lowered into the interior 16 of the lower part of the door by means of the normal window winding mechanism which may be manually operated or motorised. The inner and outer body panels 12 and 14 define the gap at the so-called waistline through which the window pane 10 is raised and lowered. It is necessary to provide a flexible sealing arrangement for sealing against the opposite faces of the window pane 10, particularly when the window pane 10 is in its closed (fully raised) position. For this purpose, seals are mounted on the body panels 12 and 14 and run along the length of the gap 18. The seal on the body panel 12 is omitted, but a form of the seal 20 on the body panel 14 will now be described. The seal 20 is made of flexible material such as plastics or rubber material and is preferably manufactured by an extrusion process. Referring to Figure 1, the seal 20 mounted on the body panel 14 is in the form of a lip 322 which is made of flexible plastics or rubber material and is integral with a body part 324 which may be made of more rigid material. However, the body part 324 incorporates an integral flexible region 326 which acts as a hinge (in a manner to be explained) and integrally connects the body part 324 with a mounting part 328 in the form of a channel which is reinforced with a metal channel-shaped carrier 330 of any suitable form. Part 328 is mounted on the body panel 14 by frictionally embracing it, lips within the part 328 helping this frictional grip. Other fixing means may, however, be used instead. The seal 20 also incorporates an integral depending leg 336 which includes a reinforcing metal strip 338. The reinforcing metal strip 338 may be a continuous unapertured strip of metal or may be apertured with a series of slits or slots to aid flexibility if this is required. Instead, however, the metal strip may be replaced by strips of other hard material such as hardened rubber or plastics. A further possibility is to make the leg 336 of hardened rubber or plastics. Different parts of the seal can be extruded integrally to have different hardnesses. As shown in Figure 1, a hollow tube 346, which runs for the length of the waistline and is air-tight, is held in position between the facing surfaces of part 328 and the depending leg 336. The interior of the air tube 346 is connected to a source of air pressure by means of which its shape can be controlled. When the tube has the shape shown in Figure 1, lip 322 is in sealing contact with the window pane. In this configuration, the window pane is in its fully closed position. When it is desired to lower the window pane, either manually or automatically, the tube 346 is inflated by air pressure into the configuration shown in Figure 2. In this configuration, the expanded air tube applies a force to the side of the leg 336, causing the body 334 of the seal 20 to hinge against the resilience of the material about the pivot axis 345. The sealing lip 322 is thus moved out of sealing configuration with the window glass. Deflation of the air tube 346 collapses it and the resilience of the material of the seal causes the lip 322 to move back into sealing engagement with the window pane 10 as shown in Figure 1. Figure 3 shows the configuration which is assumed when the air-tube 346 is collapsed to a greater degree than shown in Figure 1. In this configuration, the lip 322 is forced into closer contact with the window pane than in Figure 1 and is able to carry out a wiping or cleaning action on the window pane by causing the window pane to be moved downwards (or possibly upwards) with the lip held in this position. Means may be provided for applying a jet of cleaning fluid to the window pane to aid this process. Movement of the lip 322 into the position shown in Figure 3, and operation of the cleaning fluid jet if provided, can be controlled manually or possibly automatically in associated with the window operation. Instead of an air pressure source, a source of partial vacuum may be used to control the shape of the air-tube 346 against its natural resilience.	A sealing and wiping arrangement for sealing against a slidable window glass (10), comprising a flexible element (322) mounted adjacent to the window glass (10), and control means (346,345) for moving the element (322) between first and second positions in which it is respectively in and out of sealing contact with the window glass (10) and for controlling the force with which the flexible element (322) contacts the window glass (10), characterised in that the control means (346,345) includes means selectively operable to move the flexible element (322) into a third position (Figure 3) in which it contacts the glass (10) with a greater force than in the second position, whereby to wipe the glass (10) as the latter slides. An arrangement according to claim 1, characterised in that the flexible element (10) is resiliently biassed into the third position and is moved therefrom by the control means (346,345) against the resilient bias and into the said second and the said first positions. An arrangement according to claim 1 or 2, characterised in that the control means (346) comprises a flexible fluid pressure chamber (346) positioned adjacent to the flexible element (322) and adapted to undergo a change in its shape in response to change of the fluid pressure therein, whereby to move the element (322) between the said positions and to control the said force. An arrangement according to claim 3, characterised in that the flexible element (322) is connected to a reinforced member (336) which defines one wall of a channel, and in that the flexible fluid pressure chamber (346) is positioned within this channel so as to exert pressure against the reinforced member which in turn applies the said force to the flexible element (322). An arrangement according to claim 4, characterised in that the reinforced member (336) and the flexible element (322) are both made of extruded plastics or rubber material, and the reinforced member (336) is reinforced with embedded metal. An arrangement according to any preceding claim, characterised by cleaning fluid applying means operative when activated to apply cleaning fluid to the panel.	DRAFTEX IND LTD; DRAFTEX INDUSTRIES LIMITED	FROMMEN PETER; MAASS KLAUS PETER; FROMMEN, PETER; MAASS, KLAUS PETER
EP-0489542-B1	489,542	EP	B1	EN	19,981,021	1,992	20,100,220	new	G03F1	null	G03F1, H01L21	G03F 1/00G, G03F 1/00G4	Lithographic techniques	A phase-shifting lithographic mask is made by a procedure involving only a single patterned electron, ion, or photon beam bombardment of a resist layer. THe bombardment is arranged to produce three kinds of regions FIG. 1: 14, 16, 15) in the resist: typically, no dosage, low dosage, and high dosage. These three regions in the resist are then utilized--in conjunction with an ordinary wet development step followed by either a silylation or an optical flooding technique, and thereafter by another ordinary wet development step--to pattern the resist layer and thereby to enable forming, by dry or wet etching, an underlying double layer consisting of a patterned opaque layer (FIG. 5: 13) and a patterned transparent phase-shifting layer (FIG. 5: 12), the phase-shifting layer being located on, or being part of, a transparent substrate (11).	Background of the InventionThis invention relates to a single alignment level lithographic process such as used for the fabrication of semiconductor integrated circuit and other devices by optical lithography.In fabricating integrated circuits by optical lithography systems, diffraction effects can become important whereby the edges of the image formed by a mask ( reticle ) become fuzzy (lose their sharpness); hence the resolution of the mask features, when focused on a photoresist layer located on the surface of a semiconductor wafer, undesirably deteriorates.In a paper entitled New Phase Shifting Mask with Self-Aligned Phase Shifters for a Quarter Micron Lithography published in International Electron Device Meeting (IEDM) Technical Digest, pp.57-60 (3.3.1-3.3.4) (December 1989), A. Nitayama et al. taught the use of masks having transparent phase-shifting portions in an effort to achieve improved resolution--i.e. improved sharpness of the image of the mask features focused on the photoresist layer. More specifically, these masks contained suitably patterned transparent optical phase-shifting layers, i.e. layers having edges located at predetermined distances from the edges of the opaque portions of the mask. Each of these phase-shifting layers had a thickness t equal to λ/2(n-1), where λ is the wavelength of the optical radiation from the source 106 (FIG. 1) and n is the refractive index of the phase-shifting layers. Thus, as known in the art, these layers introduced phase shifts (delays) of π radians in the optical radiation. By virtue of diffraction principles, the presence of these phase-shifting layers should produce the desired improved resolution. Such masks are called phase-shifting masks.The mask structure described by A. Nitayama et al., op. cit. was manufactured by a single-alignment-level process involving a step of wet etching an opaque chromium layer located underneath a phase-shifting layer of PMMA which is resistant to the wet etching, whereby the etching of the chromium layer undercut the PMMA layer and formed a phase-shifting mask. However, the lateral etching of the chromium layer is difficult to control, so that the positioning of the edges of the chromium layer is likewise difficult to control. Yet this positioning of the edges of the opaque chromium must be carefully controlled in order to yield the desired improved resolution for the mask.Therefore, it would be desirable to have a more controllable single-alignment-level method of manufacturing phase-shifting masks. More generally, it would be desirable to have a more controllable single-alignment-level lithographic technique for achieving self-aligned features.FR-A-2 228 242 discloses a process in which a resist mask, whose configuration is changed during processing, is formed by varying the exposure energy across a resist layer and then conducting successive development steps using developers having increasing solvent power to remove progressively more of the resist layer with each step.Patent Abstracts of Japan, vol 11, no 162, page 579, 26 May 1987 (abstract of JP-A-61292643) discloses a method of making a phase shift layer in which a resist layer is exposed to light having a pattern of different intensities so that, after development, some areas of the resist are removed, some are reduced in thickness and some remain. Under the resist layer is a layer of chromium on a layer of silicon dioxide. Both of these layers are etched away where the resist was removed. Then the resist is dry etched to open up the areas where it was thinned and the chromium layer is etched away in these areas.Summary of the InventionIn accordance with the invention, we provide a process as set forth in claims 1 and 2. It is advantageous that the process have, in addition, the steps recited in claim 3 to 12. Claim 13 describes a method including the process.Brief Description of the Drawing FIGS. 1-5 are side elevational views in cross section of various stages in the manufacture of a phase-shifting mask, in accordance with a specific embodiment of the invention;FIGS. 6-7 are side elevational views in cross section of various stages in the manufacture of a phase-shifting mask, in accordance with another specific embodiment of the invention; andFIG. 8 is a side elevational view in cross section of a phase-shifting mask manufactured in accordance with yet another specific embodiment of the invention. Only for the sake of clarity, none of the drawings is drawn to any scale. Detailed Description Referring now to the drawings, FIG. 1 shows an early stage in the making of an illustrative portion of a desired phase-shafting mask 600 (FIG. 5) for use as a reticle such as is used in optical systems having magnifications different from unity. For the sake of definiteness it will be assumed that the feature desired in this portion of the mask is a square aperture, but it should be understood that other features can be made, such as a circular aperture or a line-space feature.Substrate 11 is transparent, typically amorphous quartz. Layer 12 is a transparent phase-shifting layer, e.g., spun-on glass, located on a major surface of the quartz substrate 11 itself. For phase-shifting by π radian, the thickness of the layer 12 is everywhere equal to λ/2(n-1), where λ is the vacuum wavelength to be used in the optical lithography system and n is the refractive index of the material in layer 12. Layer 13 is an opaque layer, typically chromium having a uniform thickness of about 0.1 µm, which has been deposited on a top major surface of the transparent layer 12. Note that if the layer 13 is electrically conductive, as is chromium, advantageously it is grounded during the electron bombardment of the overlying resist.Layer 14 is a positive tone electron beam resist, typically a mixture of a polymer such as polycresolformaldehyde and a radiation-sensitive compound such as substituted 1,2 napthoquinone diazide. This layer 14 has a uniform thickness, typically of about 0.5 µm, and it has been bombarded with electrons in regions 15 and 16 thereof, but not elsewhere. The dose of electrons received in region 15 is made different from that in region 16, as discussed further below. The contour of the boundaries of these regions, as viewed from above, are in accordance with the ultimately desired feature in the mask 600 thereat. Thus, for a square aperture feature, the edges of region 16 form a square, and the edges of the region 15 form a square-ring. For a line-space feature, the edges of the regions 15 and 16 form parallel lines.The doses of electrons received by regions 15 and 16 of the resist layer are selected such that when the resist layer is developed with a suitable developing process, region 16 of the resist layer is removed but region 15 thereof remains intact (as does region 14). For example, a developer composed of tetramethyl-ammonium hydroxide solution in water (normality 0.3 N) can be used. Thus, typically the dose in region 16 is lower than that in region 15 but is nonetheless sufficient in region 16 to enable the developing process to remove the resist therein, as known in the art. The dose in region 14 is zero. Thus, the resist layer is patterned with an aperture 21 (FIG. 2) in the resist material where the low dose was received.If etching the layer 12, in going from the situation shown in FIG. 1 to that shown in FIG. 2, would spoil the regions 14 or 15 of the resist layer--as may be the case especially where dry plasma etching of the layer 12 is used -- then the layer 12 is not etched until after the situation shown in FIG. 4 and before the situation shown in FIG. 5 is attained; that is, the layer 12 is etched using the layer 13 alone as a mask.Using the thus patterned resist layer 14 as a protective mask in conjunction with etching, the opaque chromium layer 13 is subjected to etching, whereby the aperture 21 penetrates down through the chromium and spun-on glass layers to the top surface of the quarter layer 11. For example, to etch selectively the chromium layer 13, a wet etchant such as cerric ammonium nitrate or a dry etching with a chlorinated gaseous plasma can be used.Next (FIG. 3), the resist layer is subjected to a process which renders region 17, but not region 15, immune from removal during a subsequent (FIG. 4) resist removal step. For example, the resist is treated with silicon-containing species, such as an organic silicon-containing agent (such as hexamethyldisilazane), whereby region 14 (or at least a top portion thereof) forms a silylated region 17; but region 15 does not become silylated, because the high dose of electrons to which it was originally subjected (FIG. 1) produces cross-linking of the resist material, whereby it becomes impervious to silicon and hence resistant against silylation.As a consequence of the silylation, the resist in region 17, formerly region 14, but not in region 15 becomes resistant against a second etching step, such as a treatment with an oxygen plasma. As a result of such second etching step, an aperture 22 is formed in the resist layer 17. Consequently, after such second etching step, the resist in region 15, but not in region 17, is removed (FIG. 4). Layer 12 is then dry etched with a fluorinated gaseous plasma, using the layer 13 alone as a mask. Then, using the resist remaining in region 17 as a protective mask against etching, an etching process is used of the kind which removes the portion of the chromium layer 13, but not the spun-on glass 12, underlying the aperture 22. Again, a wet etchant such as cerric ammonium nitrate can be used, for example. Thus, an aperture 23 is formed having wider lateral dimension in the chromium layer 13 than in the spun-on glass layer 12. Finally, if desired, the remaining resist layer 17 can be removed, as known in the art, to form the desired phase-shifting mask or reticle 600 (FIG. 5).Prior to the silylation, a flood exposure to mid or near ultraviolet radiation can be performed, in order to enhance the diffusion and reaction of the silylation agent in the (uncrosslinked) region 14.Instead of using a silicon-containing agent to produce silylation of the resist, a tin-containing agent can be used to diffuse into and react with the resist.In case the desired mask feature is clustered line-spaces, the procedures indicated in FIGS. 6-7 can be used. Referring now to FIG. 6, instead of bombarding the surface of the resist layer in accordance with the pattern shown in FIG. 1, the bombardment is carried out in accordance with the pattern shown in FIG. 1, the bombardment is carried out in accordance with FIG. 6. Again regions 14 represent no dose of electron bombardment, and the dose in region 16 is typically lower than that in region 15. It should be understood that all these regions extend perpendicular to the plane of the drawing as elongated regions bounded by parallel lines. Then by using the same steps described above in connection with FIGS. 1-5, a mask 800 (FIG. 7) is formed having the desired alternating line-space phase-shifting features, for use as a reticle.Instead of silylation, an optical flood exposure can be used. More specifically, after the mask being formed has been brought into the condition shown in FIG. 6, and after the region 16 together with those portions of the chromium layer 13 and the spun-on glass layer 12 underlying it have thereafter all been removed, the entire top surface of the remaining structure is exposed to optical radiation, typically mid or near ultraviolet, whereby the region 14 of the resist layer becomes susceptible to removal by a second development step, such as a second wet development which may be the same that was used earlier to remove region 16. Thus, after this second development step, the resulting pattern of removed and unremoved regions 14 and 15 of the resist layer will be complementary to that obtained by the above-described silylation procedure. In particular, region 14 will be removed, and region 15 will remain. Using region 15 as a protective layer against etching the underlying chromium layer 13, a subsequent etching of the chromium layer 13 will therefore result in the mask 900 (FIG. 8).Instead of the optical flood exposure, electron beam or ion beam flood exposure can be used. The silylation procedure, resulting in mask 800, is preferred for mostly opaque masks (i.e., most of the mask area being opaque) whereas the optical flood procedure, resulting in mask 900, is preferred for mostly transparent masks.The layer 12 in the embodiments shown in FIGS. 1-5 and 6-8 need not be present in case the etch rate of the amorphous quartz or other transparent substrate can be sufficiently controlled--typically within ±5% across the entire major surface of the substrate--so that the depth of etch penetration into the substrate satisfies the required phase-shifting within desirable diffraction limits.Although the invention has been described in detail in terms of a specific embodiment, various modifications can be made without departing from the scope of the claims. For example, instead of a feature in the form of a square aperture, a circular aperture can be formed. Also, an isolated line feature can be attained by making all the boundaries between regions 14, 15, and 16 (FIG. 1) in the form of parallel lines (when viewed from above). Clustered line-space features can be obtained by arranging regions 14, 15, and 16 in accordance with FIG. 6.Instead of using geometrically selective electron bombardment to delineate the regions 14, 15, and 16, other kinds of bombardments can be used, such as ions and/or photons, to which the resist is sensitive. The resist itself can be a negative tone resist, instead of a positive tone resist, with suitable rearrangement of the layout of regions 14, 15, and 16, if need be. Instead of chromium for the opaque layer 13, other materials having sufficient opacity can be used such as molybdenum silicide. Instead of spun-on glass for the phase-shifting layer 12, other materials can be used that can be differentially (selectively) etched with respect to the underlying (quartz) substrate, such as either silicon dioxide or silicon nitride, which has been chemically vapor deposited on the (quartz) substrate.	A single alignment level lithographic process for making a phase-shifting mask consisting essentially of the steps of: (a) forming a resist layer on the surface of a first material layer located on the surface of a second material layer located on the surface of a substrate, the first material layer being opaque and the second material layer being transparent with respect to a prescribed optical radiation;(b) subjecting first, second, and third regions of the resist layer with mutually different first, second, and third doses of a resist-modifying radiation per unit area, respectively, the first and second regions having a first common boundary, and the second and third regions having a second common boundary;(c) subjecting the resist layer to a first development procedure, whereby the first region of the resist is removed but neither the second region nor the third region thereof is removed;(d) removing the first material layer, but not the second material layer, in a region thereof underlying the original first region of the resist layer;(e) subjecting the second and third regions of the resist layer to a treatment, whereby the third region, but not the second region, of the resist layer is resistant to a removal in step (f);(f) subjecting the second and third regions of the resist layer to a second development procedure, whereby the second region, but not the third region, of the resist layer is removed;(g) removing the second material layer in a region thereof underlying the original first region of the resist layer; and(h) etching the first material layer, but not the second material layer, in regions thereof underlying the original second region, but not the original third region, of the resist layer, whereby the order of sequence of performance of the steps is (a),(b), (c),(d),(e),(f),(g),(h), whereby there is created an edge in the first material layer and an edge in the second material layer that are respectively aligned with respect to the second and first common boundaries.A single-alignment level lithographic process for making a phase-shifting mask consisting essentially of the steps of: (a) forming a resist layer on the surface of a first material layer located on the surface of a second material layer located on the surface of a substrate, the first material being opaque and the second material layer being transparent with respect to prescribed optical radiation;(b) subjecting first, second, and third regions of the resist layer with mutually different first, second, and third doses of resist-modifying radiation per unit area, respectively, the first and second regions having a first common boundary, and the second and third regions having a second common boundary;(c) developing the resist layer, whereby the first region of the resist is removed but neither the second region nor the third region thereof is removed;(d) removing the first material layer, but not the second material layer, in a region thereof underlying the original first region of the resist layer;(c) subjecting the second and third regions of the resist layer to a treatment, whereby the second region, but not the third region of the resist layer is resistant to removal in step (f);(f) developing the resist layer, whereby the third region, but not the second region, of the resist layer is removed;(g) removing the second material layer in a region thereof underlying the original first region of the resist layer; and(h) etching the first material layer, but not the second material layer, in regions thereof underlying the original third region, but not the original second region of their resist layer, wherein the order of sequence of performance of the steps is (a), (b), (c), (d), (e), (f), (g), (h), whereby there is created an edge in the first material layer and an edge in the second material layer that are respectively aligned with respect to the second and first common boundaries.The process of claim 1 or 2 in which the second material layer is part of, and has the same chemical composition as that of, the substrate.The process of any of the preceding claims in which the radiation recited in step (b) is electrons.The process of any of the preceding claims in which the first material is a metal. The process of any of the preceding claims in which step (e) includes a silylation step.The process of any of claims 1 to 5 in which step (e) includes an optical flooding step.The process of any of the preceding claims in which during step (b) the dose of radiation received by the third region of the resist layer is essentially zero.The process of any of claims 1 to 7 in which during step (b) the dose or radiation received by the second region of the resist layer is essentially zero.The process of any of the preceding claims in which the first material layer is opaque while the substrate and the second material layers are transparent with respect to optical radiation to be used in the photolithographic procedure.The process of any of the preceding claims in which the second material layer is part of the thickness of the substrate.The process of any of the preceding claims in which the first and second region have square or circular contours, whereby after the etching step an aperture bounded by the edge in the opaque layer is formed in the opaque layer.A photolithographic method including the steps of: (a) forming a phase-shifting mask in accordance with the process of any of the preceding claims;(b) directing the prescribed optical radiation onto the mask, and focusing the optical radiation propagating through the mask onto a photoresist layer located on a major surface of a wafer on a layer of material on a major surface of a wafer, respectively;(c) developing the photoresist layer, whereby an edge feature is formed therein; and (d) defining a feature at the major surface of the wafer or in the layer of material, respectively, in accordance with the edge feature in the photoresist layer.	AT & T CORP; AT&T CORP.	GAROFALO JOSEPH GERARD; KOSTELAK ROBERT LOUIS JR; PIERRAT CHRISTOPHE; VAIDYA SHEILA; GAROFALO, JOSEPH GERARD; KOSTELAK, ROBERT LOUIS, JR.; PIERRAT, CHRISTOPHE; VAIDYA, SHEILA
EP-0489543-B1	489,543	EP	B1	EN	20,011,212	1,992	20,100,220	new	H04M3	H04M1, H04B3	H04M3, H04B1	H04M 3/40, H04M 3/00E	Telephone network speech signal enhancement	The quality of voice signals transmitted by a telephone station set (S1), or similar device, are enhanced before such signals are delivered to a receiving telephone station set (S2) by restoring the level of speech energy attenuated by the transmitting set, in which such restoration is performed at a point along a telephone connection between the transmitting and receiving telephone stations, for example, at a point within a telecommunications system (100) which establishes the connection.	Field of the InventionThe invention relates to a method of processing speech signals transmitted by a telephone station set, and more particularly relates to a method of enhancing the quality of such signals before they are supplied to a receiving telephone station set.Background of the InventionIt is well-known in the art of high-fidelity and stereo recordings that the overall quality of the reproduction of sound signals obtained from a source such as magnetic tape, a record, etc., may be enhanced in certain situations (e.g. low listening levels) by raising the level of those signals having frequencies within the so-called bass region. However, the designers of telecommunications systems have heretofore taken an opposite approach and have purposely discriminated against speech signals residing in the bass region, thereby degrading the overall quality of speech signals that are delivered to an intended destination, e.g. a telephone station set.The reason for such discrimination is that surveys show that the predominant source of ambient (background) noise have most of their energy in the low frequency range. Accordingly, to prevent a telephone station set that is in use from picking up such noise, the station set transmitter is designed so that it noticeably attenuates signals below 300 Hz. In fact, the Electronics Industries Association (ETA) standard RS-470, published January 1981, and relating to the design of telephone instruments recommends such attenuation below 300 Hz. What this means is that the quality of voice signals that are received at a telephone station set is noticeably diminished as a result of severely attenuating the level of such signals below 300 Hz at the transmitting telephone station set. US Patent No. 4, 535, 445 to Lane et al. and JP-A-57 176 895 disclose changing the attenuation of a signal on an individual customer's telephone line somewhere on the customer's premises. Summary of the InventionAccording to the invention there is provided a method as claimed in Claim 1.Brief Description of the DrawingsIn the drawing: Figure 1 is a broad block diagram of a telecommunications system illustrating the effect of attenuating speech signals within the bass band;Figure 2 is a broad block diagram of the telecommunications system of Figure 1 and illustrates the effect of enhancing speech signals before such signals are supplied to a receiving telephone station set; and FIG. 3 is an illustrative block diagram of the telecommunications network of FIG. 1 in which the invention may be practiced.Detailed DescriptionTurning now to FIG. 1, there is shown a simplified block diagram of a telecommunications network 100, which may be, for example, the AT&T network. As is well-known, the AT&T network comprises, inter alia, a plurality of toll offices, such as toll offices 105 and 110, that may be interconnected to one another to provide long distance voice and data connections for its subscribers, such as the telephone users associated with station sets S1 and S2. The manner in which a telephone user, e.g., the user associated with station S1, establishes via network 100 a telephone connection to another such user, e.g., the user associated with station S2, is well-known and will not be described herein. However, it suffices to say that a telephone user (hereinafter also subscriber ) may establish such a connection by causing station S1 to go off hook and then dialing the telephone number associated with station S2. Local central office 50 associated with station S1 collects the telephone digits as they are dialed and establishes a connection 101 to a network 100 toll office, e.g., toll office 105 (also referred to herein as a toll switch). Toll office, or switch, 105, in turn, and based on the dialed telephone number that it receives from local central office 50, establishes a connection 102 to a so-called destination toll switch, such as toll switch 110. Destination toll switch 110, in turn, extends the connection to central office 75 associated with station S2 and passes to that office the dialed telephone number. The latter central office responsive to receipt of the dialed digits then extends the connection 103 to station S2. The subscribers positioned respectively at stations S1 and S2 may then begin to speak to one another via the established connection.However, as a result of the aforementioned signal attenuation that is introduced by a telephone station set, e.g., station S1, the quality of the voice signals that the station transmits will be greatly diminished and, therefore, will not represent the speaker's true voice signals. This aspect is graphically illustrated in FIG. 1, in which curve 10 depicts the frequency response characteristic of the filter applied to the speech signals that station S1 supplies to toll switch 105 via line 101.It can be seen from curve 10 that, as a result of the station S1 filter, the speaker's voice signals rolls off sharply below 300 Hz, at a rate of approximately 12 dB per octave in accord with the aforementioned EIA RS-470 standard. Accordingly, a significant amount of the speech energy within the bass range is attenuated at a transmitting station set, e.g., S1, and, therefore, is not supplied to network 100 for delivery to a receiving station set, e.g., S2, as illustrated by filter response curve 15.After carefully reviewing curves 10 and 15 and the speech processing limitation of telephone switching equipment, we have recognized that, in accordance with the invention, the quality of telephone speech signals could be readily enhanced to offset the effect of transmitter attenuation, and that such enhancement may be performed at some point along the connection between the transmitting and receiving telephone station sets. In this way, the resulting signals that are supplied to the receiving station set would be more representative of the speaker's voice than the signals outputted by the transmitting station set. It is to be understood of course that such enhancement would also increase the level of the aforementioned ambient noise. However, studies show that most telephone users prefer to listen to enhanced speech, with an attendant increase in the level of background noise, rather than speech which has not been so enhanced.Moreover, we have recognized that, in accordance with an aspect of the invention, such signal enhancement could be readily performed at a central location which is involved in establishing a telephone connection between two telephone station sets, and which may be readily adapted to enhance the quality of speech signals. Such a central location may be, for example, network 100, as shown in FIG. 2.(It can be appreciated that FIG. 2 is similar in certain respects to FIG. 1. Consequently, elements in FIG. 2 which are identical to those shown in FIG. 1 are similarly numbered.)Referring then to FIG. 2, network 100 is now arranged in accord with frequency response curve 20 to compensate the level of speech signals that it receives from a transmitting telephone station set. In particular, the frequency response of curve 20 is particularly designed to increase, or boost, the level of speech signals below a predetermined frequency--illustratively 300 Hz. Such compensation may be achieved by passing speech signals received from a transmitting telephone station set through particular circuitry, such as, for example, a digital filter, in which the coefficients of the digital filter are selected in a conventional manner to increase the level of speech signals occurring within a particular range of frequencies,--illustratively a frequency range of 100-300 Hz. In an illustrative embodiment of the invention, the digital filter may be arranged to increase the gain of speech signals occurring within the aforementioned range by, for example, 10-15 decibels (dB) relative to the gain provided at, for example, 1000 Hz. This gain treatment is illustrated by response curve 20, in which the gain within the range of frequencies of 100 Hz to 300 Hz (or 100 Hz to 400 Hz) is greater than that of the remainder of curve 20, which is relatively flatThus, the application of such compensation to speech signals received by network 100 results in restoring the speech energy that was lost at the transmitter of the transmitting telephone station set, as illustrated by frequency response curve 25, which, as a result of being virtually flat, yields a more representative speech spectrum to the subscriber at station S2 than response curve 15 (FIG.1). Accordingly, as a result of such compensation, network 100, for the first time, delivers to the receiving telephone station set speech signals that more truly represent the speaker's voice.In an illustrative embodiment of the invention, the aforementioned digital filter was implemented using a commercially available digital filter, such as, for example, the DEQ7 digital equalizer available from the YAMAHA Corporation. The DEQ7 digital equalizer is programmable, allowing a user thereof to customize the equalization of a signal to meet a desired objective. That is, the user may set the gain of any one of a plurality of frequency bands between 63Hz and 16kHz to a desired value between -18.0 db and +18.0 db, in which a preset, or default value is set at 0 db. In our illustrative implementation, the gain of the frequency bands covering 125 Hz through 360 Hz were programmed to approximately meet the aforementioned gain of 10-15 dB, and the gain of the remaining bands were programmed to meet the preset value. The programming of the DEQ7 therefore effectively covered the desired frequency range below 300 Hz.As mentioned above, such compensation may be disposed at any point along a telephone connection between two telephone sets. We have recognized, however, that selecting the optimum point for the location of such compensation within a telecommunications network is not a trivial task, and is indeed nonobvious. The reason for this is that a telephone connection involves the cooperation between complex switching equipment. For example, a large network such as the AT&T network, employs a large number of complex switching offices interconnected by thousands of miles of transmission links and many different types of transmission equipment such as echo cancelers, multiplexers, synchronization systems, etc., to establish a telephone connection between virtually any two telephone stations in the U. S. In addition, a large network using such resources provides a number of different telecommunications services, and a variety of access arrangements to deliver such services to its subscribers. Thus, the optimum location for such compensation within a telecommunications network needs to be one which does not degrade the delivery of such services.In view of the foregoing, and after carefully studying the various switching aspects and services provided by a large network, we have recognized that one such an optimum location could be, in accord with an aspect of the invention, a transmission element centrally disposed in network 100. One such transmission element is an echo canceler.As is well-known, transmission media may include, inter alia, digital circuitry for processing voice signals. Such circuitry typically includes a digital device adapted to effectively remove from digitized speech signals so-called echo signals. Such a device is commonly referred to as an echo canceler. We have recognized that an echo canceler, in accord with an aspect of the invention, represents one of a number of ideal locations within network 100 at which the inventive method may be employed to enhance the quality of speech signals.Turning then to FIG. 3, there is shown in more detail toll switching offices 105 and 110 of network 100, in which each such office includes, inter alia, a switching element, e.g., switches 105-1 and 110-1, which may be, for example, the well-known 4ESS switch available from AT&T. Offices 105 and 110 also include echo canceling circuitry, which is used to interface a switch output port, or digroup terminal (not shown) with transmission media, such as communications path 102. Communications path 102 is shown in the Fig. as two oppositely directed transmission paths 102-1 and 102-2. For the sake of brevity and clarity, only one echo canceler circuit is shown in the FIG. for each of the toll offices 105 and 110, namely circuits 105-2 and 110-2. Since echo cancelers 105-2 and 110-2 perform essentially the same functions, a discussion of one such circuit pertains equally well to the other.Specifically, as is well-known, an echo canceler performs a number of signal processing functions. One such function is the cancellation of an echo signal that may be present in speech signals. An echo signal is a reflection of a transmitted signal and typically occurs as result of an impedance mismatch between the transmission medium, e.g., telephone line, and a two-wire-to-four-wire hybrid, such as either hybrid 130 or 135. (It is noted that a hybrid is typically associated with a CO, such as COs 50 and 75 and may be disposed at either the line side or trunk side of a CO. In certain instances, a hybrid may be associated with a toll switch.) Accordingly, echo canceler 110-2 and associated circuitry operates in a well-known manner to compare transmitted speech signals received via path 102-1 with signals propagating in an opposite direction via path 102-2, and cancel the latter signals if they are found to be echoes of previously transmitted speech signals. The echo canceler contained in office 105 performs a similar function by comparing transmitted speech signals received via path 102-2 with signals traveling in an opposite direction via path 102-1.The echo canceler circuitry also includes code converters 110-21 and 110-24. Converter 110-21 operates to convert speech signals encoded in the well-known mu-255 law format (or in certain instances a so-called A-law format) into a linear format for presentation to echo canceler processor 110-23 via digital filter 110-22. Code coverter 110-24 performs an opposite function. That is, converter 110-24 converts linear encoded speech signals that it receives from canceler 10-24 into the mu-255 law format (or A-law format) before such signals are supplied to switch 110-1 for ultimate delivery to a receiving telephone station set (e.g., station set S2 shown in FIGs. 1 and 2).Digital filter 110-22 implements the inventive method in echo canceler 110-2. A similar circuit implements the invention in echo canceler 105-2. The way in which a digital filter is implemented is well-known and will not be discussed herein. However, it suffices to say that digital filter 110-22, as well as the digital filter contained within the echo canceler of trunk 105-2, multiplies the response of speech signals that it receives with the response of curve 20 shown in FIG. 2, in which the response of curve 20 is characterized by the digital filter coefficients. In this way, those speech signals having frequencies below, for example, 300 Hz, are multiplied by the response of the filter which raises the energy level of those signals by a predetermined value-illustratively 10 to 15 decibels. Speech signals having frequencies above, for example, 300 Hz, are multiplied by the remainder of the filter response, which raises the level of those signals by another predetermined value--illustratively 0 decibels.Advantageously, then, network 100 is arranged in accord with the inventive method to enhance the quality of speech signals received via one telephone line, e.g., line 101, before those signals are delivered to another telephone line, e.g., line 103, and vice-versa.The foregoing is merely illustrative of the principles of the invention. Those skilled in the art will be able to devise numerous arrangements, which, although not explicitly shown or described herein, embody those principles and are within its scope. In particular, it is recognized of course that the desired result may still be achieved even though the inventive enhancement method may be disposed at some other point along the aforementioned connection, as will be discussed below. For example, the inventive compensation method may be readily disposed within a central office. In particular, a digital circuit implementing the steps of the invention may be disposed in either a central office incoming or outgoing trunk. In this way, speech signals associated with either an intraoffice or interoffice call may enjoy such compensation. As another example, if the station sets are associated with a business communication system, such as a private branch exchange, then the inventive compensation method may be employed in the business communication system to improve the quality of speech signals that are processed solely by that system. As a further example, the steps of the inventive method may be employed in a telephone station set. However, in view of the fact that millions of such sets are currently in use in the United States, the cost of implementing the invention in such station sets would be exceedingly high. Advantageously, then, all such station sets may still enjoy the results provided by the compensation method by performing such compensation at a central location, namely, network 100, as discussed above. As a further example, the invention may be employed in a so-called enhanced telecommunication service, such as a voice mail service, or a voice announcement service.	A method of enhancing the quality of speech signals exchanged between first (S1) and second (S2) telephone station sets, said method comprising the steps of responding to receipt of a request originated by either one of said first (S1) or second (S2) telephone station sets by establishing a communication path between said first and second telephone station sets, wherein at least one of said first (S1) and second (S2) telephone station sets is arranged to attenuate by a predetermined attenuation rate those of said speech signals having frequencies below a predetermined frequency and to transmit said speech signals over said communication path, and characterised byresponding to receipt of said speech signals transmitted by said one of said first (S1) and second (S2) telephone station sets by increasing by a predetermined level said attenuated speech signals and then supplying to the other one of said first (S1) and second (S2) telephone station sets via said communication path the resulting speech signals, said step of increasing being carried out in circuitry (110-22) located in said communication path between telephone switch circuitry at which said speech signals are received from said one of said first (105) and second (110) toll switches and telephone switch circuitry from which said resulting speech signals are supplied to said other of said first (105) and second (110) toll switches.A method as claimed in Claim 1, characterised in that said circuit (110-22) is located in a toll office (110) within said telecommunications system (100).A method as claimed in Claim 1 or 2, characterised in that said circuitry is echo cancellation circuitry (110-2) associated with said toll office (110).A method as claimed in Claim 1, 2 or 3 characterised in that said predetermined frequency is substantially 300 Hz. A method as claimed in Claim 1,2 or 3 characterised in that said predetermined frequency is substantially 400 Hz.A method as claimed in Claim 1, 2 or 3 characterised in that said frequencies are substantially within a range of 100 Hz to 300 Hz.	AT & T CORP; AT&T CORP.	BOWKER DUANE O; GANLEY JOHN T; JAMES JAMES H; BOWKER, DUANE O.; GANLEY, JOHN T.; JAMES, JAMES H.
EP-0489545-B1	489,545	EP	B1	EN	19,970,813	1,992	20,100,220	new	C08K13	C08L27	C08L27, C08K5, C08K13, C08K3	C08K 3/26+L57/08, C08K 5/00P6+L57/08, C08K 13/02+L57/08	Antistatic, thermally stabilized halogen-containing resin composition	A halogen-containing resin composition containing 100 parts by weight of a halogen-containing resin, 0.01 to 10 parts by weight of a hydrotalcite, 0.01 to 10 parts by weight of a perchloric acid ion-containing hydrotalcite, and 0.01 to 5 parts by weight of at least one member selected from a β-diketone compound, an organic acid metal salt and an organic tin compound, the resin composition being thermally stabilized against heat treatment and sun light and being improved in antistatic properties.	Field of the InventionThe present invention relates to an antistatic, thermally stabilized halogen-containing resin composition. More specifically, it relates to a halogen-containing resin composition which is thermally stabilized and imparted with the capability of preventing static electricity by incorporating specific amounts of hydrotalcite, perchloric acid ion-containing hydrotalcite, a β-diketone compound, etc. Prior Art of the InventionHalogen-containing resins are inherently thermally unstable. For example, halogen-containing resins undergo a decomposition reaction based mainly on dehydrohalogenation due to heat when molded, an increase in a surface temperature due to sun light when used or the like. For this reason, articles formed therefrom suffer a decrease in mechanical properties and deterioration in color tones. Further, as an antistatic agent, a cationic surfactant or an amphoteric surfactant is generally incorporated into halogen-containing resins. In this case, the dehydrohalogenation is furthered due to heat during the molding of said resins, heat of sun light, etc., and the article quality is degraded. Moreover, since these surfactants are chemically active, they react with hydrochloric acid generated by pyrolysis to nullify or decrease the antistatic properties. J-P-A-59-152941, J-P-A-59-157035 and JP-A-59-209644 disclose the use of hydrotalcites as an agent to catch a halogen dissociated from halogen-containing resins under dehydrohalogenation. Hydrotalcites have excellent capability of catching halogens, and further have the following advantages. Hydrotalcites take halogens into their structures and further, they are non-toxic. Even when hydrotalcites are used, an antistatic agent is generally incorporated. As an antistatic agent, cationic or amphoteric surfactants are generally preferred. These antistatic agents per se exhibit excellent antistatic properties. However, the defect with these antistatic agents is that they are inferior in dispersibility in, and compatibility with, halogen-containing resins. Further, these antistatic agents are poor in heat resistance and have the capability of promoting the decomposition of halogen-containing resins. Therefore, the static electricity resistance and thermal stability of articles molded from halogen-containing resins containing these antistatic agents have not been fully satisfactory. J-P-A-59-105037 and J-P-A-60-181142 disclose an antistatic plasticizer in order to overcome the defect that the above antistatic agents are inferior in compatibility and dispersibility. This plasticizer, which is required for processing halogen-containing resins, has antistatic performance imparted. However, the antistatic performance thereof has not been fully satisfactory. EP-A-0246867 discloses a powdery polyvinyl chloride resin composition comprising PVC resin, a stabiliser which is a barium and/or zinc soap and a perchlorate ion containing hydrotalcite compound. The composition is said to be resistant to amine staining and to have a reduced tendency to mould staining. Summary of the InventionIt is an object of the present invention to provide a halogen-containing resin composition having excellent thermal stability and excellent antistatic properties. It is another object of the present invention to provide a halogen-containing resin composition which is free from degradation in mechanical properties and deterioration in color tone caused by heat treatment during the processing thereof, sun light, etc. According to the present invention, there is provided an antistatic, thermally stabilized halogen-containing resin composition containing 100 parts by weight of a halogen-containing resin, 0.01 to 10 parts by weight of a hydrotalcite, 0.01 to 10 parts by weight of a perchloric acid ion-containing hydrotalcite, and 0.01 to 5 parts by weight of at least one member selected from a β-diketone compound, an organic acid metal salt and an organic tin compound. Detailed Description of the InventionThe present inventors have found that perchloric acid ion-containing hydrotalcites have antistatic properties and further that halogen-containing resins containing a cationic surfactant, if such a hydrotalcite is incorporated, do not suffer degradation in mechanical properties and deterioration in color tone even when treated under heat. A cationic or amphoteric surfactant contained in a halogen-containing resin as an antistatic agent is decomposed due to heat during the processing of the resin, heat of sun light, etc., to generate an amine compound. The present inventors assumed that the dehydrohalogenation is promoted by this amine compound, and attempted to inactivate the amine compound with a perchloric acid ion-containing hydrotalcite, which attempt has led to a success. That is, the thermal stability and photo-stability of halogen-containing resins are remarkably increased. It is assumed that the amine compound is inactivated by a perchloric acid ion-containing hydrotalcite and a halogen generated by pyrolysis is caught in layers of the hydrotalcite by ion-exchange. Examples of the halogen-containing resin used in the present invention are resins such as polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyethylene chloride, polypropylene chloride, polyethylene bromide, chlorinated rubber, a vinyl chloridevinyl acetate copolymer, a vinyl chloride-ethylene copolymer, a vinyl chloride-propylene copolymer, a vinyl chloride-styrene copolymer, a vinyl chloride-isobutylene copolymer, a vinyl chloride-vinylidene chloride copolymer, a vinyl chloride-styrene-acrylonitrile copolymer, a vinyl chloride-butadiene copolymer, a vinyl chloride-propylene chloride copolymer, a vinyl chloride-vinylidene chloridevinyl acetate terpolymer, a vinyl chloride-maleic acid ester copolymer, a vinyl chloride-methacrylic acid copolymer, a vinyl chloride-methacrylic acid ester copolymer, a vinyl chloride-acrylonitrile copolymer and internally plasticized polyvinyl chloride; and blends of the above resins and α-olefin polymers of polyethylene, polypropylene, etc., polyolefins such as an ethylene-propylene copolymer, etc., polystyrene, an acrylic resin, a copolymer of styrene and other monomer, an acrylonitrile-butadiene-styrene copolymer and a methacrylic acid ester-butadiene-styrene copolymer. In the present invention, the foregoing objects and advantages of the present invention are achieved by utilizing the thermal stability imparted by hydrotalcite and the antistatic properties imparted with perchloric acid ion-containing hydrotalcite. Further, there is used a specified amount of at least one component selected from a β-diketone, an organic acid salt of a metal and an organic tin compound in combination with the hydrotalcites in order to prevent the coloring caused by the hydrotalcites. The hydrotalcite used in the present invention has the following formula, M2+ (1-x)Alx(OH)2CO3(x/2)·mH2O wherein M2+ is Mg2+ and/or Zn2+, x is defined by 0.1<x<0.5, preferably by 0.2≦x≦0.4, particularly preferably by 0.25≦x≦0.35, and m is defined by 0≦m<1. As disclosed in J-P-A-55-80445, hydrotalcites are excellent with regard to thermal stability and transparency. The halogen-containing resin is further improved in thermal stability and non-coloring properties by incorporating at least one compound selected from an organic acid metal salt of zinc, lead, cadmium, calcium, barium, strontium, etc., an organic tin compound and a β-diketone compound. The amount of the hydrotalcite for use per 100 parts by weight of the halogen-containing resin is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When the above amount is less than 0.01 part by weight, no sufficient thermal stability can be obtained. When the amount exceeds 10 parts by weight, undesirably, the torque during the molding of the resin increases, and a colored molded article is obtained. The perchloric acid ion-containing hydrotalcite used in the present invention has the following formula, M2+ (1-x)Alx(OH)2(CO3)y(ClO4)z·mH2O wherein M2+ is Mg2+ and/or Zn2+, and x, y, z and m are positive numbers satisfying the following formulae, 0<x<0.5, preferably 0.2≦x≦0.4, 0≦y<0.25, preferably 0≦y≦0.20, 0<z≦0.5, preferably 0.04≦z≦0.4, 2y + z = x, and 0≦m<1. The perchloric acid ion-containing hydrotalcite imparts the halogen-containing resin with antistatic properties. When the halogen-containing resin contains a surfactant, the perchloric acid ion-containing hydrotalcite also prevents the deterioration of the thermal stability caused by the surfactant. The amount of the perchloric acid ion-containing hydrotalcite for use per 100 parts by weight of the halogen-containing resin is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When the above amount is less than 0.01 part by weight, no sufficient antistatic properties can be obtained. When it exceeds 10 parts by weight, undesirably, the resin viscosity increases and it is difficult to process the resin. The perchloric acid ion-containing hydrotalcite is disclosed in J-P-B-51-20997 and J-P-B-2-36143, and it should be understood that the concerned disclosure constitutes part of the present specification. The β-diketone compound has the following formula, R1-CO-CHR2-CO-R3 wherein each of R1 and R3 is independently a linear or branched alkyl or alkenyl group having up to 30 carbon atoms, an alkyl group having 7 to 36 carbon atoms, or an aryl or alicyclic group having less than 14 carbon atoms with the proviso that the alicyclic group my contain a carbon-carbon double bond, one of R1 and R3 may be a hydrogen atom, and R2 is a hydrogen atom, an alkyl group or an alkenyl group. The β-diketone compound prevents the coloring caused by the hydrotalcites when the halogen-containing resin is processed. The amount of the β-diketone compound for use per 100 parts by weight of the halogen-containing resin is 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight. When the above amount is less than 0.01 part by weight, no sufficient effect of preventing the coloring can be obtained. Even when it exceeds 5 parts by weight, the effect of preventing the coloring is not improved any further, and such an excess amount is not economical. Examples of the β-diketone compound are dehydroacetic acid, dehydropropionylacetic acid, dehydrobenzoylacetic acid, cyclohexan-1,3-dione, dimedone, 2,2'-methylenebiscyclohexan-1,3-dione, 2-benzylcyclohexan-1,3-dione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetylcyclohexanon-1,3-dione, benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane, bis(2-hydroxybenzoyl)methane, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, bis(3,4-methylenedioxybenzoyl)methane, benzoylacetyloctylmethane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoylacetylethylmethane, benzoyltrifluoroacetylmethane, diacetylmethane, butanoylacetylmethane, heptanoylacetylmethane, triacetylmethane, distearoylmethane, stearoylacetylmethane, palmitoylacetylmethane, lauroylacetylmethane, benzoylformylmethane, acetylformylmethylmethane, benzoylphenylacetylmethane and bis(cyclohexanoyl)methane. Further, there may be used salts of these β-diketone compounds with metals such as lithium, sodium, potassium, magnesium, calcium, barium, zinc, zirconium, tin and aluminum. Particularly preferred are stearoylbenzoylmethane and dibenzoylmethane. The organic acid salt of a metal has an effect of preventing the coloring caused by the hydrotalcites. The amount of the organic acid salt of a metal for use per 100 parts by weight of the halogen-containing resin is 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight. When the above amount is less than 0.01 part by weight, no sufficient effect can be obtained. When this amount exceeds the above upper limit, the resin knitting performance is poor and undesirably, plate-out or bleedout sometimes occurs. The metal constituting the organic acid salt of a metal is selected from zinc, lead, cadmium, calcium, barium, strontium, etc., and zinc is particularly preferred. An organic acid salt of zinc and an organic acid salt of other metal may be used in combination. The organic acid which constitutes the organic acid salt of a metal is selected from monocarboxylic acids such as acetylacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enathic acid, caprylic acid, neodecanoic acid, 2-ethylhexlic acid, pelarogonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 1,2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid, actoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxophthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, aconitic acid and thiodipropionic acid, and monoesters and monoamides of these dicarboxylic acids; and tri- and tetracarboxylic acids such as hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic acid and mellitic acid, and di- or triesters of these tri- or tetracarboxylic acids. The organic tin compound has an effect of preventing the coloring caused by the hydrotalcites. The amount of the organic tin compound for use per 100 parts by weight of the halogen-containing resin is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight. When the above amount is less than 0.01 parts by weight, no intended effect can be obtained. When it exceeds 5 parts by weight, undesirably, bleedout sometimes occurs. The organic tin compound is selected, for example, from mono or dialkyltin laurates such as mono- or dimethyltin tri-or dilaurate, mono- or dibutyltin tri- or dilaurate and mono- or dioctyltin tri- or dilaurate; mono- or dialkyltin maleates such as mono- or dimethyltin maleate polymer, mono- or dibutyltin maleate polymer, mono- or dimethyltin tris- or bisisooctylmaleate, mono- or dibutyltin tris- or bisisooctylmaleate and mono- or dioctyltin tris- or bisisooctylmaleate; mono- or dialkyltin thioglycolates such as mono- or dimethyltin tris- or bisisooctylthioglycolate, mono- or dioctyltin tris- or bisisooctylthioglycolate, mono- or dibutyltin tris- or bisthioglycolate, mono- or dimethyltin thioglycolate (or 2-mercaptopropionate), mono- or dibutyltin thioglycolate (or 2-mercaptopropionate) and mono- or dioctyltin thioglycolate (or 2-mercaptopropionate); and mono- or dialkyltin mercaptides such as mono- or dimethyltin tri- or didodecylmercaptide, mono- or dibutyltin tri- or didodecylmercaptide, mono- or dioctyltin tri- or didodecylmercaptide, mono- or dimethyltin sulfide, dioctyltin sulfide, didodecyltin sulfide, mono- or dimethyl, butyl or octyltin tris- or bis-2-mercaptoethyloleate, thiobis[monomethyltin bis(2-mercaptoethyloleate)], thiobis[dimethyl, dibutyl or dioctyltin mono(2-mercaptoethyloleate] and mono- or dioctyltin-s,s'-bis(isooctylmercaptoacetate). The halogen-containing resin composition of the present invention may contain a surfactant as an antistatic agent. The surfactant may be anionic, nonionic, cationic and amphoteric. The present invention produces a remarkable effect particularly when a cationic or amphoteric surfactant is used. The amount of the antistatic agent for use per 100 parts by weight of the halogen-containing resin is generally 0.01 to 10 parts by weight. When the above amount is less than 0.01, any intended effect is obtained. When it exceeds 10 parts by weight, bleeding sometimes occurs on a resin surface undesirably to render the surface sticky. Examples of the cationic surfactant as an antistatic agent are an aliphatic amine salt, a primary amine salt, a tertiary amine salt, a quaternary ammonium salt and an pyridinium derivative. Examples of the amphoteric surfactant as an antistatic agent are surfactant of a carboxylic acid derivative, an imidazoline derivative type, a higher alkyl amino type (betaine type), a sulfuric acid ester type, a phosphoric acid ester type and a sulfonic acid type. More specific examples of the surfactants are as follows. Quaternary ammonium chloride of formula (1) Quaternary ammonium sulfate of formula (2) Quaternary ammonium nitrate of formula (3) In the above formulae (1), (2) and (3), R is a linear or branched alkyl group having 2 to 22 carbon atoms or an amido group. Alkylbetaine types of formulae (4), (5) and (6) In the above formulae (4), (5) and (6), R1 is a linear or branched alkyl group having 12 to 18 carbon atoms, and each of R2 and R3 is independently an alkyl group having 1 to 4 carbon atoms. In the above formula (7), R is a linear or branched alkyl group having 12 to 20 carbon atoms. In the above formula (8), R is a linear or branched alkyl group having 12 to 18 carbon atoms. The resin composition of the present invention may contain a variety of additives such as a generally used stabilizer containing Ca, Ba or Sr, an ultraviolet absorber, an antioxidant, and the like as required. The present invention will be further detailed hereinbelow by reference to Examples, in which part stands for part by weight and % , for % by weight unless otherwise specified. Example 1 and Comparative Example 1Resin compositions of which the components and mixing ratios are shown below were kneaded with rolls at 180°C for 5 minutes to obtain rolled sheets having a thickness of 1 mm. The rolled sheets were placed in a gear oven at 180°C and examined on changes of thermal stability and coloring with time. Further, three sheets was taken from each of the rolled sheets, and stacks each of which consisted of the three sheets were respectively pressed with a pressing machine at a pressure of 100 kg/cm2 under heat of 190°C for 5 minutes to give press plates having a thickness of 1 mm. The press plates were measured for a volume resistivity at 23°C at a relative humidity of 50 % according to JIS K 6723. Table 1 shows the results. <Components and mixing ratio>Example 2 and Comparative Example 2Resin compositions of which the components and mixing ratios are shown below were kneaded with rolls at 180°C for 5 minutes to obtain rolled sheets having a thickness of 1 mm. The rolled sheets were placed in a gear oven at 200°C and examined on changes of thermal stability and coloring with time. Further, three sheets was taken from each of the rolled sheets, and stacks each of which consisted of the three sheets were respectively pressed with a pressing machine at a pressure of 100 kg/cm2 under heat of 190°C for 5 minutes to give press plates having a thickness of 1 mm. The press plates were measured for a volume resistivity in the same manner as in Example 1. Table 2 shows the results. <Components and mixing ratio>Polyvinyl chloride (polymerization degree 1,300)100 parts Dioctyl phthalate50 parts Hydrotalcite2.0 parts Zinc octylate0.3 part Perchloric acid ion-containing hydrotalciteper Table 2 MARK 1500 (phosphite)0.5 part Example 3 and Comparative Example 3Resin compositions of which the components and mixing ratios are shown below were kneaded with rolls at 180°C for 5 minutes to obtain rolled sheets having a thickness of 0.7 mm. The rolled sheets were placed in a gear oven at 190°C and examined on changes of thermal stability and coloring with time. Further, three sheets was taken from each of the rolled sheets, and stacks each of which consisted of the three sheets were respectively pressed with a pressing machine at a pressure of 100 kg/cm2 under heat of 190°C for 5 minutes to give press plates having a thickness of 1 mm. The press plates were measured for a volume resistivity in the same manner as in Example 1. Table 3 shows the results. <Components and mixing ratio>Polyvinyl chloride (polymerization degree 700)100 parts Dioctyltin bisisooctylthioglycolate1.0 part Hydrotalcite1.0 parts Perchloric acid ion-containing hydrotalciteper Table 3 Calcium stearate (Ca-St)per Table 3 Anon BFper Table 3 Pperchloric acid ion-containing hydrotalcite Ca-St Anon BF Volume resistivity Type Amount (part) (part) (part) (Ω·cm) Ex.3-1A1.001.09.0 x 1015Ex.3-2B1.001.06.5 x 1015Ex.3-3A1.00.51.08.8 x 1015CEx.3-1---1.0CEx.3-2 --0.51.0 CEx.3-3 - ---1.3 x 1016Ex. = Example, CEx = Comparative Example Thermal stability at 190°C (minute) 0 5 10 15 20 30 40 50 60 Ex.3-100123710 Ex.3-21234510 Ex.3-3011235810 CEx.3-110 CEx.3-210 CEx.3-30001235810 Ex. = Example, CEx = Comparative Example	Claims for the following Contracting States : DE, GB, FR, IT, NL, BEAn antistatic, thermally stabilized halogen-containing resin composition containing 100 parts by weight of a halogen-containing resin, 0.01 to 10 parts by weight of a hydrotalcite, 0.01 to 10 parts by weight of a perchloric acid ion-containing hydrotalcite, and 0.01 to 5 parts by weight of at least one of a β-diketone compound, an organic acid metal salt and an organic tin compound. A composition according to claim 1, which further contains 0.01 to 10 parts by weight of at least one antistatic agent selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant. A composition according to claim 2, wherein the cationic surfactant is an aliphatic amine salt, a primary amine salt, a tertiary amine salt, a quaternary ammonium salt or a pyridinium derivative. A composition according to claim 2, wherein the amphoteric surfactant is a carboxylic acid derivative, an imidazoline derivative, a higher alkylamino, betaine, surfactant, a sulfuric acid ester, a phosphoric acid ester or a sulfonic acid ester. A composition according to any one of the preceding claims wherein the hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2CO3(x/2).mH2O wherein M2+ is Mg2+ and/or Zn2+, x is defined by 0.1<x<0.5 and m is defined by 0≦m<1. A composition according to any one of the preceding claims wherein the perchloric acid ion-containing hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2(CO3)y(ClO4)z.mH2O wherein M2+ is Mg2+ and/or Zn2+, and x, y, z and m are positive numbers satisfying the following formulae, 0<x<0.5, 0≦y<0.25, 0<z≦0.5, 2y + z = x and 0≦m<1. A composition according to any one of the preceding claims wherein the β-diketone compound has the formula, R1-CO-CHR2-CO-R3 wherein each of R1 and R3 is independently a linear or branched alkyl or alkenyl group having up to 30 carbon atoms, an alkyl group having 7 to 36 carbon atoms, or an aryl or alicyclic group having less than 14 carbon atoms with the provisos that the alicyclic group may contain a carbon-carbon double bond and one of R1 and R3 may be a hydrogen atom, and R2 is a hydrogen atom, an alkyl group or an alkenyl group. A composition according to any one of the preceding claims wherein the organic acid metal salt is an organic acid salt of Zn, Pb, Cd, Ca, Ba or Sr. Shaped articles formed from a composition as claimed in any one of the preceding claims. Claims for the following Contracting State : ESA process for producing an antistatic, thermally stabilized halogen-containing resin composition which process comprises mixing 100 parts by weight of a halogen-containing resin, 0.01 to 10 parts by weight of a hydrotalcite, 0.01 to 10 parts by weight of a perchloric acid ion-containing hydrotalcite, and 0.01 to 5 parts by weight of at least one of a β-diketone compound, an organic acid metal salt and an organic tin compound. A process according to claim 1, which comprises mixing additionally 0.01 to 10 parts by weight of at least one antistatic agent selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant. A process according to claim 2, wherein the cationic surfactant is an aliphatic amine salt, a primary amine salt, a tertiary amine salt, a quaternary ammonium salt or a pyridinium derivative. A process according to claim 2, wherein the amphoteric surfactant is a carboxylic acid derivative, an imidazoline derivative, a higher alkylamino, betaine, surfactant, a sulfuric acid ester, a phosphoric acid ester or a sulfonic acid ester. A process according to any one of the preceding claims wherein the hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2CO3(x/2).mH20 wherein M2+ is Mg2+ and/or Zn2+, x is defined by 0.1<x<0.5 and m is defined by 0≤m<1. A process according to any one of the preceding claims wherein the perchloric acid ion-containing hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2(CO3)y(ClO4)z.mH2O wherein M2+ is Mg2+ and/or Zn2+, and x, y, z and m are positive numbers satisfying the following formula, 0<x<0.5, 0≤y<0.25, 0<z≤0.5, 2y + z = x and 0≤m<1. A process according to any one of the preceding claims wherein the β-diketone compound has the formula, R1-CO-CHR2-CO-R3 wherein each of R1 and R3 is independently a linear or branched alkyl or alkenyl group having up to 30 carbon atoms, an alkyl group having 7 to 36 carbon atoms, or an aryl or alicyclic group having less than 14 carbon atoms with the provisos that the alicyclic group may contain a carbon-carbon double bond and one of R1 and R3 may be a hydrogen atom, and R2 is a hydrogen atom, an alkyl group or an alkenyl group. A process according to any one of the preceding claims wherein the organic acid metal salt is an organic acid salt of Zn, Pb, Cd, Ca, Ba or Sr. Shaped articles formed from a composition produced by a process according to any one of the preceding claims. An antistatic, thermally stabilized halogen-containing resin composition containing 100 parts by weight of a halogen-containing resin, 0.01 to 10 parts by weight hydrotalcite, 0.01 to 10 parts by weight of a perchloric acid ion-containing hydrotalcite, and 0.01 to 5 parts by weight of at least one of a β-diketone compound, an organic acid metal salt and an organic tin compound. A composition according to claim 10, which further contains 0.01 to 10 parts by weight of at least one antistatic agent selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant. A composition according to claim 11, wherein the cationic surfactant is an aliphatic amine salt, a primary amine salt, a tertiary amine salt, a quaternary ammonium salt or a pyridinium derivative. A composition according to claim 11, wherein the amphoteric surfactant is a carboxylic acid derivative, an imidazoline derivative, a higher alkylamino, betaine, surfactant, a sulfuric acid ester, a phosphoric acid ester or a sulfonic acid ester. A composition according to any one of claims 10 to 13, wherein the hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2CO3(x/2).mH2O wherein M2+ is Mg2+ and/or Zn2+, x is defined by 0.1<x<0.5 and m is defined by 0≤m<1. A composition according to any one of claims 10 to 14, wherein the perchloric acid ion-containing hydrotalcite is of the formula, M2+ (1-x)Alx(OH)2(CO3)y(ClO4)z.mH2O wherein M2+ is Mg2+ and/or Zn2+, and x, y, z and m are positive numbers satisfying the following formulae, 0<x<0.5, 0≤y<0.25, 0<z≤0.5, 2y + z = x and 0≤m<1. A composition according to any one of claims 10 to 15, wherein the β-diketone compound has the formula, R1-CO-CHR2-CO-R3 wherein each of R1 and R3 is independently a linear or branched alkyl or alkenyl group having up to 30 carbon atoms, an alkyl group having 7 to 36 carbon atoms, or an aryl or alicyclic group having less than 14 carbon atoms with the provisos that the alicyclic group may contain a carbon-carbon double bond and one of R1 and R3 may be a hydrogen atom, and R2 is a hydrogen atom, an alkyl group or an alkenyl group. A composition according to any one of claims 10 to 16, wherein the organic acid metal salt is an organic acid salt of Zn, Pb, Cd, Ca, Ba or Sr. Shaped articles formed from a composition as claimed in any one of claims 10 to 17.	KYOWA CHEM IND CO LTD; KYOWA CHEMICAL INDUSTRY CO., LTD.	NAGAE YOSHIYUKI; NOSU TSUTOMU; NAGAE, YOSHIYUKI; NOSU, TSUTOMU
EP-0489547-B1	489,547	EP	B1	EN	19,980,729	1,992	20,100,220	new	C07D209	C07D209, C07C205	A61K31, C07C205, A61P27, A61P9, A61P43, A61P37, C07D209, A61P17, C07C53, A61P11, C07C211	C07D 209/18, C07C 53/50, C07D 209/24, M07D209:18, C07D 209/08, C07C 205/61, C07C 53/21, M07D209:08, C07C 211/15, M07D209:24	A process for the preparation of a 3-alkylated indole, intermediates, and a process for the preparation of a derivative thereof	A process for the preparation of a 3-alkylated indole, which comprises:- a) reacting a N-(2-nitrostyryl) enamine with an alkylating agent to afford an imine salt, b) optionally reacting the imine salt with water to afford a (2-nitrophenyl)acetaldehyde, and c) reacting the imine salt or the (2-nitrophenyl)acetaldehyde with a reducing agent capable of selectively reducing the nitro group, to afford the desired 3-alkylated indole.	The present invention relates to a process for the preparation of certain 3-substituted indoles, and to certain intermediates which are useful in this process.3-Substituted indoles are useful as chemical intermediates, for example in the preparation of pharmaceuticals. Examples of such pharmaceuticals include compounds disclosed in European Patent Applications publication numbers EP-A2-0199543 and EP-A2-0220066. Other pharmaceuticals include those based upon the 3-substituted indoles tryptophan, serotonin and melatonin.It is known that indoles may be alkylated at the 3-position, for example by reaction with an alkyl halide. However, the reaction often proceeds with some difficulty, and may be accompanied by alkylation at the 1- and/or 2-position.J. HeterocyclicChem., (1988), 25, 1-8 discloses certain processes for preparing particular 3-alkylated indoles. Synthesis, (1977), 848-849 discloses an enamine-alkylation procedure for the synthesis of 1-benzyl-2-indanones and 1-benzyl-2-tetralones. United States patent number 3,979,410 discloses a process for preparing o-nitrobenzylketones which may be used to prepare 2-substituted indoles. EP-A-0220066 discloses a process for preparing 3-alkylated indoles by alkylation of an indole unsubstituted at the 3-position.United States patent number 3,976,639 discloses a process for preparing 3-unsubstituted indoles which comprises reacting a N-(2-nitrostyryl) enamine with a reducing agent capable of selectively reducing the nitro group. It is noted at column 6, lines 49 to 52 that the 3-unsubstituted indoles can be utilised as intermediates in the preparation of tryptophan and and serotonin, both of which are 3-substituted indoles.The invention provides a process for the preparation of a 3-alkylated indole, which comprises:- a) reacting a N-(2-nitrostyryl) enamine of the formula IV (formula set out hereinafter) with a compound of the formula V (formula set out hereinafter) to afford an imine salt, wherein each R independently represents a (1-4C)alkyl group or together represent a 4- or 5- membered alkylene or heteroalkylene chain, X is a leaving atom or group, T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group,b) optionally reacting the imine salt with water to afford a (2-nitrophenyl)acetaldehyde, andc) reacting the imine salt or the (2-nitrophenyl)acetaldehyde with a reducing agent selected from iron in the presence of an acid; stannous chloride; titanium trichloride; sodium dithionite; hydrazine with Raney nickel; and hydrogen in the presence of a transition metal hydrogenation catalyst; to afford the desired 3-alkylated indole.The process according to the invention has been found to afford 3-alkylated indoles in improved yield, without contamination by 1- and/or 2-alkylated indoles.In the process, the imine salt is preferably reacted with water to afford a (2-nitrophenyl)acetaldehyde. The aldehyde is a stable intermediate, unlike the imine salt, and hence can readily be handled on a manufacturing scale.The N-(2-nitrostyryl) enamine used in the process according to the invention is a tertiary amine having a (2-nitrostyryl) group as one of the substituents of the nitrogen atom of the tertiary amino group. Thus it is a 2-nitro- -(disubstituted amino)styrene. The remaining two substituents of the nitrogen atom are alkyl groups, for example (1-4C) alkyl groups such as methyl or ethyl, or the two ends of a 4- or 5-membered alkylene or heteroalkylene chain, thereby forming a 5- or 6-membered ring such as a pyrrolidine, piperidine or morpholine ring. Accordingly, the N-(2-nitrostyryl) enamine may be, for example, a 2-nitro-β-(di(1-4C)alkylamino)styrene such as a 2-nitro-β-(dimethylamino)styrene or a 2-nitro-β-(diethylamino)styrene, or a 2-nitro-β-(1-pyrrolidinyl)styrene, a 2-nitro-β-(1-piperidinyl)styrene or a 2-nitro-β-(4-morpholinyl)styrene.A leaving atom or group, X, is preferably a halide, for example a bromide or iodide, or an optionally substituted hydrocarbylsulphonyloxy ester, for example a p-toluenesulphonyloxy, p-bromophenylsulphonyloxy, methanesulphonyloxy or trifluoromethanesulphonyloxy ester. Most preferably it is a halide.In our initial British Patent Application number 8927981.4, filed on 11th December, 1989, the compound 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide is disclosed. This compound has the formula I (formula set out hereinafter). This compound has been found to antagonise the action of one or more of the arachidonic acid metabolites known as leukotrienes. It is useful wherever such antagonism is required. Thus, it may be of value in the treatment of those diseases in which leukotrienes are implicated, for example, in the treatment of allergic or inflammatory diseases, or of endotoxic or traumatic shock conditions.The compound of formula I is preferably in the substantially pure (R)-form.The compound of formula I may be prepared by acylating 2-methyl-4,4,4-trifluorobutylamine of formula II (formula set out hereinafter) or an acid addition salt thereof such as the hydrochloride with a carboxylic acid of formula III wherein U is carboxy or a reactive derivative thereof. The acylation is conveniently performed in the presence of a dehydrating agent, such as 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride, optionally together with an organic base, for example, 4-dimethylaminopyridine.The compound of formula III may be prepared from a compound of formula VI (formula set out hereinafter) in which T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group, for example phenyl, benzyl, or (1-6C)alkyl optionally bearing an acetoxy, (1-4C)alkoxy or (1-4C)alkylthio substituent. Particular values for Rh and Rj are, for example, methyl, ethyl, propyl, t-butyl, acetoxymethyl, methoxymethyl, 2-methoxyethyl, methylthiomethyl, phenyl or benzyl.Thus a compound of formula VI may be converted into a corresponding compound of formula VII (formula set out hereinafter) by reaction with a conventional methylating agent, for example methyl iodide or dimethylsulphate.The compound of formula VII may then be converted into another compound of formula VII in which T represents a carboxy group by selective conversion of the group COORh, for example by treatment with an alkali metal hydroxide such as sodium hydroxide or lithium hydroxide and water.The compound of formula VII in which T represents a carboxy group may then be converted into a compound of formula VII in which T represents COCl by reaction with a chlorinating agent, for example thionyl chloride.The compound of formula VII in which T represents COCl may then be reacted with 2-methylbenzenesulphonamide to afford a compound of formula III in which U is COORj or a salt thereof.The compound of formula III in which U is COORj may then be converted into a compound of formula III in which U is a carboxy group by decomposing the ester group COORj, for example by treatment with sodium hydroxide and water.The compound of formula II may be prepared in racemic form or in the form of a substantially pure enantiomer, for example the (R)-enantiomer. The compound of formula II in racemic form may be prepared from 2-methyl-4,4,4-trifluorobutyric acid, or a reactive derivative thereof such as the hydrochloride, by reaction with ammonia followed by reduction of the resultant amide, for example using lithium aluminium hydride.The compound of formula II in the form of the substantially pure (R)-enantiomer may be prepared from 4,4,4-trifluorobutyric acid as follows.4,4,4-Trifluorobutyric acid may be converted into 4,4,4-trifluorobutyryl chloride by treatment with oxalyl chloride. The 4,4,4-trifluorobutyryl chloride may then be converted into (4R,5S)-4-methyl-3-(4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone by reaction with (4R,5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone in the presence of butyl lithium. The product of this reaction may then be methylated by treatment with sodium bis(trimethylsilylamide) followed by methyl iodide to afford (4R,5S)-4-methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone. This product may then be treated with lithium aluminium hydride to afford (R)-2-methyl-4,4,4-trifluorobutan-1-ol. Treatment of this alcohol with phthalimide in the presence of triphenylphosphine and diethyl azodicarboxylate affords (R)-2-(2-methyl-4,4,4-trifluorobutyl)-1H-isoindol-1,3(2H)-dione. Treatment of this product with hydrazine monohydrate followed by hydrochloric acid affords the desired (R)-2-methyl-4,4,4-trifluorobutylamine as the hydrochloride salt.As stated previously, the compound of formula I possesses leukotriene antagonist properties. Thus, it antagonises at least one of the actions of one or more of the arachidonic acid metabolites known as leukotrienes, for example, C4, D4 and/or E4, which are known to be powerful spasmogens (particularly in the lung), to increase vascular permeability and to be implicated in the pathogenesis of asthma and inflammation, as well as of endotoxic shock and traumatic shock. The compound of formula I is thus useful in treatment of diseases in which leukotrienes are implicated and in which antagonism of their action is desired. Such diseases include, for example, allergic pulmonary disorder such as asthma, hay fever and allergic rhinitis and certain inflammatory diseases such as bronchitis, ectopic and atopic eczema, and psoriasis, as well as vasospastic cardiovascular disease, and endotoxic and traumatic shock conditions.The compound of formula I is a potent leukotriene antagonist and is useful whenever such activity is desired. For example, the compound of formula I is of value as a pharmacological standard for the development and standardisation of new disease models and assays for use in developing new therapeutic agents for treating the diseases in which the leukotrienes are implicated. When used in the treatment of one or more of the above mentioned diseases, the compound of formula I is generally administered as an appropriate pharmaceutical composition which comprises the compound of formula I as defined hereinbefore together with a pharmaceutically acceptable diluent or carrier, the composition being adapted for the particular route of administration chosen. Such compositions may be obtained employing conventional procedures and excipients and binders and may be in a variety of dosage forms. For example, they may be in the form of tablets, capsules, solutions or suspensions for oral administration; in the form of suppositories for rectal administration; in the form of sterile solutions or suspensions for administration by intravenous or intramuscular injection or infusion; in the form of aerosols or nebuliser solutions or suspension for administration by inhalation; and in the form of powders together with pharmaceutically acceptable inert solid diluents such as lactose for administration by insufflation. If a solid form of a compound of formula I is required, it may be preferred to use an amorphous form, which amorphous form may be prepared by adding an aqueous acid, for example hydrochloric acid, to a solution of the sodium salt of the compound of formula I in an alcohol-water mixture, for example methanol-water mixture, to precipitate the compound of formula I. For oral administration a tablet or capsule containing up to 250 mg (and typically 5 to 100 mg) of the compound of formula I may conveniently be used. Similarly, for intravenous or intramuscular injection or infusion a sterile solution or suspension containing up to 10% w/w (and typically 0.05 to 5% w/w) of the compound of formula I may conveniently be used. The dose of the compound of formula I to be administered will necessarily be varied according to principles well known in the art taking account of the route of administration and the severity of the conditions and the size and age of the patient under treatment. However, in general, the compound of formula I will be administered to a warm-blooded animal (such as man) so that a dose in the range of, for example, 0.01 to 25 mg/kg (and usually 0.1 to 5 mg/kg) is received. The leukotriene antagonist properties of the compound of formula I may be demonstrated using standard tests. Thus, for example, they may be demonstrated invitro using the standard guinea-pig tracheal strip preparation described by Krell (J. Pharmacol. Exp. Ther., 1979, 211, 436) and as also described in European Patent Application publication number 220,066 and in U.S. patent 4,859,692.The selectivity of action of compounds as leukotriene antagonists as opposed to non-specific smooth muscle depressants may be shown by carrying out the above invitro procedure using the non-specific spasmogen barium chloride at a concentration of 1.5 x 10-3M, again in the presence of indomethacin at 5 x 10-6M.Alternatively, the antagonistic properties of the compound of formula I can be demonstrated invitro by a receptor-ligand binding assay described by Aharony (Fed. Proc., 1987, 46, 691).In general, the compound of formula I tested demonstrated statistically significant activity as LTC4, LTD4 and/or LTE4 antagonists in one of the above tests at a concentration of about 10-8M or much less. For example, a pKi value of 9.4 was typically determined for a compound of formula I substantially in the form of the (R)- enantiomer.Activity as a leukotriene antagonist may also be demonstrated invivo in laboratory animals, for example, in a routine guinea-pig aerosol test described in Snyder, et al. (J.Pharmacol. Methods., 1988, 19, 219). In this test the particularly useful leukotriene antagonist properties of the carbamoyl derivative of formula I may be demonstrated. According to this procedure, guinea-pigs are pre-dosed with test compound as a solution in poly(ethylene glycol) (generally 1 hour) before an aerosol challenge of leukotriene LTD4 (starting with 2 ml of a 30 microgram/ml solution) and the effect of the test compound on the average time of leukotriene initiated change in breathing pattern (such as onset of dyspnea) recorded and compared with that in undosed, control guinea-pigs. Percent protection engendered by a test compound was calculated from the time delay to the onset of dyspnea compared to that for control animals. Typically, an ED50 of 1.1 mol/kg for a compound of formula I substantially in the form of the (R)- enantiomer following oral administration was determined, without any indication of untoward side-effects at several multiples of the minimum effective dose. By way of comparison, an oral ED50 of 19.2 mol/kg was measured for the compound of Example 10 of European Patent Application publication number 220,066.The invention provides a process for the preparation of a 3-alkylated indole of formula VI (formula set out hereinafter) in which U is COORj and T is COORh wherein Rh and Rj are each independently a conveniently removed acid protecting group, for example, phenyl, benzyl, or (1-6C)alkyl optionally bearing an acetoxy, (1-4C)alkoxy or (1-4C)alkylthio substituent. Particular values for Rh and Rj are, for example, methyl, ethyl, propyl, t-butyl, acetoxymethyl, methoxymethyl, 2-methoxyethyl, methylthiomethyl, phenyl, or benzyl.The reaction between the N-(2-nitrostyryl) enamine and the alkylating agent is conveniently effected at a temperature in the range of from 0 to 120 C, preferably from 15 to 80 C. Suitable solvents for the reaction include nitriles such as acetonitrile; halogenated hydrocarbons such as methylene chloride; ethers such as tetrahydrofuran; hydrocarbons such as toluene; esters such as ethyl acetate; and amides such as dimethylformamide or dimethylacetamide.The product of the alkylation reaction is an imine salt. This salt is conveniently reacted with water directly, without isolation. The reaction is conveniently effected at a temperature in the range of from 0 to 100°C, preferably from 15 to 35°C. Suitable solvents for the reaction include those listed above for the alkylation reaction.The reaction of the imine salt with water affords a (2-nitrophenyl)acetaldehyde.According to another aspect, the invention provides a (2-nitrophenyl)acetaldehyde of formula VIII (formula set out hereinafter) wherein U and T have the meanings given above. The (2-nitrophenyl)acetaldehydes of formula VIII are useful as intermediates in the preparation of the aforementioned leukotriene antagonist, 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide.The (2-nitrophenyl)acetaldehyde is converted into the desired indole by reaction with a reducing agent selected from iron in the presence of an acid e.g. an inorganic acid such as hydrochloric acid or a carboxylic acid such as acetic acid or propanoic acid; stannous chloride; titanium trichloride; sodium dithionite; hydrazine with Raney nickel; and hydrogen in the presence of a transition metal hydrogenation catalyst such as palladium or Raney nickel. Surprisingly good results have been obtained using iron in the presence of an acid, such as acetic acid. The reduction is conveniently effected at a temperature in the range of from 0 to 120°C, preferably from 15 to 100°C. Suitable solvents include aromatic hydrocarbons such as toluene, benzene and the xylenes; ethers such as tetrahydrofuran; alcohols such as ethanol; water and esters such as ethyl acetate. When using iron in the presence of acetic acid, an excess of acetic acid may conveniently be used as solvent.The N-(2-nitrostyryl) enamine starting material may be prepared from a 2-nitrotoluene according to the method described in United States patent number 3,979,410 or Organic Synthesis, Volume 63, 1985, pages 214 to 225. For example, it may be prepared by reacting a 2-nitrotoluene with dimethylformamide dimethyl acetal. The reaction is preferably performed in the presence of pyrrolidine, in which case the N-(2-nitrostyryl) enamine product is a mixture of a (2-nitrostyryl) dimethylamine and a (2-nitrostyryl)pyrrolidine.As stated hereinbefore, the process according to the present invention, and the novel intermediates of formula VIII are particularily useful in the preparation of the compound of formula I. According to a further aspect therefore, the invention provides the use of a (2-nitrophenyl)acetaldehyde of formula VIII in the preparation of 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]-carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide.The invention also provides a process for the preparation of 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-yl-methyl]-3-methoxy-N-o-tolylsulphonylbenzamide, which comprises a) reacting a compound of formula V with a compound of formula IV, wherein each R independently represents a (1-4C)alkyl group or together represent a 4- or 5- membered alkylene or heteroalkylene chain, X is a leaving atom or group, T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group, to afford an imine salt, b) reacting the imine salt with water to afford a (2-nitrophenyl)acetaldehyde of formula VIII,c) reacting the (2-nitrophenyl)acetaldehyde of fomula VIII with a reducing agent selected from iron in the presence of an acid; stannous chloride; titanium trichloride; sodium dithionite; hydrazine with Raney nickel; and hydrogen in the presence of a transition metal hydrogenation catalyst, to afford a compound of formula VI,d) methylating the compound of formula VI to afford a compound of formula VII,e) converting the group T into a 2-methylbenzenesulphonamidocarbonyl group by removing the protecting group Rh, and reacting the resultant carboxylic acid or a reactive derivative thereof with 2-methylbenzenesulphonamide or a salt thereof, andf) converting the group U into a 2-methyl-4,4,4-trifluorobutylaminocarbonyl group by removing the protecting group Rj, and reacting the resultant carboxylic acid or a reactive derivative thereof with 2-methyl-4,4,4-trifluorobutylamine or an acid addition salt thereof.It will be appreciated that the steps e) and f) can be carried out in the order stated or in the reverse order.The following Examples illustrate the invention. Notes: NMR data is in the form of delta values, given in parts per million relative to tetramethylsilane as internal standard. Kieselgel is a trade mark of E Merck, Darmstadt, Germany. Yields are for illustration only and are not to be construed as the maximum attainable after conventional process development. Unless otherwise stated, procedures were carried out at ambient temperature and pressure. EXAMPLE 1Preparation of Methyl 4-(5-methoxycarbonylindol-3-ylmethyl)-3-methoxybenzoatea) Methyl 3-methyl-4-nitrobenzoate. To a stirred suspension of 3-methyl-4-nitrobenzoic acid (100 g, 0.55 mole) in methanol (400 ml) was added thionyl chloride (36 g, 0.30 mole), over a period of 1 hour (the temperature of the reaction mixture rising to about 35-40 °C). The mixture was heated to reflux for 1.5 hours, then cooled to 50-55 °C and maintained at this temperature for 30 minutes prior to cooling to ambient temperature. Water (100 ml) was added over 30 minutes, with cooling applied to maintain the temperature at 20-25 °C. Filtration was followed by washing of the solid with water (2 x 100 ml), and drying at 40°C under vacuum, to afford 103 g (95%) of methyl 3-methyl-4-nitrobenzoate as a yellow solid; m.p. 83-85 °C; NMR (250 MHz, CDCl3), 2.62 (s, 3H, ArCH3), 3.98 (s, 3H, CO2CH3), 8.01 (m, 3H).b) 5-Methoxycarbonyl-2-nitro-β-(1-pyrrolidinyl)styrene and 5-methoxycarbonyl-2-nitro-β-(dimethylamino)styrene. A mixture of the product of step a) (1000 g, 5.13 mole), N,N-dimethylformamide dimethyl acetal (1219 g, 10.26 mole) and pyrrolidine (382 g, 5.38 mole) in N,N-dimethylformamide (3000 ml) was heated to reflux over about 45 minutes, and maintained at a gentle reflux for 2.5 hours. After cooling the reaction mixture to ambient temperature, it was added over 20 minutes to 10 l of ice/water. The resulting slurry was stirred for 30 minutes prior to filtration and washing of the solid with cold water (3 x 1500 ml). Drying at 50 °C under vacuum afforded 1208 g (83.3%) of an 82:18 mixture of 5-methoxycarbonyl-2-nitro-β-(1-pyrrolidinyl)styrene and 5-methoxycarbonyl-2-nitro-β-(1-dimethylamino)styrene as a dark red solid; m.p. 109-112 °C; NMR (250 MHz, CDCl3), 1.97 (m, 0.82 x 4H), 2.95 (s, 0.18 x 6H, N(CH3)2), 3.37 (m, 0.82 x 4H), 3.93 (s, 3H, CO2CH3), 5.77 (d, 0.82 x 1H), 5.78 (d, 0.18 x 1H), 7.08 (d, 0.18 x 1H), 7.39 (d, 0.82 x 1H), 7.49 (dd, 0.82 x 1H), 7.53 (dd, 0.18 x 1H), 7.82 (d, 1H), 8.13 (m, 1H).c) 2-(5-methoxycarbonyl-2-nitro)phenyl-2-(2-methoxy-4-methoxycarbonyl)benzylacetaldehyde. The product of step b) (800 g, 2.95 mole) and methyl 4-bromomethyl-3-methoxybenzoate (770 g, 2.97 mole) in acetonitrile (2000 ml) were heated to reflux over 20 minutes and held at this temperature for 50 minutes. More benzoate (35 g, 0.135 mole) was then added and heating continued for a total of 4 hours. After cooling to ambient temperature, the mixture was diluted with water (2000 ml), added over 5 minutes, during which time a dark brown solid precipitated. The mixture was stirred for 30 minutes and filtered, the precipitate being washed with acetonitrile (500 ml), and dried at 45 °C under vacuum. This afforded 2-(5-methoxycarbonyl-2-nitro)phenyl-2-(2-methoxy-4-methoxycarbonyl)benzylacetaldehyde as a pale brown solid, 914.5 g (77.3 %); m.p. 117-120 °C; NMR (250 MHz, CDCl3): 3.11 (dd, 1H), 3.50 (dd, 1H), 3.82, 3.90, 3.97 (each s, 3H, OCH3 plus 2 x CO2CH3), 4.65 (dd, 1H), 7.00 (d, 1H), 7.46 (m, 2H), 7.88 (d, 1H), 7.93 (d, 1H), 8.04 (dd, 1H), 9.82 (s, 1H).d) Methyl 4-(5-methoxycarbonylindol-3-ylmethyl)-3-methoxybenzoate A stirred suspension of the product of step c) (600 g, 1.49 mole) and iron powder (600 g, 10.7 mole) in acetic acid (2.2 l) and toluene (3.8 l), was heated carefully to reflux. An exotherm occurred at 95 °C, resulting in the mixture reaching reflux without external heating. Heating was then applied as necessary to maintain reflux for a total of 2 hours. The mixture was allowed to cool to ambient temperature, and then cooled at 5 °C for 30 minutes prior to filtration and washing of the solid with toluene (2 x 200 ml). The combined filtrates and washings were washed with 15% brine (3.8 l) and 5% sodium bicarbonate solution (3.8 l), and evaporated under reduced pressure. The resulting solid was recrystallised from methanol (2 1) to afford methyl 4-(5-methoxycarbonylindol-3-ylmethyl)-3-methoxybenzoate (420 g, 79.9 %), m.p. 136-138 °C; NMR (250 MHz, CDCl3): 3.88, 3.90, 3.92 (each s, 3H, OCH3 plus 2 x CO2CH3), 4.16 (s, 2H, ArCH2Ar'), 6.98 (d, 1H), 7.12 (d, 1H), 7.33 (d, 1H), 7.52 (m, 2H), 7.89 (dd, 1H), 8.30 (br.s, 1H), 8.36 (d, 1H).Comparative ExamplePreparation of Methyl 4-(5-benzyloxycarbonylindol-3-ylmethyl)-3-methoxybenzoate by alkylation of benzyl indole-5-carboxylate.A solution of benzyl indole-5-carboxylate (86.8 g), methyl 4-bromomethyl-3-methoxybenzoate (89.5 g) and potassium iodide (57.4 g) in N,N-dimethylformamide (900 ml) was heated to 80 °C for 10 hours. The reaction mixture was evaporated and partitioned between diethyl ether and water. The organic layer was separated and washed with water. The aqueous washes were combined and extracted with diethyl ether. The combined organic extract was dried (MgSO4) and evaporated. The residue was purified by flash chromatography, eluting sequentially with 0:1:1, 2:48:50, 4:46:50, 5:45:50, and 10:40:50 ethyl acetate:hexane:methylene chloride, to afford methyl 4-iodomethyl-3-methoxybenzoate (27.8 g), recovered benzyl indole-5-carboxylate (29.6 g), and the crude product as a tan solid (50.6 g). Treatment of the recovered benzyl indole-5-carboxylate (29.6 g) in N,N-dimethylformamide (250 ml) with methyl 4-iodomethyl-3-methoxybenzoate (29.8 g) at 80 °C for 12 hours, followed by evaporation, gave a dark residue, which was dissolved in diethyl ether and washed with water (3 times). The aqueous washes were combined and extracted with diethyl ether. The combined organic extract was dried (MgSO4) and evaporated. The residue was purified by flash chromatography, eluting sequentially with 0:1:1, 2:48:50, 5:45:50, and 10:40:50 ethyl acetate:hexane:methylene chloride, to give further crude product as a tan solid (31.9 g). The combined crude product (82.5 g) was suspended in diethyl ether (400 ml), heated to reflux for 30 min, cooled and filtered to obtain methyl 4-(5-benzyloxycarbonylindol-3-ylmethyl)-3-methoxybenzoate as an ivory solid (46.1 g, 31%); partial NMR (250 MHz, CDCl3): 3.84 (s, 3H, CO2CH3), 3.88 (s, 3H, OCH3), 4.14 (s, 2H, CH2), 5.35 (s, 2H, OCH2), 6.97 (d, 1H, indole-H(2)), 8.15 (br, 1H, NH), 8.37 (s, 1H, indole-H(4)).This Comparative Example demonstrates the lower yield of 3-alkylated product obtainable by direct alkylation of an indole compared with that obtainable by the process according to the invention.REFERENCE EXAMPLE 2Preparation of Methyl 3-benzylindole-5-carboxylatea) 2-(5-Methoxycarbonyl-2-nitro)phenyl-2-benzylacetaldehyde. The product of Example 1b) (5.42 g, 20 mmole) and benzyl bromide (2.39 ml, 20 mmole) in acetonitrile (15 ml) were heated at reflux under an atmosphere of nitrogen for 5 hours. Water (2 ml) was added and the solution was then concentrated in vacuo. The residue was passed through a silica column (50 g Kieselgel 60), with dichloromethane (300 ml) as eluant. Concentration in vacuo gave the intermediate aldehyde as a dark oil, 5.8 g; NMR (250 MHz, CDCl3): 3.11 (dd, 1H), 3.57 (dd, 1H), 3.97 (s, 3H, OCH3), 4.56 (dd, 1H), 7.03-7.40 (m, 5H, Ph), 7.95 (m, 2H), 8.10 (dd, 1H), 9.82 (s, 1H, CHO).b) Methyl 3-benzylindole-5-carboxylate. The product of step a) (5.8 g) was heated in toluene (40 ml) and acetic acid (26.4 ml) with iron powder (5.17 g, 92.7 mmole), at 95 °C under an atmosphere of nitrogen for 3.5 hours. After cooling overnight, the solid was removed by filtration and washed with toluene (2x20 ml). The combined filtrate and washings were washed with 15% brine (40 ml) and saturated aqueous sodium bicarbonate (40 ml), and concentrated in vacuo. The residue was passed through a silica column (35 g Kieselgel 60), with dichloromethane (100 ml) as eluant, and the eluate concentrated in vacuo. Crystallisation of the residue from toluene (15 ml) gave 2.65 g (50% overall from the enamine) of methyl 3-benzylindole-5-carboxylate; NMR (250 MHz, CDCl3): 3.91 (s, 3H, OCH3), 4.14 (s, 2H, ArCH2Ar'), 6.92 (d, 1H), 7.15-7.36 (m, 6H), 7.90 (dd, 1H), 8.25 (br.s, 1H, NH), 8.32 (s, 1H); microanalysis found: C, 76.8; H, 5.6; N, 5.1%; C17H15NO2 requires: C, 77.0; H, 5.7; N, 5.3%.REFERENCE EXAMPLE 3Preparation of Methyl 3-(3-methylbut-2-enyl)indole-5-carboxylatea) 2-(5-Methoxycarbonyl-2-nitro)phenyl-2-(3-methyl-but-2-enyl)acetaldehyde. The product of Example 1b) (5.42 g, 20 mmole) and 1-bromo-3-methylbut-2-ene (2.33 ml, 20 mmole) in acetonitrile (15 ml) was stirred overnight at ambient temperature, followed by heating to 50 °C for one hour. The solution was then worked up as in Example 2 to yield 2-(5-methoxycarbonyl-2-nitro)phenyl-2-(3-methyl-but-2-enyl)acetaldehyde as a dark red oil, 5.46 g; NMR (250 MHz, CDCl3): 1.51 (s, 3H, CCH3), 1.63 (s, 3H, CCH3), 2.57 (m, 1H), 2.90 (m, 1H), 3.97 (s, 3H, OCH3), 4.24 (m, 1H), 5.04 (m, 1H, C=CH), 8.00 (m, 2H), 8.11 (dd, 1H), 9.82 (s, 1H, CHO).b) Methyl 3-(3-methylbut-2-enyl)indole-5-carboxylate. The product of step a) was reduced following the method described in Example 2b) to afford a yellow oil which crystallised on standing. Recrystallisation from cyclohexane (20 ml) afforded 3.14 g (64.6% overall from the enamine) of methyl 3-(3-methylbut-2-enyl)-indole-5-carboxylate, m.p. 88-91 °C; NMR (250 MHz, CDCl3): 1.78 (s, 6H, C(CH3)2), 3.48 (d, 2H, ArCH2), 3.95 (s, 3H, OCH3), 5.43 (m, 1H, C=CH), 7.00 (s, 1H), 7.33 (d, 1H), 7.90 (dd, 1H), 8.22 (br.s, 1H, NH), 8.38 (s, 1H); microanalysis found: C, 74.1; H, 7.2; N, 5.8%. C15H17NO2 requires: C, 74.0; H, 7.0; N, 5.8%.REFERENCE EXAMPLE 4Preparation of methyl 3-methoxycarbonylmethylindole-5-carboxylatea) 2-(5-Methoxycarbonyl-2-nitro)phenyl-2-methoxycarbonylmethylacetaldehyde. The product of Example 1b) (5.42 g, 20 mmole), methyl bromoacetate (1.89 ml, 20 mmole) and sodium iodide (3.00 g, 20 mmole) in acetonitrile (15 ml) was heated at 65 °C under an atmosphere of nitrogen for 24 hours. The cooled mixture was treated with water (3 ml), concentrated in vacuo and partitioned between water (50 ml) and ethyl acetate (50 ml). The organic layer was washed with 10% aqueous sodium sulfite (50 ml) and concentrated in vacuo. Chromatography on silica (200 g Kieselgel 60), eluted with 1000 ml dichloromethane afforded 2-(5-methoxycarbonyl-2-nitro)phenyl-2-methoxycarbonylmethylacetaldehyde as a red gum, 2.35 g; NMR (250 MHz, CDCl3): 2.80 (dd, 1H), 3.30 (dd, 1H), 3.69 (s, 3H, OCH3), 3.97 (s, 3H, OCH3), 4.70 (t, 1H), 7.96 (d, 1H), 8.06 (d, 1H), 8.17 (dd, 1H), 9.78 (s, 1H, CHO).b) Methyl-3-methoxycarbonylmethylindole-5-carboxylate. The product of step a) was reduced following the method described in Example 2b) to afford a dark solid. Recrystallisation from dichloromethane-toluene (15 ml) gave 1.24 g (25.6% overall from the enamine) of methyl 3-methoxycarbonylmethylindole-5-carboxylate, m.p. 131-133 ° C; NMR (250 MHz, CDCl3): 3.73 (s, 3H, OCH3), 3.81 (s, 2H, ArCH2), 3.95 (s, 3H, OCH3), 7.20 (d, 1H), 7.32 (d, 1H), 7.90 (dd, 1H), 8.37 (s, 1H), 8.50 (br.s, 1H, NH); microanalysis found: C, 63.0; H, 5.3; N, 5.6%. C13H13NO4 requires: C, 63.2; H, 5.3; N, 5.7%.EXAMPLE 5Preparation of (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]-carbamoyl)-1-methylindol-3-yl-methyl]-3-methoxy-N-o-tolylsulphonylbenzamidea) Methyl 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoate. To a stirred solution of the product of Example 1d) (50 g, 142 mmole) and methyl iodide (87.5 ml, 1.42 mole) in tetrahydrofuran (333 ml) was added concentrated sodium hydroxide liquor (40 ml, 0.71 mole). After 7.5 hours water (200 ml) was added, and the organic layer separated and washed with brine (150 ml) and finally water (150 ml). After removal of 300 ml distillate under reduced pressure, a solid precipitated which was collected by filtration and washed with hexane (50 ml). Drying of the beige solid at 40 °C under vacuum afforded 48.0 g (91.3%) of methyl 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoate, m.p. 137-140 °C; NMR (250 MHz, DMSO-d6): 3.91 (s, 3H, N-CH3), 3.98 (s, 6H, 2 x CO2CH3), 4.07 (s, 3H, OCH3), 4.22 (s, 2H, ArCH2Ar'), 7.34 (m, 2H), 7.61 (m, 3H), 7.90 (dd, 1H), 8.33 (d, 1H).b) 4-(5-Methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid. To a solution of the product of step a) (33.50 g, 91.3 mmole) in tetrahydrofuran (335 ml) and methanol (100 ml) was added water (67 ml) and lithium hydroxide monohydrate (4.025 g. 95.8 mmole). After the reaction mixture had stirred at ambient temperature for about 20 hours, it was heated to reflux and about 250 ml distillate collected. The residual solution was cooled to room temperature, diluted with water (210 ml) and toluene (210 ml), and the organic layer separated and extracted with water (40 ml). Combined aqueous layers were treated dropwise with acetic acid (4.18 ml, 73.0 mmole) and stirred for around 30 minutes prior to collection of the precipitate by filtration. After washing with water (2 x 67 ml) and methanol (2 x 67 ml), 28.07 g (84.1%) of 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid were obtained as a white solid, m.p. 228-230 °C; NMR (250 MHz, DMSO-d6): 3.77, 3.83, 3.93 (each s, 3H, OCH3 plus NCH3 plus CO2CH3), 4.08 (s, 2H, ArCH2Ar'), 7.17 (d, 1H), 7.23 (s, 1H), 7.49 (m, 3H), 7.77 (dd, 1H), 8.21 (d, 1H).c) 4-(5-Methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoyl chloride. A solution of thionyl chloride (2.42 ml, 33 mmole) in dichloromethane (10 ml) was added dropwise over 5 minutes to a suspension of the product of step b) (10.59 g, 30 mmole) in dichloromethane (90 ml) containing N,N-dimethylformamide (0.2 ml), stirred at reflux under an atmosphere of nitrogen. After 2 hours, solvent was removed from the resulting yellow solution by distillation, approximately 85 ml distillate being collected. Dilution of the residue with methyl t-butyl ether was followed by stirring at 15 °C for 30 minutes prior to collection of the solid precipitate by filtration. After washing with methyl t-butyl ether (2 x 20 ml), 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoyl chloride was obtained as an off-white solid, 10.10 g (90.6%); m.p. 147-149 °C; NMR (250 MHz, DMSO-d6): 3.76, 3.92, 3.97 (each s, 3H, NCH3 plus OCH3 plus CO2CH3), 4.16 (s, 2H, ArCH2Ar'), 6.87 (s, 1H), 7.20 (d, 1H), 7.29 (d, 1H), 7.54 (d, 1H), 7.66 (dd, 1H), 7.92 (dd, 1H), 8.32 (d, 1H).d) 4-(5-Methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide. A solution of 4-(dimethylamino)pyridine (8.17 g, 66.9 mmole) in dichloromethane (20 ml) was added over 15 minutes to a stirred suspension of the product of step c) (9.94 g, 26.8 mmole) and 2-methylbenzenesulfonamide (6.87 g, 40.1 mmole) in dichloromethane (30 ml). After 45 minutes the solution was heated to reflux and 20 ml distillate collected. Acetone (150 ml) was added and a further 80 ml distillate collected. The mixture was allowed to cool overnight and finally stirred at 15 °C before collection of the solid by filtration. This was then slurry-washed with methanol (3 x 30 ml) to afford 16.22 g (96.4%) of 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide, as its 4-(dimethylamino)pyridine salt; m.p. 185-187 °C (with partial melting and resolidification at 138-140 ° C); NMR (250 MHz, DMSO-d6): 2.53 (s, 3H, ArCH3), 3.13 (s, 6H, N(CH3)2), 3.76, 3.83, 3.86 (each s, 3H, OCH3 plus NCH3 plus CO2CH3), 4.02 (s, 2H, ArCH2Ar'), 6.92 (d, 2H), 7.02 (d, 1H), 7.11-7.32 (m, 4H), 7.39-7.53 (m, 3H), 7.75 (dd, 1H), 7.88 (d, 1H), 8.20 (m, 3H).e) 4-(5-Carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide. A mixture of the product of step d) (15 g, 23.8 mmole), concentrated sodium hydroxide liquor (6.75 ml, 119 mmole), water (85 ml) and tetrahydrofuran (18 ml) was stirred for three hours at 65 °C, and the now homogeneous solution cooled to 50-55 °C and maintained at this temperature during the subsequent acidification and extraction. Concentrated hydrochloric acid was added to a pH of 7-8, followed by addition of tetrahydrofuran (44 ml) and n-butyl acetate (29 ml), and further adjustment of the pH to 1-2. The reaction mixture was allowed to settle and the lower aqueous layer separated. The organic layer was washed with 5% brine solution (2 x 20 ml). The tetrahydrofuran was removed by distillation (ca 40 ml distillate collected at a jacket temperature of 95 °C), and the residual mixture cooled to 15-20 °C. The product was collected by filtration, washed with butyl acetate (15 ml) and dried at 50 °C. The yield of 4-(5-carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)-benzamide was 11.08 g (94%); m.p. 264-267 °C; NMR (250 MHz, DMSO-d6): 2.63 (s, 3H, ArCH3), 3.78 (s, 3H, NCH3), 3.95 (s, 3H, OCH3), 4.08 (s, 2H, ArCH2Ar'), 7.18 (d, 1H), 7.22 (s, 1H), 7.38-7.65 (m, 6H), 7.79 (d, 1H), 8.06 (d, 1H), 8.20 (s, 1H).f) (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide. To a mixture of 4-(5-carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide (103.5 g), 4-dimethylaminopyridine (112.4 g), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydro-chloride (51.8 g) in tetrahydrofuran (distilled from sodium benzophenone ketyl) (2.0 L), which had been stirred for 2 hours, was added (R)-2-methyl-4,4,4-trifluorobutylamine hydrochloride (42.6 g); and the reaction mixture was stirred overnight (about 18 hours, incomplete reaction) then heated to reflux for two hours (complete reaction). The cooled reaction mixture was diluted with ethyl acetate (2 L) washed with 1 N hydrochloric acid (twice) and brine, dried (MgSO4) and evaporated. The residue (138.6 g) was combined with impure product from similar procedures (28.0 g) and purified by flash chromatography, eluting with methylene chloride:ethyl acetate (sequentially, 1:0, 9:1 and 3:1) to afford a solid which was triturated twice with ether to give the crude title compound (135.2 g) which was recrystallized from ethanol (1.2 L) and acetone (0.3 L) (concentrated by boiling to about 0.9 L and refrigerated) and dried under vacuum to provide the title compound (117.1 g, 65% recovery) as a white crystalline solid; m.p. 141.5-143.5 °C; NMR (300 MHz, DMSO-d6): 1.01 (d, 3H, CH3), 2.0-2.2 (m, 2H, CF3CH2), 2.3-2.5 (m, 1H, CHCH3), 2.61 (s, 3H, ArCH3), 3.23 (br t, 2H, CH2N), 3.76 (s, 3H, NCH3), 3.92 (s, 3H, OCH3), 4.07 (s, ArCH2Ar'), 7.13 (s, 1H), 7.17 (d, 2H), 7.38-7.69 (m, 6H), 7.72 (d, 1H), 8.05 (d, 1H), 8.11 (s, 1H), 8.46 (br t, 1H, NHCO); analysis for C31H32F3N3O5S: calculated: C, 60.48; H, 5.24; N, 6.83%, found: C, 60.47; H, 5.27; N, 6.67%The starting amine hydrochloride was prepared as follows: a. 4,4,4-Trifluorobutyric acid. A solution of lithium hydroxide monohydrate (324 g) in water (1.8 l) was added to a stirred solution of ethyl 4,4,4-trifluorobutyrate (436 g) in methanol (2.0 l) and dry tetrahydrofuran (2.0 l) and the suspension was stirred overnight. After the suspension was partially evaporated, the residue was diluted with water and washed with diethyl ether. The aqueous layer was acidified with 6M hydrochloric acid and extracted with diethyl ether. The combined extracts were washed (brine), dried (MgSO4), and filtered. The filtrate was evaporated and the residue distilled (b.p. 165-168 °C) to give 4,4,4-trifluorobutyric acid (347 g, 95%); m.p. 27-30 °C; partial NMR; (300 MHz, CDCl3): 2.33-2.57 (m, 2H, CF3CH2), 2.66 (t, 2H, CH2CO2H).b. 4,4,4-Trifluorobutyryl chloride. Dimethyl formamide (1.0 ml) and oxalylchloride (239 ml) were added to a 0 °C solution of 4,4,4-trifluorobutyric acid (343 g) in dry methylene chloride (230 ml) and warmed to room temperature overnight. The methylene chloride was removed by distillation and the residue distilled to yield 4,4,4-trifluorobutyryl chloride (328 g, 85%); bp 103-106 °C; partial NMR (300 MHz, CDCl3): 2.47-2.64 (m, 2H, CF3CH2) 3.19 (t, H, CH2COCl).c. (4R,5S)-4-Methyl-3-(4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone. A solution of n-butyllithium (2.0 mole) in hexane was added to a stirred solution of (4R,5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone (353 g) in dry tetrahydrofuran (2500 ml) at -78 °C under an inert atmosphere. The solution was stirred at -70 °C for 15 min, then 4,4,4-trifluorobutyryl chloride (320 g) was added over 30 min at -60 °C and the mixture warmed to room temperature and stirred overnight. The mixture was evaporated and the residue was partitioned between diethyl ether and water. The ethereal layer was washed (1N hydrochloric acid, brine (twice)), dried (MgSO4), and evaporated to yield crude product (604 g, about 100%). Filtration through 3000 ml of silica gel using 1:1 methylene chloride:hexanes as the eluent afforded a white solid. Recrystallization from methylene chloride:hexanes afforded (4R,5S)-4-methyl-3-(4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (519 g, 86%); m.p. 93-95 °C; partial NMR (300 MHz, CDCl3): 0.91 (d, 3H, CH3), 2.45-2.65 (m, 2H, CF3CH2), 3.18-3.40 (m, 2H, CH2CO), 4.78 (m, 1H, 4-H oxazolidinone), 5.70 (d, 1H, 5-H oxazolidone), 7.30-7.44 (m, 5H, Ar).d. (4R,5S)-4-Methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone. To a stirred solution of sodium bis(trimethylsilylamide) (1.9 mole) in tetrahydrofuran (1900 ml) cooled to -40 °C was added a solution of (4R,5S)-4-methyl-3-(4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (517 g) in dry tetrahydrofuran (800 ml) under an inert atmosphere. The mixture was maintained at -40 °C for one-half hour, and warmed to -35 °C over an additional one-half hour. To this mixture was added iodomethane (142 ml) over approximately 15 min while maintaining the internal reaction temperature between -35 °C and -30 °C. The mixture was stirred for an additional 2 h at -30 °C and the cold reaction mixture was poured over chilled aqueous ammonium chloride (700 g in 2 l water). The mixture was diluted with diethyl ether (1 l) and the layers separated. The organic layer was washed (25% w/v aqueous sodium bisulfate, brine). The aqueous portions were extracted with 1:1 methylene chloride:diethyl ether and methylene chloride. The combined organic layers were dried (MgSO4) and evaporated to afford crude product (595 g) as a reddish oil. Filtration through silica gel (3000 ml), using a gradient of 1-5% ethyl acetate in hexanes, followed by evaporation, afforded a white solid (490 g) which was a mixture of the named product, the diastereomeric methylated side product and unmethylated starting material. Crystallization from diethyl ether:hexanes afforded (4R,5S)-4-methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (370 g, 68 %) as a white solid; m.p. 68-70°C. Analysis by HPLC (Zorbax silica gel, 4.6 mm x 25 cm, 1:9 ethyl acetate:hexanes, FR = 1.5 ml/min, UV detector at 254 nm) showed this sample to be about 99% pure (retention volume = 2.6). A second recrystallization of this white solid from diethyl ether:hexanes afforded an analytical sample of (4R,5S)-4-methyl-3-((2R)-2-methyl-4,4,4-trifluoro-butyryl)-5-phenyl-2-oxazolidinone (300 g, 55%) as transparent colourless needles; m.p. 74.5-75 °C; partial NMR (300 MHz, CDCl3): 0.89 (d, 3H, 4-CH3 of oxazolidinone), 1.33 (d, 3H, CH(CH3)CO), 2.10-2.31 (m, 1H, CF3CH2), 2.74-2.97 (m, 1H, CF3CH2), 4.03-4.17 (m, 1H, CHCO), 4.79 (m, 1H, 4-H of oxazolidinone), 5.71 (d, 1H, 5-H of oxazolidinone), 7.26-7.44 (m, 5H, phenyl). HPLC analysis as above showed 99.9% purity; analysis for C15H16F3NO3: calculated: C, 57.14; H, 5.11; N, 4.44%, found: C, 57.17; H, 5.16; N, 4.59%e. (R)-2-Methyl-4,4,4-trifluorobutan-1-ol. Lithium aluminium hydride (10.26 g) was added to a stirred solution of (4R,5S)-4-methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (28 g) in dry diethyl ether (200 ml) at -20 °C under an inert atmosphere, then the mixture was warmed to 0 °C. After 2 h at 0 °C, water (10.27 ml), 10% w/v sodium hydroxide (10.27 ml) and water (31 ml) were added, and the mixture was stirred 20 min. The salts were filtered and washed with distilled diethyl ether. The diethyl ether solution was dried (K2CO3) and diluted with pentane. This resulted in precipitation of recovered (4R,5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone which was isolated by filtration. Concentration of the filtrate by distillation afforded several fractions. The first fractions (bath temperature to 60 °C) were pentane and diethyl ether; a second set of fractions (bath temperature 60 °C to 100 °C) was 12 g of a oil that was a 40:60 mixture of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (calculated as 4.8 g alcohol) and diethyl ether by NMR. Warming the remaining tarry residue (bath temperature 85 °C) under vacuum (13,330 Pa) afforded an additional 7.2 g of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (total yield, 12.0 g, 94%); partial NMR (300 MHz, CDCl3-D2O shake): 1.06 (d, 3H, CH3), 1.41 (br t, 1H, OH), 1.86-2.07 (m, 2H, CH(CH3) plus one CF3CH2), 2.31-2.42 (m, 1H, one CF3CH2), 3.49 (dd, 1H, one CH2OH), 3.58 (dd, 1H, one CH2OH). f. (R)-2-(2-Methyl-4,4,4-trifluorobutyl)-1H-isoindol-1,3(2H)-dione. Diethyl azodicarboxylate (15.4 ml) was added to a 0 °C, stirred slurry of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (about 12.0 g), phthalimide (13.4 g), and triphenylphosphine (23.7 g) in diethyl ether (about 6.5 g, see above) and dry tetrahydrofuran (110 ml), warmed to room temperature overnight, and stirred an additional 8 h. The mixture was evaporated, methylene chloride was added to the residue, and the slurry was filtered. The filtrate was purified by flash chromatography, eluting with 1:1 methylene chloride:hexanes, to give (R)-2-(2-methyl-4,4,4-trifluorobutyl)-1H-isoindol-1,3(2H)-dione (17.1 g, 75%) as a white solid; m.p. 45-47 °C; partial NMR (400 MHz, CDCl3): 1.08 (d, 3H, CH3), 1.94-2.07 (m, 1H, CF3CH2), 2.14-2.31 (m, 1H, CF3CH2), 2.36-2.50 (m, 1H, CHCH3), 3.58 (dd, 1H, CH2N), 3.64 (dd, 1H, CH2N).g. (R)-2-Methyl-4,4,4-trifluorobutylamine hydrochloride. Hydrazine monohydrate (3.1 ml) was added to a stirred solution of (R)-2-(2-methyl-4,4,4-trifluorobutyl)-1H-isoindole-1,3(2H)-dione (17.1 g) in anhydrous ethanol (85 mL) and heated to reflux. After three hours' reflux, the solution was cooled; ethanol (40 mL) was added; and the solution was acidified to pH 1 by addition of concentrated hydrochloric acid and was filtered. The filtrate was evaporated, and the residue was purified by sublimation (bath temperature 170 °C, at 6.6 Pa) to yield (R)-2-methyl-4,4,4-trifluorobutylamine hydrochloride as a white solid (9.89 g, 88%); m.p. 187-191 °C; partial NMR (300 MHz, DMSO-d6-D2O shake): 1.05 (d, 3H, CH3), 2.06-2.36 (m, 2H, CF3CH2) 2.36-2.54 (m, 1H, CHCH3) 2.73 (dd, 1H, CH2N), 2.87 (dd, 1H, CH2N) 8.20 (br s, 2H, NH2).EXAMPLE 6A solution of the product of Example 1b) (26.0 g, 100 mmol) and methyl 4-bromomethyl-3-methoxybenzoate (26.7 g, 103 mmol) in acetonitrile (66 ml) was heated to reflux for 3.3 h, the solvents removed at reduced pressure and the resulting dark brown gum stored under nitrogen for 18 h. The residue was dissolved in acetic acid (284 ml) and iron powder (16.6 g, 300 mmol) added. The mixture was heated at 100°C for 2.5 h, cooled to room temperature, held at that temperature for 0.5 h, filtered and the residue washed with acetic acid (2 x 20 ml). Water (240 ml) was added to the combined filtrates over 20 min. and the mixture allowed to stand at room temperature for 66 h. The solidified residue was pulverised and filtered. The residue was recrystallized from methanol to afford 18.6 g of methyl 4-(5-methoxycarbonylindol-3-ylmethyl)-3-methoxy benzoate as a white solid. FORMULAE	A process for the preparation of a 3-alkylated indole, which comprises:- a) reacting a N-(2-nitrostyryl) enamine of the formula IV with a compound of the formula V to afford an imine salt, wherein each R independently represents a (1-4C)alkyl group or together represent a 4- or 5- membered alkylene or heteroalkylene chain, X is a leaving atom or group, T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group,b) optionally reacting the imine salt with water to afford a (2-nitrophenyl)acetaldehyde, andc) reacting the imine salt or the (2-nitrophenyl)acetaldehyde with a reducing agent selected from iron in the presence of an acid; stannous chloride; titanium trichloride; sodium dithionite; hydrazine with Raney nickel; and hydrogen in the presence of a transition metal hydrogenation catalyst; to afford the desired 3-alkylated indole.A process as claimed in claim 1, in which the imine salt is reacted with water to afford a (2-nitrophenyl)acetaldehyde.A process as claimed in claim 1 or 2, in which the reducing agent is iron in the presence of acetic acid.A process as claimed in claim 1, 2 or 3, in which the alkylation is effected at a temperature in the range of from 0 to 120 C, and the reduction is effected at a temperature in the range of from 0 to 120 C.A process as claimed in any one of claims 1 to 4, in which the imine salt is reacted with water at a temperature in the range of from 0 to 100 C.A (2-nitrophenyl)acetaldehyde of formula VIII wherein T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group selected from phenyl, benzyl, and (1-6C)alkyl optionally bearing an acetoxy, (1-4C)alkoxy or (1-4C)alkylthio substituent.The use of a (2-nitrophenyl)acetaldehyde as claimed in claim 6 in the preparation of 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]-carbamoyl)-l-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide. A process as claimed in Claim 1 which comprises (a) reacting a compound of formula V with a compound of formula IV wherein each R independently represents a (1-4C)alkyl group or together represent a 4- or 5- membered alkylene or heteroalkylene chain, X is a leaving atom or group, T is COORh, U is COORj, and Rh and Rj are each independently a conveniently removed acid protecting group to afford an imine salt,(b) reacting the imine salt with water to afford a (2-nitrophenyl)acetaldehyde of formula VIII, and(c) reacting the (2-nitrophenyl)acetaldehyde of formula VIII with a reducing agent selected from iron in the presence of an acid; stannous chloride; titanium trichloride; sodium dithionite; hydrazine with Raney nickel; and hydrogen in the presence of a transition metal hydrogenation catalyst, to afford a compound of formula VI followed by the subsequent reaction steps ofd) methylating the compound of formula VI to afford a compound of formula VII e) converting the group T into a 2-methylbenzenesulphonamidocarbonyl group by removing the protecting group Rh, and reacting the resultant carboxylic acid or a reactive derivative thereof with 2-methylbenzenesulphonamide or a salt thereof, andf) converting the group U into a 2-methyl-4,4,4-trifluorobutylaminocarbonyl group by removing the protecting group Rj, and reacting the resultant carboxylic acid or a reactive derivative thereof with 2-methyl-4,4,4-trifluorobutylamine or an acid addition salt thereof, to give 4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide.	ZENECA LTD; ZENECA LIMITED	BROOK STEPHEN ALAN; COSTELLO GERARD FRANCIS; HARRISON PETER JOHN; JACOBS ROBERT TOMS; BROOK, STEPHEN ALAN; COSTELLO, GERARD FRANCIS; HARRISON, PETER JOHN; JACOBS, ROBERT TOMS

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