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EP-0489548-B1
| 489,548 |
EP
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B1
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EN
| 19,941,214 | 1,992 | 20,100,220 |
new
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C07C209
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C07D209, C07C211, C07C231
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C07C311, A61P37, A61K31, C07C211, C07D209, C07C209, C07C231, C07C233, A61P11
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C07C 231/18, C07C 211/15, M07D209:24, C07C 209/50, C07D 209/24
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A process for the preparation of 2(R)-methyl-4,4,4-trifluorobutylamine, intermediates, and a process for the preparation of a derivative thereof
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A process for the preparation of (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof which comprises a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; and c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof. The product may be acylating with a carboxylic acid of formula III wherein U is carboxy, or a reactive derivative thereof to afford (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-yl-methyl]-3-methoxy-N-o-tolylsulphonylbenzamide. The indole is useful as a leukotriene antagonist, for example in the treatment of asthma or allergic rhinitis.
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The present invention relates to the preparation of a pharmaceutical intermediate. European Patent Application Publication Number EP432984, which claims priority from British Patent Application number 8927981.4, filed on 11th December, 1989 discloses the compound 4-[5-(N-[4,4,4-trifluoromethylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide. This compound has the formula I set out hereinafter. The 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, for example in the treatment of those diseases in which leukotrienes are implicated, such as in the treatment of allergic or inflammatory diseases, or of endotoxic or traumatic shock conditions. The 4,4,4-trifluoro-2-methylbutyl substituent in the compound of formula I has a chiral centre. Thus the compound has (R)- and (S)-forms. The (R)-form is preferred to the (S)-form. Accordingly, the compound of formula (I) is preferably enriched in the (R)-form. In the following, a compound containing the 4,4,4-trifluoro-2-methylbutyl substituent which is enriched in the (R)- or (S)-form will be identified by the prefix (R)- or (S)-respectively. Where a compound is not identified by such a prefix, it may be in any form. The compound of formula I enriched in the (R)-form may be prepared by acylating (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof such as the hydrochloride with a carboxylic acid of formula III (formula set out hereinafter) wherein U is carboxy, or a reactive derivative thereof. The acylation is preferably performed in the presence of a dehydrating agent, such as 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, optionally together with an organic base, for example, 4-dimethylaminopyridine. A new process has now been found for preparing (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof. The present invention provides a process for the preparation of (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof, which comprises:- a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; and c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof. As stated hereinabove, (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof is useful as an intermediate in the preparation of (R)-3-methoxy-4-[1-methyl-5-(2-methyl-4,4,4-trifluorobutylcarbamoyl)indol-3-ylmethyl]-N-(2-methylphenylsulfonyl)benzamide, which is a potent leukotriene antagonist disclosed in European Patent Application Publication Number EP432984 According to a preferred aspect of the invention, (S)-diastereomeric butyramide obtained in step b) is treated with a strong base, and the resultant butyramide is recycled to step b). The function of the strong base is to catalyse the inversion by racemisation of molecules of the (S)-form of the butyramide into the (R)-form. Preferably the (S)-diastereomeric butyramide is racemised by the strong base. It will be appreciated that 2-methyl-4,4,4-trifluorobutanoic acid, being a fluorinated compound, is expensive to obtain. Accordingly, it is highly advantageous to be able to convert both the (R)- and (S)-enantiomers of this compound into the desired (R)-enantiomer of 2-methyl-4,4,4-trifluorobutylamine. The strong base may be, for example, an alkali metal alkoxide such as sodium or potassium ethoxide or t-butoxide, an alkali metal amide such as lithium isopropylamide, or an alkali metal hydroxide such as sodium hydride. The optically active amine used in the process according to the invention may be a primary or secondary amine. Examples of optically active amines include alpha-substituted benzylamines, such as alpha-(1-6C)alkyl benzylamines, for instance (S)-phenylethylamine; oxazolidinones, for example (4R,5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone or (4S)-(-)-4-isopropyl-2-oxazolidinone; ephedrine; norephedrine; amino acids and their esters such as proline, proline esters, glutamic acid and valine; glucosamine and 2-amino-1-butanol. Particularly good results have been obtained using an alpha-substituted benzylamine. The acylation of the optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid may be effected using a conventional method. Thus the optically active amine may be reacted with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof, optionally in the presence of a base and/or a dehydrating agent. A reactive derivative of the acid may be, for example, an acid halide such as the chloride, the anhydride or a mixed anhydride such as that formed with ethanoic acid. Suitable bases for the acylation include, for example, tertiary amines such as 4-dimethylaminopyridine. Examples of suitable dehydrating agents include, for example, carbodiimides, for instance dicyclohexylcarbodiimide or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and carbonyldiimidazole. The acylation is conveniently performed in the presence of a suitable solvent such as an aromatic hydrocarbon, for example, toluene; a halogenated hydrocarbon, for example, dichloromethane; or an ether, for example, tetrahydrofuran or t-butyl methyl ether. Conveniently, the acylation is effected at a temperature in the range of, for example, from 0 to 120°C, preferably from 15 to 60°C. In step b) of the process according to the invention, (R)-diastereomeric butyramide may be separated from (S)-diastereomeric butyramide by a conventional physical technique for separating diastereomers, for example by crystallisation or chromatography. Preferably it is separated by crystallisation. Depending upon the particular optically active amine which has been used in step a), and the crystallisation solvent, either (R)- or (S)-diastereomeric butyramide may crystallise out. This may be determined by routine experimentation. Thus the (R)-diastereomeric amide may conveniently be identified by converting both diastereomers into 2-methyl-4,4,4-trifluorobutylamine, and comparing the properties of these amine products with those of an authentic sample of (2R)-methyl-4,4,4-trifluorobutylamine. Suitable solvents for the crystallisation include, for example, aromatic hydrocarbons such as toluene, saturated hydrocarbons such as petroleum ether, alcohols such as as aqueous industrial methylated spirits, and halogenated hydrocarbons. It has been found that when an alpha-substituted benzylamine is used as the optically active amine, for example (1S)-phenylethylamine, (R)-diastereomeric butyramide may be separated from (S)-diastereomeric butyramide by crystallisation. The (R)-diastereomeric butyramide may be converted into the desired (2R)-methyl-4,4,4-trifluorobutylamine or an acid addition salt thereof, by a method known for a conversion of this type. According to one method, the (R)-diastereomeric butyramide may be hydrolysed, for example by heating with an acid, such as dilute hydrochloric acid, or a weak base to afford (2R)-methyl-4,4,4-trifluorobutanoic acid, which may then be converted into (2R)-methyl-4,4,4-trifluorobutyramide by treatment with ammonia. Alternatively, the (R)-acid may be converted into a reactive derivative thereof, for example the chloride, prior to treatment with ammonia. This amide may then be reduced to afford the desired amine. An advantage of this method is that the optically active amine may be recovered after the hydrolysis. According to another method an (R)-diastereomeric butyramide which is derived from an oxazolidinone may be reduced, for example with lithium aluminium hydride, to afford (R)-2-methyl-4,4,4-trifluorobutan-1-ol; then this butanol may be reacted with phthalimide to afford an isoindol-1,3(2H)-dione; and then this dione may be reacted with hydrazine monohydrate to afford the desired amine. According to another method, an (R)-diastereomeric butyramide which is derived from an alpha-substituted benzylamine may be reduced to the corresponding amine, and then hydrogenolysed to afford the desired (2R)-methyl-4,4,4-trifluorobutylamine. The reduction may conveniently be effected using a hydride reducing agent such as borane, lithium aluminium hydride or sodium borohydride, optionally in the presence of a Lewis acid such as aluminium chloride. Preferably borane is used as the reducing agent. It has been found that when borane is used, the optical purity of the resultant product is exceptionally high. The reduction is conveniently effected in the presence of a solvent such as an ether, e.g. tetrahydrofuran, at a temperature in the range of, for example, -10 to 100°C, preferably from 0 to 80°C. The hydrogenolysis is conveniently effected using a transition metal based hydrogenation catalyst, for example a palladium, platinum or rhodium-based catalyst such as palladium on charcoal. The upper limit for the pressure is not critical. Conveniently the pressure is in the range of from 1 to 10 bar, preferably from 2 to 5 bar. The temperature is conveniently from 0 to 120°C, preferably 30 to 100°C. If desired, the amine product may be converted into an acid addition salt by treatment with an acid, for example hydrochloric acid. According to another aspect, the invention provides a process for the preparation of (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide, which comprises preparing (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof, by a process as described above, and then acylating this with a carboxylic acid of formula III (formula set out hereinafter) wherein U is carboxy, or a reactive derivative thereof. Thus, for example, an indole carboxylic acid of formula III may be reacted with a suitable dehydrating agent, for example, with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, or with a hydrochloride or hydrobromide salt thereof, optionally together with an organic base, for example, 4-dimethylaminopyridine, and with 2-methyl-4,4,4-trifluorobutylamine, or with a salt thereof, especially a hydrochloride or hydrobromide salt, optionally together with an organic base, for example, 4-dimethylaminopyridine, in the presence of a suitable solvent or diluent, for example tetrahydrofuran or 1,2-dimethoxyethane, at a temperature in the range of, for example 10 to 85 °C, for example in tetrahydrofuran at or near 67 °C. Alternatively, a reactive derivative of an indole acid of formula III, for example, an acid halide (such as the acid chloride), acid anhydride or mixed acid anhydride (such as that formed with ethyl chloroformate in the presence of an organic base such as, for example triethylamine or 4-dimethylaminopyridine) or a lower alkyl ester (such as the methyl ester) may be used as the acylating agent, conveniently together with a suitable inert solvent or diluent, for example dichloromethane, tetrahydrofuran or 1,2-dimethoxyethane. The compound of formula III may be prepared as follows: A compound of formula IV (formula set out hereinafter) wherein U represents COORj wherein Rj is 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, is reacted with a compound of formula V wherein T represents COORh wherein Rh is a conveniently removed acid protecting group for example phenyl, benzyl or (1-6C) alkyl optionally bearing an acetoxy, (1-4C) alkoy or (1-4C) alkylthio substituent to afford a compound of formula VI. The 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. 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 lithium hydroxide or sodium 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 COC1 by reaction into 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. 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. 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 disorders 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 standardization 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. It may be obtained employing conventional procedures and excipients and binders and may be in a variety of dosage forms. For example, it 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 suspensions 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 condition 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 1.5x10⁻³M, again in the presence of indomethacin at 5x10⁻⁶M. 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 compounds 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 the 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 by 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 mmol/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 mmol/kg was measured for the compound of Example 10 of European Patent Application publication number 220,066. The following non-limiting 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 1a) (RS)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]-butyramide.A solution of 2-methyl-4,4,4-trifluorobutanoic acid (10.0g, 0.064 moles) in dichloromethane (150ml) was treated with 4-(N,N-dimethylaminopyridine (7.8g, 0.064 moles) and the mixture was stirred for 15 mins. A solution containing (1S)-phenylethylamine (7.8g, 0.064 moles) in dichloromethane (50ml) was added, the mixture was stirred for a further 15 mins, and then a solution of dicyclohexylcarbodiimide (15.9g, 0.077 moles) in dichloromethane (100ml) was added. Stirring was continued for 15 hours, then the precipitated dicyclohexylurea was removed by filtration and the filtrate was concentrated to an oil under reduced pressure. The oil was partitioned between aqueous hydrochloric acid (2N, 100ml) and ether (100ml) and the two phase mixture was filtered to remove a further quantity of dicyclohexylurea. The layers were separated and the ether fraction was washed sequentially with aqueous hydrochloric acid (2N, 100ml), aqueous sodium hydroxide solution (2N, 100ml) and saturated brine (100ml). The solution was dried over magnesium sulphate, filtered, and concentrated under reduced pressure to an oil, which solidified on standing. The solid, which comprised a mixture of the two diastereomeric butyramides was used directly in the next step. b) (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]-butyramide.The product of step a) was dissolved in warm toluene (180ml) and petroleum ether (b.p. 100-120°C) (180ml) was added. The mixture was stirred at room temperature for 15 hours during which time crystallisation occurred. The white crystalline solid was filtered, washed with petroleum ether (b.p. 100-120°C) and dried at 60°C to give impure title compound (4.07g), contaminated with ca.3% of the unwanted diastereomer, as estimated by HPLC analysis. The crystallisation mother liquors, which were enriched in the unwanted (S)-diastereomer, were recycled as follows: The mother liquors (containing ca. 14.0g of amide mixture) were concentrated under reduced pressure to give an oil, which was redissolved in tetrahydrofuran (150ml) and treated with potassium tert-butoxide (12.1g, 2 molar equivalents). The colourless solution became yellow and a slight exotherm was noted. The mixture was stirred for 1 hour, by which time complete equilibration of the diastereomers had occurred, as monitored by HPLC analysis. Water (100ml) was added, the mixture was stirred for 10 mins, then extracted with ether (2 x 100ml). The combined ether extracts were washed with water (2 x 100ml) and saturated brine (100ml) then concentrated to an oil. The oil was dissolved in toluene (130ml) and petroleum ether (b.p. 100-120°C) (130ml) was added. The solution was seeded with the desired (R)-diasteromeric butyramide and stirred at room temperature for 15 hours. The white crystalline precipitate was filtered, washed with petroleum ether (b.p. 100-120°C) and dried at 60°C to give crude title compound (0.99g), contaminated with ca.4.0% of the unwanted diastereomer as monitored by HPLC analysis. The combined crude title compound was recrystallised from petroleum ether (b.p. 100-120°C) to give material containing less than 1.0% of the unwanted diastereomer, in ca. 95% recovery, based on combined crude material. NMR (δ, CDCl₃): 1.2 (3H,d,J=7Hz), 1.5 (3H,d,J=7Hz), 2.0-2.3 (1H,m), 2.4-2.6 (1H,m), 2.6-2.9 (1H,m), 5.0-5.3 (1H,m), 5.6-5.9 (1H,br s) and 7.2-7.5 (5H,m)ppm. c) (2R)-Methyl-4,4,4-trifluorobutyl-((1S)-phenylethyl)amine.A solution of borane-tetrahydrofuran complex in tetrahydrofuran (1.0M, 35ml, 0.035 moles) was cooled to <5°C under a nitrogen atmosphere and a solution of the product of step b) (3.5g, 0.0135 moles) in tetrahydrofuran (17.5ml) was added dropwise over 20 mins, maintaining the temperature below 5°C throughout. The mixture was then heated to reflux for 3 hours. The mixture was cooled to room temperature and a solution of concentrated hydrochloric acid (5.25ml) in water (20ml) was added. The mixture was heated to reflux for 30 mins, then cooled to room temperature and concentrated under reduced pressure to give a damp white solid. The solid was suspended in water (100ml) and concentrated sodium hydroxide liquor was added to pH12. The mixture was extracted with ether (3 x 75ml), the combined organic extracts were dried over magnesium sulphate and the filtered solution was concentrated under reduced pressure to give (2R)-methyl-4,4,4-trifluorobutyl-((1S)-phenylethyl)amine (3.21g) as a waxy solid. NMR (δ, CDCl₃): 1.05 (3H,d,J=7Hz), 1.35 (3H,d,J=7Hz), 1.5-2.6 (5H,m), 3.6-3.8 (1H,m) and 7.2-7.5 (5H,m)ppm. d) (2R)-Methyl-4,4,4-trifluorobutylamine hydrochloride.A solution of the product of step c) (3.21g, 0.013 moles) in industrial methylated spirit (100ml) was treated with 10% palladium on carbon (50% water wet paste, 400mg) and the resulting mixture was hydrogenolysed at 65°C under a pressure of 3 bar for 3 hours. The mixture was filtered through diatomaceous earth to remove catalyst, concentrated hydrochloric acid (7.5ml) was added, and the mixture was concentrated under reduced pressure. The residue was dried by azeotropic distillation with toluene (2 x 75ml) giving a tan coloured solid (2.07g). A sample of the solid (1.75g) was recrystallised form dichloromethane (13ml) and ether (13ml) to give (2R)-methyl-4,4,4-trifluorobutylamine hydrochloride (1.21g) as a white solid, m.p. 223-225°C. 19F NMR (500MHz, proton decoupled, CFCl₃ as reference, 1 mg of title compound and 50 mg of (R)-(-)-2,2,2-trifluoro-1-(9-anthryl)ethanol in CDCl₃): -63.86 (s)ppm. NMR shows presence of 3.6% of the (S)-enantiomer at -63.83 (s)ppm. Preparation of starting materials1) Ethyl (2E)-2-methyl-4,4,4-trifluorobutenoate.A suspension of (carbethoxyethylidene)triphenylphosphorane (400g, 1.10 moles) in tetrahydrofuran (600 ml) was treated with aqueous fluoral hydrate (71.5% w/w, 180g, 1.10 moles) over a period of 4 hours. During the addition the reaction temperature rose to 45°C and all of the solid dissolved to give a clear brown solution. The mixture was allowed to stand for 15 hours and was then heated under reflux for 3.5 hours. The solution was distilled at 20mm Hg (26.6 mbar) until the temperature in the distillation flask reached 140°C giving ethyl (2E)-2-methyl-4,4,-4-trifluorobutenoate as a solution in tetrahydrofuran (Solution (A), 0.75l, containing a maximum of 201g of alkene. NMR(δ, CDCl₃): 1.3(3H,t,J=7Hz), 2.1 (3H,br s), 4.3 (2H,q,J=7Hz) and 6.7 (1H,m)ppm, (plus signals due to tetrahydrofuran). 2) Ethyl 2-methyl-4,4,4-trifluorobutanoate.Solution (A) (0.75l) was treated with 10% palladium on carbon (20g, 50% water wet paste) and the resulting mixture was hydrogenated under a pressure of 2bar. The reaction was complete after an uptake of hydrogen of 25.91. The catalyst was removed by filtration through kieselguhr to give ethyl 2-methyl-4,4,4- trifluorobutanoate as a solution in tetrahydrofuran (Solution (B), ca. 1l, containing ca. 200g of ester) which was used directly in the next stage. 3) 2-Methyl-4,4,4-trifluorobutanoic acid.Solution (B) (ca. 1l) was treated sequentially with water (500ml) and lithium hydroxide monohydrate (150g, 3.6 moles) and was then heated under reflux (70°C) for 2 hours. The mixture was allowed to cool to room temperature and the tetrahydrofuran was removed by distillation at 20mm Hg (26.6 mbar). The resulting aqueous slurry was treated with concentrated hydrochloric acid to pH2, by which point all solid had dissolved and an oil had separated. The mixture was allowed to stand for 4 days, then the aqueous layer was decanted and extracted with ether (2 x 200ml). The separated oil was partitioned between water (500ml) and ether (500ml) and the combined ether extracts were dried over magnesium sulphate. Filtration and evaporation under reduced pressure at room temperature gave the crude acid (171.5g). Distillation of a 45g sample of crude acid gave 2-methyl- 4,4,4-trifluorobutanoic acid (23.7g) as a colourless oil, b.p. 173-176°C (760mm Hg), ca. 95% pure by GC analysis. NMR(δ CDCl₃): 1.35 (3H,d,J=7Hz), 2.05-2.30 (1H,m), 2.55-2.95 (2H,m) and 10.2-11.1 (1H, br s)ppm. Example 2Preparation of (R)-3-Methoxy-4-[1-methyl-5-(2-methyl-4,4,4-trifluorobutylcarbamoyl)indol-3-ylmethyl]-N-(2-methylphenylsulfonyl)benzamide.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 hydrochloride (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 titlecompound (117.1 g, 65% recovery) as a white crystalline solid; mp 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 material 5-carboxyindole derivative may be prepared as follows: a. 4-(5-Methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid.To a solution of methyl 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoate (105.1 g) in tetrahydrofuran (1.4 l) was added methanol (450 ml) and deionized water (450 ml), followed by an equimolar amount of lithium hydroxide monohydrate (12.00 g). After the reaction mixture had stirred about 20 hours, it was acidified to pH 2 by addition of 6N hydrochloric acid (60 ml). Evaporation of the organic solvents resulted in the precipitation of a crude product (104.2 g) which was filtered and dried under vacuum before it was recrystallized by dissolving it in boiling tetrahydrofuran (600 ml), addition of toluene (about 1.2 l) and concentration to about one liter. Following cooling and stirring overnight, filtration, and drying under vacuum, a first crop is (71.1 g) was obtained. A second, similar recrystallization of this material from tetrahydrofuran (500 ml) and toluene (1 l) afforded 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (58.3 g, 57.7%) as an off-white solid; NMR (300 MHz, DMSO-d₆): 3.78 (s, 3H, NCH₃), 3.83 (s, 3H, CO₂CH₃), 3.92 (s, 3H, OCH₃), 4.07 (s, ArCH₂Ar′), 7.17 (d, 1H), 7.18 (s, 1H), 7.43-7.50 (m, 3H), 7.75 (dd, 1H), 8.19 (d, 1H); the same benzoic acid obtained by a similar procedure, but purified by flash chromatography, eluting with (methylene chloride:tetrahydrofuran:acetic acid (sequentially, 1:0:0, 1:9:0, and 0:400:1) followed by isolation and drying under vacuum of crystals formed on standing in methylene chloride:tetrahydrofuran fractions, had mp 228.0-229.5 °C. An additional amount of the benzoic acid (23.6 g, 23.3%), as well as recovered diester (11.5 g, 10.7%), was obtained by concentration and flash chromatography of the mother liquors, eluting with methylene chloride:tetrahydrofuran (sequentially, 1:0, 3:1, 2:1). b. 4-(5-Methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide.To a solution of 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoic acid (125.9 g) in tetrahydrofuran (3.0 l, distilled from sodium benzophenone ketyl) (prepared by heating at 50 °C until dissolution was complete, followed by cooling to room temperature with an ice-water bath) was added 4-dimethylaminopyridine (56.6 g) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (102.4 g), and the mixture was stirred one hour. To the mixture was added 2-methylbenzene-sulfonamide (67.1 g), and the reaction mixture was stirred about 3 days (for convenience). The reaction mixture was diluted with ethyl acetate (2.0 l) and washed with 1N hydrochloric acid (twice) and brine (3 times, until neutral), and the aqueous extracts were back washed with ethyl acetate. The combined ethyl acetate solution was dried (MgSO₄), and partially evaporated to give a slurry of solid in ethyl acetate (about 0.5 l) which was refrigerated overnight. Collection of the solid afforded the crude product (158.5 g, 88%, essentially pure by TlC) as a light pink solid. Recrystallization by dissolution in hot tetrahydrofuran (1.5 l), filtration while hot, dilution with ethyl acetate (2.0 l), and boiling down to a final volume of about 2.5 l afforded a first crop of 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide (105.5 g, 59%) as a white solid; mp 211-213 °C; NMR (250 MHz, DMSO-d₆): 2.60 (s, 3H, ArCH₃), 3.76 (s, 3H, NCH₃), 3.82 (s, 3H, CO₂CH₃), 3.92 (s, 3H, ArOCH₃), 4.04 (s, 2H, ArCH₂Ar′), 7.15 (d, 1H), 7.22 (s, 1H), 7.38-7.58 (m, 6H), 7.75 (dd, 1H), 8.03 (dd, 1H), 8.17 (d, 1H). (Two additional crops (35.5 g, 20%) and crude product (39.5 g) from concentration of the mother liquors were also obtained.) c. 4-(5-Carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)benzamide.A mixture of 4-(5-methoxycarbonyl-1-methyl-indol-3-ylmethyl)-3-methoxy-N-(2-methylphenylsulfonyl)-benzamide (130.0 g), tetrahydrofuran (1.0 l) and 1 N sodium hydroxide (1.0 l) was heated to about 60 °C overnight, then treated with additional 1N sodium hydroxide (200 ml) and heated an additional 5 hours at 60 °C (likely unnecessary). The cooled reaction mixture was acidified with 6 N hydrochloric acid (250 ml) and extracted with ethyl acetate. The ethyl acetate solution was washed with brine (three times), dried (MgSO₄) and evaporated to give a solid which was dried at 50 °C under vacuum to give 4-(5-carboxy-1-methylindol-3-ylmethyl)-3-methoxy-N-(2-methylphenyl-sulfonyl)benzamide (12.9 g, 100% when calculated as 0.45 hydrate), mp 255-257 °C; NMR (300 MHz, DMSO-d₆): 2.60 (s, 3H, ArCH₃), 3.76 (s, 3H, NCH₃), 3.91 (s, 3H, OCH₃), 4.05 (s, 2H, ArCH₂Ar′), 7.15 (d, 1H), 7.19 (s, 1H), 7.39-7.51 (m, 5H), 7.58 (br t, 1H), 7.72 (dd, 1H), 8.03 (dd, 1H), 8.14 (d, 1H); anaylsis for C₂₆H₂₄N₂O₆S.0.45 H₂O: calculated: C, 62.37; H, 5.01; N, 5.60%, found: C, 62.60; H, 5.03; N, 5.52% Methyl 4-(5-methoxycarbonyl-1-methylindol-3-ylmethyl)-3-methoxybenzoate, used in step a., above, may be obtained from methyl indole-5-carboxylate and methyl 4-bromomethyl-3-methoxybenzoate, for example by reaction in the presence of potassium iodide in dimethylformamide, followed by methylation, for example by treatment with sodium hydride in dimethylformamide followed by iodomethane. Example 3a) (4R,5S)-4-Methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone.To a mixture of (4R,5S)-(+)-4-methyl-5-phenyl-2-oxazolidinone (3.22g) and tetrahydrofuran (35ml) at -70°C, under nitrogen was added 1.625M n-butyllithium (12.31mL) and the mixture was stirred for 15 min. 2-Methyl-4,4,4-trifluorobutyryl chloride (3.5g) was added to the reaction mixture which was stirred for 15 min at -70°C and then at 0°C for 1 hour. The reaction was quenched with ammonium chloride and extracted with ethyl acetate. The organic phase was washed (saturated NaHCO₃, brine) and dried (MgSO₄). Evaporation and flash chromatography, eluting with 5:95 then 1:9 ethyl acetate:petroelum ether, afforded the two diastereomeric products. Recrystallization from hexane at 20°C gave (4R,5S)-4-methyl-3-((2R)--2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (2.376g, 42%) as colorless needles; mp 72.5-73.5°C; TLC, Rf = 0.43, 1:9 ethyl acetate:petroleum ether; MS(CI): 316 (M+H). b) (R)-2-Methyl-4,4,4-trifluorobutan-1-ol.Lithium aluminium hydride (10.26g) was added to a stirred solution of (4R,5S)-4-methyl-3-((2R)-2-methyl-4,4,4-trifluorobutyryl)-5-phenyl-2-oxazolidinone (28g) in dry diethyl ether (200mL) at -20°C under an inert atmosphere, then the mixture was warmed to 0°C. After 2h at 0°C, water (10.27mL), 10% w/w sodium hydroxide (10.27mL) and water (31mL) 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 dilued 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 12g of a oil that was a 40:60 mixture of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (calculated as 4.8g alcohol) and diethyl ether by NMR. Warming the remaining tarry residue (bath temperature 85°C) under vacuum (13,330 Pa) afforded an additional 7.2g of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (total yield, 12.0g, 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). c) (R)-2-(2-Methyl-4,4,4-trifluorobutyl)--1H-isoindol-1,3(2H)-dione.Diethyl azodicarboxylate (15.4mL) was added to a 0°C, stirred slurry of (R)-2-methyl-4,4,4-trifluorobutan-1-ol (about 12.0g), phthalimide (13.4g), and triphenylphosphine (23.7g) in diethyl ether (about 6.5g, see above) and dry tetrahydrofuran (110 mL), warmed to room temperature overnight, and stirred an additional 8h. 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 (17.1g, 75%) as a white solid; mp 45-47°C; partial NMR (400MHz, 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). d) (R)-2-Methyl-4,4,4-trifluorobutylamine hydrochloride.Hydrazine monohydrate (3.1mL) was added to a stirred solution of (R)-2-(2-methyl-4,4,4-trifluorobutyl)-1H-isoindole-1,3(2H)-dione (17.1g) in anhydrous ethanol (85mL) was heated to reflux. After three hours reflux, the solution was cooled; ethanol (40mL) was added; and the solution was acidified to pH1 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 6.6Pa) to yield (R)-2-methyl-4,4,4-trifluorobutylamine hydrochloride as a white solid (9.89g, 88%); mp 187-191°C; partial NMR (300 MHz, DMSO-d₆-D₂) 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 4a) Impure (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramideCarbonyldiimidazole (22.85 g) was stirred under nitrogen in toluene (80 ml) at ambient temperature. 2-Methyl-4,4,4-trifluorobutanoic acid (20.0 g) was then added dropwise from a dropping funnel, while maintaining the temperature at about 25 °C, and the dropping funnel was then washed through with toluene (20 ml). The mixture was then stirred under nitrogen for 1.5 hours. (1S)-Phenylethylamine (15.53 g) was then added dropwise, and the dropping funnel was then washed through with toluene (20 ml). The mixture was then heated to 80 °C, and stirring was continued for 1 hour. Hydrochloric acid (2M, 60 ml) was then added, and the mixture was stirred at 80 °C for 15 minutes. The organic layer was then separated and washed with hydrochloric acid (2M, 80 ml), while maintaining the temperature at 80 °C. More toluene (175 ml) was then added, and the mixture was concentrated to a volume of 265 ml by distillation at atmospheric pressure. Petroleum ether (b.p. 100 - 120 °C, 265 ml) was then added, keeping the temperature above 80 °C. The mixture was allowed to cool to 42 °C, and was then seeded with (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]-butyramide and then kept at 40 °C for 1 hour. The mixture was then allowed to cool to 30 °C, and was stirred at 30 °C overnight. The crystalline product was then filtered and dried at 65 °C to afford (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide (25-29%), contaminated with about 5% of the undesired (S) diastereomer. b) (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramideImpure 4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide (94(R):6(S)) (5.0g), prepared by a method similar to that described in step a) above, was dissolved in industrial methylated spirits (18.75 ml) by heating under reflux with stirring. Water (18.75 ml) was then added slowly, while continuing to heat the solution under reflux. The mixture was then heated under reflux for a further 45 minutes, and was then allowed to cool to room temperature, with continued stirring, overnight. The mixture was then filtered, and the crystalline product was washed with water (10 ml) and dried at 65 °C to give the titlecompound 4.45 g (89%). The product contained only 0.3% of the unwanted (S)-diastereomer. c) Recovery of (S)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide from mother liquorsMother liquors (740 ml, containing at most 30.45 g of 4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide) obtained by a procedure similar to that described in step a) above were concentrated to 100 ml by distillation at atmospheric pressure. Petroleum ether (b.p. 100 - 120 °C) (100 ml) was then added, and the mixture was allowed to cool to room temperature with stirring overnight. The mixture was then cooled to between 0 and 5 °C for three hours and was then filtered. The crystalline product was then washed with petroleum ether (b.p. 100 - 120 °C) (30 ml, twice) and dried at 65 °C to afford 24.8 g (81.4%) of 4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide. The ratio of (S) to (R) diastereomer in the product was 2:1. d) Epimerisation of recovered (S)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide10 g of 4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide (diastereomer ratio 2(S):1(R), prepared by a method similar to that described in step c)above) was dissolved in tetrahydrofuran (25 ml) with stirring. Potassium t-butoxide (2.02 g) was then added, together with tetrahydrofuran (5 ml). The resultant solution was then stirred for one hour, by which time complete equilibration of the diastereomers had occured, as monitored by HPLC analysis. Water was then added with cooling to maintain the temperature at 20-25°C. The solution was then stirred for 10 minutes, and then toluene (25 ml) was added, and the stirring was continued for a further 15 minutes. The organic layer was then separated, washed with water (12.5 ml) and concentrated by distillation at atmospheric pressure to a temperature of 110 ° C. The volume was adjusted to 80 ml by adding toluene, and the mixture heated under reflux. Petroleum ether (b.p. 100 - 120 °C) (80 ml) was then added. The solution was then allowed to cool to 40 °C, seeded with (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide and held at 40 °C for 2 hours. The mixture was then allowed to cool to 30 °C, and was stirred overnight. The crystalline product was then filtered off, washed with petroleum ether (b.p. 100 - 120 °C) and dried at 65 °C to afford 3.20 g (32%) of (R)-4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide contaminated with about 6 % of the undesired (S) diastereomer. FORMULAE
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Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, GR, IT, LI, LU, NL, SEA process for the preparation of (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof, which comprises:- a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; and c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof. A process as claimed in claim 1, in which (S)-diastereomeric butyramide obtained in step b) is treated with a strong base, and the resultant butyramide is recycled to step b). A process as claimed in claim 2, in which the strong base is an alkali metal alkoxide, an alkali metal amide or an alkali metal hydroxide. A process as claimed in any one of claims 1 to 3, in which the optically active amine is an alpha-substituted benzylamine. A process as claimed in any one of claims 1 to 4, in which the (R)-diastereomeric butyramide is separated from the (S)-diastereomeric butyramide by crystallisation. A process as claimed in claim 4 or claim 5, in which the (R)-diastereomeric butyramide is converted into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof by reduction to the corresponding amine, and then hydrogenolysis to afford the desired (2R)-methyl-4,4,4-trifluorobutylamine. A process as claimed in claim 6, in which the (R)-diastereomeric butyramide is reduced using borane. 4,4,4-trifluoro-2-methyl-N-[(S)-1-phenylethyl]butyramide. (2R)-Methyl-4,4,4-trifluorobutyl-((1S)-phenylethyl)amine, or an acid addition salt thereof. A process for the preparation of (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide, which comprises a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof; and d) acylating the (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof with a carboxylic acid of formula III: wherein U is carboxy, or a reactive derivative thereof. Claims for the following Contracting State : ESA process for the preparation of (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof, which comprises:- a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; and c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof. A process as claimed in claim 1, in which (S)-diastereomeric butyramide obtained in step b) is treated with a strong base, and the resultant butyramide is recycled to step b). A process as claimed in claim 2, in which the strong base is an alkali metal alkoxide, an alkali metal amide or an alkali metal hydroxide. A process as claimed in any one of claims 1 to 3, in which the optically active amine is an alpha-substituted benzylamine. A process as claimed in any one of claims 1 to 4, in which the (R)-diastereomeric butyramide is separated from the (S)-diastereomeric butyramide by crystallisation. A process as claimed in claim 4 or claim 5, in which the (R)-diastereomeric butyramide is converted into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof by reduction to the corresponding amine, and then hydrogenolysis to afford the desired (2R)-methyl-4,4,4-trifluorobutylamine. A process as claimed in claim 6, in which the (R)-diastereomeric butyramide is reduced using borane. A process for the preparation of (R)-4-[5-(N-[4,4,4-trifluoro-2-methylbutyl]carbamoyl)-1-methylindol-3-ylmethyl]-3-methoxy-N-o-tolylsulphonylbenzamide, which comprises a) acylating an optically active amine with 2-methyl-4,4,4-trifluorobutanoic acid or a reactive derivative thereof to afford a butyramide; b) separating (R)-diastereomeric butyramide from (S)-diastereomeric butyramide; c) converting the (R)-diastereomeric butyramide into the desired (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof; and d) acylating the (2R)-methyl-4,4,4-trifluorobutylamine, or an acid addition salt thereof with a carboxylic acid of formula III: wherein U is carboxy, or a reactive derivative thereof.
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ZENECA LTD; ZENECA LIMITED
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BERNSTEIN PETER ROBERT; BREWSTER ANDREW GEORGE; JACOBS ROBERT TOMS; SEPENDA GEORGE JOSEPH; YEE YING KWONG; BERNSTEIN, PETER ROBERT; BREWSTER, ANDREW GEORGE; JACOBS, ROBERT TOMS; SEPENDA, GEORGE JOSEPH; YEE, YING KWONG
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EP-0489549-B1
| 489,549 |
EP
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B1
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EN
| 19,960,131 | 1,992 | 20,100,220 |
new
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H01R9
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H01R23, H01R4
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H01R12, H01R4
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H01R 23/66C, H01R 4/24B3C1B
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An electrical wire connector
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An electrical wire connector (2) comprises a female insulating housing (4) receiving a male insulating housing (8). The female housing (4) has anchored therein, a plurality of electrical terminals (6) each having a wire receiving part (30) comprising a pair of arms (28) connected by a bight (32) and defining a wire receiving slot (44) between upper parts (36) of the arms (28). The arms (28) are resiliently deflectable away from each other as a wire (W) is inserted into the wire receiving slot (44) up to wire contact surfaces (37) between the upper parts (36) of the arms (28). The male housing (8) has a row of wire receiving passageways (48) each intersecting a slot (56) in the male housing (8), which slot receives the wire receiving part (30) of a respective terminal (6) when the male housing (8) has been fully inserted into the female housing (4). Wires (W) previously inserted into the wire receiving passages (48) are forced into the wire receiving slots (44) of the terminals (6) during the insertion of the male housing (8) into the female housing (4). The parts (34 and 36) of each arm (28) are so dimensioned that the wire insertion force is desirably low. Since the arms (28) of the terminals (6) are not plastically deformed by the insertion of the wires (W), the connector (2) can be used as a switch.
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This invention relates to an electrical wire connector comprising mating first and second insulating housings, the first housing containing a plurality of electrical terminals each defining a wire receiving slot, and being secured in the first housing, the second housing defining a like plurality of terminal receiving slots and a wire receiving passage communicating with each terminal receiving slot, the housings being mateable to cause each terminal to enter a respective one of the terminal receiving slots,thereby to force a wire inserted into the wire receiving passage communicating with that terminal receiving slot, into the wire receiving slot of that terminal. The present invention consists in an electrical wire connector as defied in claim 1. US-A-4 652 070 discloses a connector according to the preamble of claim 1. Embodiments of the invention will now be described by way of example with reference to the accompanying drawings in which: FIGURE 1 is a diagrammatic side view shown partly in section, of an electrical wire connector comprising a female housing containing a plurality of wire receiving electrical terminals, and a male housing for mating with the female housing and for receiving stripped end portions of insulated electrical leads; FIGURE 2 is a front view of the female housing shown partly in section and with parts omitted; FIGURE 3 is a diagrammatic sectional view of the male housing illustrating an aspect of the operation of the connector where the terminals thereof are according to the embodiment of Figure 9; FIGURE 4 is a side view of a conventional bare wire receiving terminal; FIGURE 5 is an isometric view of one of the terminals; FIGURES 6 and 7 are of similar views to that of Figure 5 but illustrating successive stages in the insertion of a stripped wire end portion into the terminal; FIGURE 8 is a graph illustrating the force exerted by the terminal shown in Figure 4 and a terminal of the connector against a wire inserted thereinto, plotted against the depth of insertion of the wire into the terminal; FIGURE 9 is an enlarged isometric view similar to that of Figure 7 but showing a terminal according to another embodiment and further illustrating that aspect of the operation of the connector, which is illustrated in Figure 3; FIGURE 10 is an isometric view of the female housing; FIGURE 11 is an enlarged isometric view of the male housing; FIGURE 12 is an isometric view of the connector showing the male housing partially mated with the female housing for the insertion of the end portions of the insulated electrical leads into the male housing; FIGURE 13 is a similar view to that of Figure 12, shown partly in section and showing the lead end portions inserted into the male housing; FIGURE 14 is a similar view to that of Figure 13 showing the male housing fully mated with the female housing; and FIGURE 15 is an isometric view showing the male housing fully mated with the female housing. An electrical wire connector 2 for making galvanic connection to the stripped end portions of insulated electrical leads will now be described with particular reference to Figures 1 to 9. The connector 2 comprises a one piece molded female insulating housing 4, having wire receiving electrical terminals 6 secured therein, and a one piece molded male insulating housing 8 for mating with the housing 4. The female housing 4 comprises a base 10 having through, terminal receiving slots 12 therein front and rear side walls, 14 and 16, respectively, and opposite end walls 18, upstanding from the base 10. The walls 14, 16 and 18 cooperate with the base 10 to define an elongate socket 20. The rear side wall 16 comprises an upstanding resilient latch arm 17 having a latching shoulder 19. Each terminal 6, which has been stamped and formed from a single piece of sheet metal stock is uniplanar and is of rectangular cross section. Each terminal 6 comprises a pin 22, extending from one side of a substantially square anchoring part 24 from the opposite side of which projects a neck 26 supporting a slotted, resilient wire receiving part 30. The part 30 comprises a bight 32 connecting a pair of arms 28, parts 34 of which converge towards each other in a direction away from the bight 32 and which, at their position of closest convergence merge at junctions 35 with upper, parallel parts 36 of the arms 28 terminating in chamfered surfaces 38 defining a wire guiding mouth 40. Inner faces of the arms 28, cooperate to define a slot having a part 42 tapering away from the neck 26 and adjoining a narrow rectilinear wire receiving part 44 of the slot. The opposite planar inner faces of the parts 36 of the arms 28 cooperate to provide final wire contact surfaces 37 immediately adjacent to the parts 34 of the arms 28. Each arm 38 has a lever length 11 between its chamfered surface 38 and the bottom of the bight 32, the length 12 between the contact surfaces 37 and the bottom of the bight 32 being greatly shorter than the length 11 as will be apparent from Figure 6. The arms 28 are capable of resilient torsional movement about their junctions with the bight 32. The ratio of the lengths 11 and 12 is approximately 4:2.5. In contradistinction, in a conventional slotted, wire receiving terminal 6a shown in Figure 4, the arms 28a converge towards each other from the wire receiving mouth and thereafter extend parallel to each other up to the anchoring part of the terminal. As shown in Figure 1, the male housing 8 comprises an elongate block 46 having a row of five wire receiving passages 48 (only one of which is shown in Figure 1) extending in parallel relationship from a transverse wire receiving channel 50 defined by a hood 51 projecting forwardly from the block 46 and having an enlarged insulating receiving mouth 52 opening into a forward face 53 of the hood 51. There intersects each of the passages 48, a respective one of five terminal arm receiving slots 56 extending perpendicularly to the passages 48 and each opening both into a top face 58 of the block 46 and a bottom face 60 thereof. The block 46 has on a rear face 64 thereof, opposite to the hood 51, a latch member 66 resting on the top of the latch arm 17 for subsequent latching under the latching shoulder 19 of the latch arm 17 of the female housing 4. As shown in Figure 3, each slot 56 has therein a pair of abutment shoulders 68, the shoulders 68 being located on each side of the respective passage 48 with which the slot 56 communicates the shoulders 68 being provided where the terminals are according to the embodiment of Figure 9. In use of the connector 2, the male housing 8 is located in the female housing 4 in an initial position shown in Figure 1 with the hollow plug 62 of the housing 8 partially inserted into the socket 20 of the housing 4. The end portions of five insulated wires W (only one of which is shown in Figure 1) of insulated leads L, for example of a ribbon cable, are stripped of their insulation I for termination by means of the connector 2. Each wire W is inserted into a respective one of the passages 48 in the direction of the arrow A in Figure 1 by way of the mouth 52 of the hood 51 so that the stripped portion of each wire W is fully received in the passage 48, the end portion of the insulation I of the wire being received in the hood 51. The housing 8 is then depressed in the direction of the arrow B in Figure 1, so that the latch member 66 after resiliently displacing the latch arm 17 snaps under the latching shoulder 19 at which time the plug 62 is fully inserted into the socket 20. During the insertion of the plug 62, the arms 28 of each terminal 6 enter a respective slot 56 of the housing 8, so that, initially, as shown in Figure 6, the wire W in its passage 48 is forced into the rectilinear wire receiving part 44 of the slot of the terminal 6, guided by the chamfered surfaces 38 thereof. As the plug 62 is pushed home into the socket 20, the wire W is forced down between the parts 36 of the arms 28 of the respective terminal 6 until, as shown in Figure 7, wire W reaches the final wire contact surfaces 37, at which time the plug 62 bottoms on the base 10 of the socket 20 so that the wire W is retained in its final position between the contact surfaces 37 of the arms 28. Each wire W is thereby securely galvanically connected to a respective one of the terminals 6. In the graph of Figure 8, the ordinate represents the contact force F exerted by the arms 28 against the inserted wire W and the abscissa represents the insertion depth D of the wire W between the arms 28. The curve X indicates the wire insertion characteristic of a terminal 6, whereas the curve Y indicates the wire insertion characteristic of a conventional bare wire receiving terminal 6a shown in Figure 4. By virtue of the long lever length 11 and the shorter length 12 referred to above, and thus the soft spring characteristic of the parts 30 of the terminals 6, the curve X rises gradually and does not peak so that the force needed to insert the housing 8 fully into the housing 4 is desirably low, which is of considerable advantage given that five wires W need to be inserted simultaneously into respective terminals 6. In contradistinction to the curve X, the curve Y rises initially very steeply as the wire is forced down between the arms 28a. In the terminal 6' shown in Figure 9, the arms 28' have been pretorsioned during manufacture of the terminal, about their parts 38' so that their parts 36' are angled with respect to each other. If a lead L is accidentally pulled in the direction of the arrow C in Figures 3 and 9, the galvanic connection between the wire W and the arms 28' will still be maintained, since, as will appear from Figures 3 and 9, arms 28' will be torsioned resiliently about their junctions with the bight 32 as shown in Figure 9, whereby the parts 36' of the arms 28' will be swung about their longitudinal axes Z as indicated by the arrows E in Figure 3, so as to engage against the shoulders 68 in the respective passage 48, whereby corners of the parts 36' of the arms 28' of the terminals 6 are driven against the wire W. Upon the tension on the wire W being released, the parts 36' will be returned to their initial positions by virtue of the natural resilience of the arms 28'. The connector 2 will now be further described with particular reference to Figures 10 to 15. As best seen in Figure 10, the rear side wall 16 of the housing 4 comprises two end portions 70 between which the latch arm 17 upstands beyond them. The latching shoulder 19 is provided by the upper end of a vertical slot in the arm 17. Each latching shoulder is provided by the upper end of a vertical slot in the arm 17. Each side wall 18 is in the form of a further latch arm, having a central vertical slot, the upper end of which provides a latching shoulder 72. The five terminals 6 are arranged in an array comprising a front row of three terminals 6 and a rear row of two terminals 6. Each side wall 18 is separated from the adjacent rear wall portion 70 by a vertical keyway 74, the bottom of which is provided by the base 10 of the housing 4. As shown in Figure 11, there projects from each end of the plug 62 of the housing 8, a latch member 76 (only one of which is shown) and rearwardly of the latch member 76 a vertical key 78 extending over the full height of the block 46 and the plug 62. The slots 56 are arranged in the same array as the terminals 6, namely an array comprising a front row of three slots 56 and rear row of two slots 56. The housing 8 is of substantially the same length as the distance between the side walls 18 of the housing 4, that is to say of substantially the same length of the socket 20. As shown in Figure 12, in the aforesaid initial position of the housing 8, the latch member 66 engages against the upper edge of the latch arm 17, each key 78 of the housing 8 engaging in a respective keyway 74 of the housing 4, each latch member 76 of the housing 8 engaging against the latching shoulder 72 of a respective side wall 18. The housing is stabilized in the housing 4 by the engagement of the keys 78 in the keyways 74. As the housing 8 is inserted into its initial position of the housing 4, the side walls 18 are spread resiliently part by the latch members 76 of the housing 8 and then resile as the latch members 76 pass the shoulders 72, whereby the housing 8 is captive in the housing 4. Figure 13 shows the wires W when they have been inserted in the direction of the arrow A in Figures 1 and 12, into the wire receiving passages 48, with the insulation I of the leads L received in the hood 51. As shown in Figure 13, in said initial position, each wire W lies just above the mouth 40 of a respective one of the terminal 6. Figure 14 shows the connector 2 when the housing 8 has been fully depressed in the direction of the arrow B in Figure 1, guided by the engagement of the keys 78 in the keyways 74, so that each wire W lies between the contact surfaces 37 of the respective terminal 6, the latch member 66 being engaged against the shoulder 19 of the latch arm 17. As indicated in Figure 15, the housing 8 can be withdrawn from the housing 4 back to its initial position, by manually pulling back the latch arm 17 in the direction of the arrow X, while simultaneously withdrawing the housing 8 in the direction of the arrow Y, thereby disconnecting wires on the terminals 6. The connector 2 can accordingly act as a switch, aided by the soft spring characteristics of the arms 28 of the terminals 6. The connector 2, is, therefore, suitable for use in an apparatus, for example domestic television or video apparatus, in which circuits are required to be broken when the apparatus is serviced. By virtue of the long insertion length of each wire W between the parts 36 of the arms 28, the wire engaging surfaces of these parts clean from the wire any intermatallics arising from the production of the wire, before the wire reaches the contact surfaces 37.
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An electrical wire connector (2) comprising mating first and second insulating housings (4 and 8), the first housing containing an electricai terminal (6) having a wire receiving slot (44), the second housing (8) having a wire receiving passage (48) communicating with a terminal receiving slot (56), the housings (4 and 8) being mateable to force a wire (W) inserted into the wire receiving passage (48) into the wire receiving slot (44) of the terminal (6); wherein said first housing (4) contains a socket (20) having a plurality of discrete electrical wire receiving terminals (6) positioned in an array in said socket (20), said second housing (8) being mateable with said first housing (4) with said second housing being at least partly insertable in said socket (20) and being movable relative thereto, said second housing (8) having a plurality of discrete terminal receiving slots (56) for enclosing individual wire terminals (6); characterized in that said second housing (8) has a cable receiving channel (50) profiled for receiving a flat cable, the channel (50) being in communication with a plurality of wire receiving passages (48) transversely communicating with said terminal receiving slots (56), said wire receiving passages (48) being profiled to receive bared wires (W) therein, and to align them with said wire receiving slots (56) of the terminals (6), whereby movement of said second housing into said socket, positions the wires (W) in said wire receiving terminals (6). The electrical wire connector of claim 1, characterised in that each wire receiving passage (48) has a reduced diameter portion for receiving the respective bared wire (W) and an enlarged insulating receiving mouth (52) profiled to guide said flat cable into said channel (50). A connector as claimed in claim 1 or 2, characterized in that the first housing (4) is a female housing defining a socket (20) having a base (10) in which anchoring parts (24) of the terminals (6) are secured, part of a side wall (16) of the socket (20) being formed as a first latch arm (17), the second housing (8) being a male housing having a plug portion (62) for reception in the socket (20) of the female housing (4), and a first latch member (66) for latching engagement with the latch arm (17) of the female housing (4), the latch arm (17) projecting above the remainder of the side wall (16) to provide a handle for unlatching the latch arm (17) from the latch member (66) when the plug (62) of the male housing (8) is fully received in the socket (20) of the female housing (4). A connector as claimed in claim 3, characterized in that the socket (20) has a pair of end walls (18) constructed as second latch arms having second latching shoulders (72) and being adjacent to said side wall (16) but each end wall (18) being separated from the said side wall (16) by a keyway (74), the male housing (8) having end second latch members (76) for engaging the respective ones of the second latching shoulders (72) in an initial, wire insertion position of the male housing (8) with the first latch member (66) resting on the first latch arm (17), the male housing (8) being depressible to flex the first latch arm (17) so that the first latch member (66) latches beneath the latching shoulder (19) of the first latch arm (17), whereby the second latch members (76) are displaced from the second latching shoulders (72) and keys (78) engaging in said keyways (74) guide the male housing (8) with respect to the female housing (4).
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WHITAKER CORP; THE WHITAKER CORPORATION
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GILISSEN HERMANUS PETRUS JOHAN; SOES LUCAS; GILISSEN, HERMANUS PETRUS JOHANNES; SOES, LUCAS
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EP-0489550-B1
| 489,550 |
EP
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B1
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EN
| 19,950,621 | 1,992 | 20,100,220 |
new
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C08F8
| null |
C08F12, C08F8
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C08F 8/12+12/22
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Process for the preparation of 4-hydroxystyrene polymers from 4-acetoxystyrene polymers
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Homopolymers and/or copolymers of 4-hydroxystyrene are produced by hydrolyzing homopolymers and/or copolymers of 4-acetoxystyrene with hydroxylamine.
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Technical Field of the Invention.The present invention relates to the field of polymers of 4-hydroxystyrene and, more particularly, to a process for the preparation of such polymers. Still more particularly, the present invention discloses a method of preparing polymers of 4-hydroxystyrene by hydrolyzing polymers of 4-acetoxystyrene with hydroxylamine. Background of the Invention.Homopolymers and copolymers of 4-hydroxystyrene, a compound which is also known as p-vinylphenol, are well known compositions which are used in the manufacturing of metal treatment compositions, photoresists, epoxy resins and epoxy resin curing agents. Polymers of 4-hydroxystyrene can be produced by polymerizing the 4-hydroxystyrene monomer. That monomer, however, is an unstable compound under room temperature and must be stored under low temperatures provided by refrigeration to prevent its spontaneous polymerization. Even under low temperatures, the monomer slowly polymerizes to low molecular weight polymers. Because of the instability of the 4-hydroxystyrene monomer, alternative routes for preparing polymers of 4-hydroxystyrene have been utilized using 4-acetoxystyrene, the acetic acid ester of 4-hydroxystyrene, as the starting compound. 4-Acetoxystyrene is a stable monomer which can be readily polymerized and copolymerized to low, medium and high molecular weight polymers. Those processes involve the polymerization of the 4-acetoxystyrene monomer, followed by the hydrolysis of the phenolic ester groups of the 4-acetoxystyrene polymers to produce 4-hydroxystyrene polymers. Corson, et al., Preparation of Vinylphenols and Isopropenylphenols, 23 J. Org. Chem. 544-549 (1958) (hereinafter referred to as Corson, et al. ), discloses a process for making 4-hydroxystyrene from phenol. According to that process, phenol is acylated to 4-hydroxyacetophenone which is then acetylated to 4-acetoxyacetophenone. The latter compound is hydrogenated to 4-acetoxyphenyl- methylcarbinol which is, then, dehydrated to 4-acetoxystyrene. The 4-acetoxystyrene is saponified to 4-hydroxystyrene using potassium hydroxide. Packham, Chelating Polymers Derived from Poly-4-hydroxystyrene, 1964 J. of the Chemical Society 2617-2624, describes the hydrolysis of cross-linked poly (4-hydroxystyrene) by refluxing the polymer in alkaline aqueous dioxan. Arshady, et al., Phenolic Resins for Solid-Phase Peptide Synthesis: Copolymerization of Styrene and p-Acetoxystyrene, 12 J. of Polymer Science 2017-2025 (1974), describes the hydrolysis of copolymers of styrene and p-acetoxystyrene to the vinylphenol polymer using hydrazine hydrate in dioxane. Chen, et al., A Morphological Analogue of Japanese Lacquer. Grafting of p-Hydroxystyrene onto Pullutan by Ammonium Persulfate Initiation in Dimethylsulfoxide, 23 J. Polymer Science: Polymer Chem. Ed. 1283-1291 (1985) describes the hydrolysis of p-acetoxystyrene grafted pullulan to p-hydroxystyrene pullulan with hydrazine hydrate. Nakamura, et al, Effect of Substituent Groups on Hydrogen Bonding of Polyhydroxystyrene Derivatives, 15 Polymer J. 361-366 (1983), describes the hydrolysis of poly(p-acetoxystyrene) dissolved in acetone to poly(p-hydroxystyrene) with hydrochloric acid. U.S. Patent No. 2,276,138 discloses the ester interchange reaction of poly (4-acetoxystyrene) in methanol using sodium methylate. About 84 percent of the acetate groups are removed by the interchange reaction. U.S. Patent No. 3,547,858 discloses a process for the production of polymers containing hydroxyl groups which comprises subjecting a polymer of an ester of an unsaturated alcohol to the action of a hydrolyzing agent while the polymer is in the molten state. In the hydrolysis reaction, the ester groups are replaced by hydroxyl groups. Water and, preferably, a lower alkyl alcohol can be used as a hydrolyzing agent. U.S. Patent No. 4,544,704 discloses the hydrolysis of a copolymer of styrene and p-isopropenylphenylacetate with aqueous sodium hydroxide in methanol and toluene using a small amount of benzyltrimethylammonium chloride as a phase transfer agent. U.S. Patent No. 4,678,843 discloses a process for hydrolyzing polymers of 4-acetoxystyrene to polymers of p-vinylphenol. Ammonia is the hydrolysis catalyst. The 4-acetoxystyrene polymer is dissolved in a solvent which is miscible with water. Ammonia gas or ammonium hydroxide is added to the solution and the hydrolysis reaction is carried out at a temperature of about 50°C to about 150°C for a time sufficient to hydrolyze the acetoxy groups to phenol groups. At the end of the hydrolysis reaction, wet carbon dioxide gas is introduced into the reaction solution as a sparge below the solution surface to remove the ammonium salt. The 4-hydroxystyrene polymer is recovered for use as an organic solvent solution and can be recovered as a solid by removal of all solvents by vacuum distillation or by precipitating the polymer from the solution. U.S. Patent No. 4,689,371 discloses the production of poly-(4-vinylphenol) by hydrolyzing polymers of 4-acetoxystyrene by methanolysis with quaternary ammonium hydroxides as the catalyst. The 4-acetoxystyrene polymer is dissolved in a solvent which is miscible with water. Ammonium hydroxide is added and the reaction is carried out at a temperature of about 50°C to about 80°C for a time sufficient to hydrolyze the acetoxy group. The reaction product is heated to a temperature of about 50°C to about 150°C to distill off methyl acetate and the decomposition products of the quaternary ammonium hydroxide. The 4-vinylphenol polymer can be used per se as a solution or it can be recovered as a solid by removal of all solvents by vacuum distillation or by precipitating the polymer from the solution. U.S. Patent No. 4,822,862 discloses the production of homopolymers and copolymers of p-vinylphenol by hydrolyzing homopolymers or copolymers of 4-acetoxystyrene with a base such as an alkali metal hydroxide, an ammonium hydroxide, a quaternary ammonium hydroxide or a water soluble amine. The hydrolysis reaction occurs in an emulsion containing the polymers of 4-acetoxystyrene in water, without isolating the polymer. The vinylphenol polymer is recovered from the emulsion by acidifying the reaction mass and by filtering, washing and drying the solid polymer or by coagulating the emulsion with alum and, after acidification, recovering, washing and drying the solid polymer. U.S. Patent No. 4,857,601 discloses the selective hydrolysis of copolymers of p-acetoxystyrene and dialkyl muconates or alkyl sorbates to copolymers of p-vinylphenol and dialkyl muconates or alkyl sorbates using acid or base catalysts in an alcohol or water. The reactant copolymer is slurried in an alcohol or aqueous base. The product is dissolved in the alcohol or aqueous base and is recovered as a solution. U.S. Patent No. 4,868,256 discloses the hydrolysis of polymers of 3,5-dibromo-4-acetoxystyrene to polymers of 3,5-dibromo-4-acetoxystyrene with a base or an acid such as tetramethyl ammonium hydroxide, aqueous NH₃, NaOH, KOH, HCl, and H₂SO₄. U.S. Patent No. 4,877,843 discloses the selective hydrolysis of copolymers of 4-acetoxystyrene and allyl esters of unsaturated acids slurried in an alcohol or water to copolymers of p-vinylphenol and allyl esters of unsaturated acids with an acid or a base. If the reaction is an alcoholysis reaction in alcohol, the polymer can be recovered by precipitating and coagulating the polymer in water. If the hydrolysis reaction is carried out in aqueous base, the polymer can be recovered from solution by precipitation with acid. The alcohols used are the one to four carbon alcohols. The acids used are mineral acids and organic acids with dissociation constants in aqueous solution of less than 2. The bases used are alkali metal hydroxides and alkoxides and quaternary ammonium hydroxides. U.S. Patent No. 4,898,916 discloses the production of polymers of 4-vinylphenol by the acid catalyzed transesterification of polymers of 4-acetoxystyrene in an alcohol. Polymers of 4-acetoxystyrene are slurried in an alcohol and are hydrolyzed to polymers of 4-vinylphenol in the presence of a mineral or organic acid as well as Lewis acids which have dissociation constants in aqueous solution of less than 2. The alcohols used are one to four carbon alcohols. The 4-vinylphenol polymer product is recovered as a solution in the alcohol to be used as such or it can be further recovered as a solid from such solutions by utilizing well known techniques. U.S. Patent No. 4,912,173 describes the hydrolysis of polymers of 4-acetoxystyrene suspended in water in finely divided particulate form to polymers of 4-hydroxystyrene using aqueous nitrogen bases. The nitrogen bases used are ammonia, primary, secondary or tertiary water soluble amines and water soluble quaternary ammonium hydroxides. When ammonium hydroxide is used as the base, the suspended polymer product remains in suspension and the water is removed by filtration, decantation or centrifugation. After washing and drying the polymer is ready for use. When other bases are used, the particles are sometimes softened or solubilized. Agglomerated polymers can be recovered by removing the water, washing and drying, as described above. Solubilized polymers are recovered after precipitation with acid. U.S. Patent No. 4,962,147 discloses the hydrolysis of poly(4-acetoxystyrene), in suspension in its polymerization medium, to poly(4-hydroxystyrene) with ammonia. Ammonia is preferably used as ammonium hydroxide. It can also be used in gaseous form which is preferably introduced below the surface of the aqueous reaction medium. During the hydrolysis reaction, the suspended polymer remains in suspension in solid finely divided form. U.S. Patent No. 4,965,400 discloses the hydrolysis of 3,5-disubstituted-4-acetoxystyrene to form substituted 4-hydroxystyrene analogs. The hydrolysis agents are NH₃, NaOH, KOH, tetramethylammonium hydroxide, HCl or H₂SO₄. In most of the above referenced processes, the reaction was carried out with the reactants being in solution or the 4-hydroxystyrene polymer product was recovered as a solution. As a result, a large reactor volume was required to accommodate the reaction. Furthermore, in order to recover the product as a solid from the solution, certain steps had to be used such as precipitation with a nonsolvent, acidification of the salt form of the polymer, spray drying or the like. Such steps were time-consuming and uneconomical because they required additives and/or energy. According to the present invention, the hydrolysis reaction is carried out in suspension and the polymer product thereof is in suspension. The solid product is intact and is easily and economically recovered by well known techniques such as filtration. Another disadvantage of prior processes was that, oftentimes, a satisfactory degree of hydrolysis of copolymers of 4-acetoxystyrene to copolymers of 4-hydroxystyrene could not be achieved when the amount of 4-acetoxystyrene in the reactant polymer was less than about 50 weight percent of the total weight attributed to 4-acetoxystyrene and the copolymer polymerizable therewith. According to the present invention, copolymers of 4-acetoxystyrene are hydrolyzed to a satisfactory degree with hydroxylamine regardless of the amount of 4-acetoxystyrene present therein. These and other advantages of the present invention will become apparent from the following description. Summary of the InventionHomopolymers or copolymers of 4-acetoxystyrene are hydrolyzed with hydroxylamine to produce homopolymers or copolymers of 4-hydroxystyrene. The hydroxylamine is available to the reaction as a free base or from an acid salt of hydroxylamine which is neutralized with a base to provide the hydroxylamine. The reaction is carried out with the reactants and the products being in suspension. The products are solid intact particles which are easily and economically recoverable by filtration or similar techniques. In the case of homopolymers, the reactants are hydrolyzed to a high degree, with the hydrolysis in most cases being more than 99.5 percent. In the case of copolymers, the reactants are hydrolyzed to a satisfactory degree, even in cases wherein the amount of 4-acetoxystyrene present in the reactant copolymer is substantially less than 50 percent of the total weight attributed to 4-acetoxystyrene and the copolymer polymerizable therewith. Detailed Description of the Invention.According to the present invention, a process for the production of polymers of 4-hydroxystyrene is disclosed by hydrolyzing polymers of 4-acetoxystyrene with hydroxylamine. In the process, the acetoxy groups of the 4-acetoxystyrene parts of the polymer are replaced with hydroxy groups to produce the 4-hydroxystyrene polymer. The process is used to convert homopolymers of 4-acetoxystyrene to homopolymers of 4-hydroxystyrene and copolymers of 4-acetoxystyrene to copolymers of 4-hydroxystyrene. The term polymer, as used herein, refers to a homopolymer or a copolymer. The reactant polymers of 4-acetoxystyrene are in suspension in the form of beads and are hydrolyzed by the hydroxylamine to produce polymers of 4-hydroxystyrene in suspension in the form of suspended intact solid particulates whereby the use of solvents and the difficulties associated therewith are eliminated. The solid polymer products are separated from the remaining compounds of the reaction mass by filtration, decantation or centrifugation and, after washing and drying, they are ready for use. When a sufficient amount of hydroxylamine is used, more than 98.0 percent and, in most cases, more than 99.5 percent of the polymers of 4-acetoxystyrene are hydrolyzed to the corresponding polymers of 4-hydroxystyrene. The monomer 4-acetoxystyrene is a well known compound which can be produced by the method described in Corson et al or by any other method known to those skilled in the art. The monomer readily polymerizes in solution, suspension, emulsion or bulk using well known free radical catalysts such as, for example, the peroxide and azo compounds. Such polymerization can take place in the absence of comonomers whereby the resultant product is a homopolymer or in the presence of comonomers whereby the resultant product is a copolymer. Examples of processes used for the production of homopolymers or copolymers of 4-acetoxystyrene are the processes disclosed in U.S. Patent Nos. 4,822,862, 4,912,173 and 4,962,147. Other well known processes can also be used. In the case of copolymerization, the most commonly used comonomer is styrene. Other comonomers include vinyltoluene; alpha-methylstyrene; ortho-, meta-, and para- chloro - and bromostyrene; the diene monomers such as butadiene; the acrylate and methacrylate ester monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate and 2-ethylhexyl acrylate; acrylonitrile; methacrylonitrile; the polymerizable acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid; and the allyl ester comonomers described in U.S. Patent No. 4,877,843. It should be noted that, although copolymers of 4-acetoxystyrene and maleic anhydride are hydrolyzable by hydroxylamine, such hydrolysis is not desirable for the production of copolymers of 4-hydroxystyrene and maleic anhydride because the hydroxylamine opens the rings of the maleic anhydride. Useful copolymers of 4-acetoxystyrene contain 1 to 99 parts by weight of 4-acetoxystyrene to 99 to 1 part of comonomer polymerizable therewith. Alternatively stated, in useful copolymers, the amount of 4-acetoxystyrene is in the range of 1 to 99 weight percent of the total weight attributed to 4-acetoxystyrene and the comonomer polymerizable therewith. Preferred copolymers contain about 25 to about 75 parts by weight of 4-acetoxystyrene to about 75 to about 25 parts by weight of comonomer. In the prior hydrolysis processes, copolymers containing an amount of 4-acetoxystyrene of about fifty (50) or more weight percent of the total weight attributed to 4-acetoxystyrene and the comonomer polymerizable therewith were hydrolyzed to a satisfactory degree. Copolymers, however, containing a lesser amount of 4-acetoxystyrene were difficult to hydrolyze to a satisfactory degree because the comonomer inhibited the hydrolysis of the 4-acetoxystyrene parts of the polymer. According to the present invention, 4-acetoxystyrene copolymers containing an amount of 4-acetoxystyrene as low as 1 weight percent of the total weight attributed to 4-acetoxystyrene and the comonomer polymerizable therewith are hydrolyzed to a degree wherein more than 98.0 percent of the 4-acetoxystyrene parts of the copolymer are hydrolyzed to 4-hydroxystyrene parts. The hydrolyzing agent of the present invention is hydroxylamine. Hydroxylamine is available to the reaction as a free base or from an acid salt thereof such as hydroxylamine hydrochloride or hydroxylamine sulfate which is neutralized with aqueous ammonia or with any other base which does not interfere with the hydrolysis of the polymer reactant with the hydroxylamine. The stoictiiometric amount of hydroxylamine required is 1 mole of hydroxylamine per mole of 4-acetoxystyrene monomer present in the reaction. An excess amount of about 110 to about 400 mole percent is used, however, to ensure satisfactory completion of the hydrolysis of the 4-acetoxystyrene parts. The hydroxylamine diffuses into the solid reactant polymers of 4-acetoxystyrene and interacts with the acetoxy parts thereof to convert them to hydroxy parts. In carrying out the hydrolysis reaction, homopolymers or copolymers of 4-acetoxystyrene are suspended as solid articles in water. The size of the particles is in the range of 0.01 to 2.0 millimeters. A suspension agent which is inert to the reaction may be used to assist the suspension. An example of such agent is a polyacrylic acid solution having a molecular weight of about 190,000, previously being known by the trademark Acrysol A3, but presently being known by the trademark Acumer 1530, manufactured by Rohm and Haas Company and described in Rohm and Haas Company Technical Bulletin FC-103, dated 1990 (hereinafter referred to as Acrysol A3 ). The use of a suspension agent, however, is not necessary. When hydroxylamine is used as a free base, hydroxylamine which is preferably in an agueous solution is added to the suspension. When the hydroxylamine is available to the reaction from a salt of the hydroxylamine, that salt and the base for neutralizing such salt to obtain the hydroxylamine are added to the suspension. The reactants are continuously stirred by well known stirring means to maintain the homogeneity of the suspension and are heated to a temperature of 50°C to 95°C until the desired amount of hydrolysis is obtained. Depending on the degree of heating and the nature of the reactants, the hydrolysis takes place in about 1 to about 6 hours with more than 98.0 percent and, in most cases, more than 99.5 percent of the 4-acetoxystyrene parts of the polymer being converted to 4-hydroxystyrene. The reaction is carried out in a batch mode under atmospheric or slightly above atmospheric conditions. In order to obtain a polymer product with a desirable color, the reaction is carried out under an oxygen-free environment. Accordingly, nitrogen is provided to the reaction mass to maintain such environment. It should be understood, however, that an oxygen-free environment is necessary only for the purpose of obtaining a desirable polymer color and that the hydrolysis reaction described herein can proceed, even in the presence of oxygen. In the latter case, the polymers have a dark, undesirable color. The 4-hydrostyrene polymer products are white solid particles which are intact and which do not dissolve in the reaction mass. The solid particles are easily separated from the reaction mass by filtration, centrifugation or decantation. The separated particles are washed and dried and are ready for use. The following examples further illustrate the invention. Example 1A 250 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, an overhead stirrer and an external heating mantel. 100 grams of deionized water, 4 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 20 grams (0.12 moles) of a homopolymer of 4-acetoxystyrene having a weight average molecular weight of 8750, and an aqueous solution of hydroxylamine containing 9.46 grams of water and 9.46 grams (0.29 moles) of hydroxylamine free base were added to the flask. The reaction mixture was stirred to suspend the 4-acetoxystyrene polymer and heated to 83°C over a period of 2 hours and 45 minutes. At the end of that period, a sample of the suspended polymer beads was taken and analyzed by Fourier Transform Infrared Analysis (herein referred to as FTIR ). The analysis showed that the sample was completely hydrolyzed to 4-hydroxystyrene polymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 2A 250 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, a magnetic stirrer and an external heating mantel. 100 grams of deionized water, 4 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 15 grams (0.093 moles) of a homopolymer of 4-acetoxystyrene having a molecular weight of 16,000, and 20.4 grams of hydroxylamine hydrochloride were added to the flask. The reaction mixture was stirred to suspend the 4-acetoxystyrene polymer and heated to 85°C over a period of 3 hours. At the end of that period, a sample of the suspended polymer beads was removed from the flask and was placed in methanol. The sample did not dissolve in methanol, an indication that the sample was substantially unreacted 4-acetoxystyrene polymer. The reaction mixture was then treated with a minimum amount of 28 percent by weight aqueous ammonia to raise its pH to 10. One hour later, a sample of the polymer beads was taken and was placed in methanol wherein it dissolved. A sample was then analyzed by FTIR. The analysis showed that the sample was completely hydrolyzed to 4-hydroxystyrene polymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 3A 500 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, an overhead stirrer and an external heating mantel. 100 grams of deionized water, 4 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 20 grams of a 25/75 mole ratio of a copolymer of 4-acetoxystyrene/styrene having a weight average molecular weight of 20,700, and 32.65 grams of hydroxylamine sulfate were added to the flask. The reaction mixture was treated with a minimum amount of 28 weight percent by weight aqueous ammonia to raise its pH to 10. The reaction mixture was stirred to suspend the 4-acetoxystyrene/styrene copolymer and heated to 85°C over a period of 3 hours. At the end of that period, a sample of the suspended solid bead was placed in methanol and did not dissolve. 1 hour and 10 minutes later, another sample was analyzed by FTIR and the analysis showed that the hydrolysis was not complete. 2 hours later ( 6 hours and 10 minutes from the start of the procedure), another sample of the suspended polymer beads was taken and analyzed by FTIR. The analysis showed that the sample was completely hydrolyzed to 4-hydroxystyrene copolymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 4A 500 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, an overhead stirrer and an external heating mantel. 100 grams of deionized water, 4 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 15 grams of a 10/90 mole ratio copolymer of 4-acetoxystyrene/styrene having a weight average molecular weight of 19,800, and 8.16 grams of hydroxylamine sulfate were added to the flask. The pH of the mixture was raised to 10 with a minimum amount of 28 weight percent by weight aqueous ammonia. The reaction mixture was stirred to suspend the 4-acetoxystyrene/styrene copolymer and heated to 87°C over a period of 5.5 hours. At the end of that period, a sample of the suspended polymer beads was taken and analyzed by FTIR. The analysis showed that the sample was hydrolyzed more than 50 percent to 4-hydroxystyrene/ styrene copolymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 5A 300 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, a magnetic stirrer and an external heating mantel. 75 grams of deionized water, 3 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 15 grams of a 10/90 mole ratio copolymer of 4-acetoxystyrene/styrene having a weight average molecular weight of 19,700, and 8.19 grams of hydroxylamine hydrochloride were added to the flask. The pH of the mixture was raised to 10 as described in the prior examples with aqueous ammonia. The reaction mixture was stirred to suspend the 4-acetoxystyrene polymer and heated to 85°C over a period of 5.5 hours. At the end of that period, a sample of the suspended polymer beads was taken and analyzed by FTIR. The analysis showed that the sample was hydrolyzed more than 90 percent to 4-hydroxystyrene/styrene copolymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 6A 250 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, an overhead stirrer and an external heating mantel. 100 grams of deionized water, 4 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), ten (10) grams of a 25/75 mole ratio copolymer of 4-acetoxystyrene/styrene having a molecular weight of 20,700, and 6.15 grams of hydroxylamine hydrochloride were added to the flask. The pH of the mixture was raised to 10 as described in the previous examples. The reaction mixture was stirred to suspend the 4-acetoxystyrene/styrene copolymer and heated to 89°C over a period of 4 hours. At the end of that period, a sample of the suspended polymer beads was taken and analyzed by FTIR. The analysis showed that the sample was completely hydrolyzed to 4-hydroxystyrene/styrene copolymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then they were washed with deionized water and dried overnight in a vacuum oven at 70°C. Example 7A 250 milliliter round bottom flask was fitted with a chilled water reflux condenser, a thermowell with a thermocouple, a nitrogen purge fitting, an overhead stirrer and an external heating mantel. 80 grams of deionized water, 3.2 grams of a 25 weight percent aqueous polyacrylic acid solution (the suspension agent previously referred to as Acrysol A3), 15 grams of a 50/50 mole ratio copolymer of 4-acetoxystyrene/ethyl acrylate having a weight average molecular weight of 34,400, and 55.61 grams of hydroxylamine hydrochloride were added to the flask. The pH of the mixture was raised to 10 as described in the previous examples. The reaction mixture was stirred to suspend the 4-acetoxystyrene/ethyl acrylate copolymer and heated to 43°C for 1 hour, 50°C for 1 hour and 61°C for 2 hours. At the end of that period, a sample of the suspended polymer beads was taken and analyzed by FTIR. The analysis showed that the sample was completely hydrolyzed to 4-hydroxystyrene/ethyl acrylate polymer. The reaction mixture was cooled and the suspended solid particles of the product were removed from the reaction mass by filtration. Then, they were washed with deionized water and dried overnight in a vacuum oven at 70°C.
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A process for producing a polymer of 4-hydroxystyrene, comprising the step of reacting a polymer of 4-acetoxystyrene with hydroxylamine. A process according to claim 1 wherein the polymer of 4-acetoxystyrene is a homopolymer of 4-acetoxystyrene and the polymer of 4-hydroxystyrene is a homopolymer of 4-hydroxystyrene. A process according to claim 1 wherein the polymer of 4-acetoxystyrene is a copolymer of 4-acetoxystyrene and a comonomer and the polymer of 4-hydroxystyrene is a copolymer of 4-hydroxystyrene and the comonomer. A process according to claim 1, 2 or 3 wherein the reacting step includes the step of hydrolyzing the polymer of 4-acetoxystyrene with hydroxylamine. A process according to any of claims 1 to 4 wherein the hydroxylamine is in the form of a free base. A process according to any of claims 1 to 4 further including the step of deriving the hydroxylamine from an acid salt of the hydroxylamine prior to the reacting step. A process according to any of claims 1 to 6 wherein more than 99.5 percent of the 4-acetoxystyrene parts of the 4-acetoxystyrene polymer are converted to 4-hydroxystyrene parts. A process according to any of claims 1 to 7 wherein the reacting step is carried out under a temperature of 50°C to 95°C. A process according to any of claims 1 to 8 wherein the polymer of 4-acetoxystyrene is in its solid state. A process according to any of claims 1 to 9 wherein the polymer of 4-acetoxystyrene is in suspension. A process according to claim 10 wherein the polymer of 4-acetoxystyrene is suspended in an aqueous medium. A process according to claim 10 or 11 wherein the polymer of 4-acetoxystyrene is in the form of particles ranging from 0.01 to 2.0 millimeters in size. A process according to any of claims 1 to 12 wherein the hydroxylamine is in an aqueous solution. A process according to claim 3 wherein the amount of 4-acetoxystyrene in the 4-acetoxystyrene copolymer is in the range of 1 to 99 weight percent of the weight of the 4-acetoxystyrene copolymer which is attributed to the 4-acetoxystyrene and the comonomer. A process according to claim 1 further including the step of forming the polymer of 4-hydroxystyrene in its solid state as a result of the reacting step. A method of preparing a polymer of 4-hydroxystyrene in suspension, comprising the step of hydrolyzing a 4-acetoxystyrene polymer in suspension with hydroxylamine. A method of preparing a polymer of 4-hydroxystyrene, comprising the step of interacting a solid polymer of 4-acetoxystyrene with hydroxylamine. A method according to claim 17 wherein the polymer of 4-hydroxystyrene is solid. A method according to any of claims 1 to 15 wherein the reacting step is carried out in the absence of oxygen.
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HOECHST CELANESE CORP; HOECHST CELANESE CORPORATION
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SHEEHAN MICHAEL T; SMITH BRAD L; SHEEHAN, MICHAEL T.; SMITH, BRAD L.
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EP-0489551-B1
| 489,551 |
EP
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B1
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EN
| 19,960,508 | 1,992 | 20,100,220 |
new
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H04R1
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H04R1
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H04R1
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H04R 1/28C, H04R 1/28B, H04R 1/22D
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Loudspeaker system having multiple subchambers
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A loudspeaker system has at least a first electroacoustical transducer ( 12 ) having a vibratable diaphragm for converting an input electrical signal into a corresponding acoustic output signal. An enclosure is divided into at least first, second and third subchambers (V₁,V₂,V₃) by at least first (13) and second (11) dividing walls. The first dividing wall (13) supports and coacts with the first electrical transducer (12) to bound the first and second subchambers (V₁,V₂). At least a first passive radiator (P₁) intercouples the first and third subchambers. At least a second passive radiator (P₂) intercouples at least one of the second and third subchambers with the region outside the enclosure. Each passive radiator (P₁,P₂) has an acoustic mass and each subchamber (V₁, V₂, V₃) has an acoustic compliance. The acoustic masses and acoustic compliances coact to establish at least three spaced frequencies in the passband of the loudspeaker system at which the deflection characteristic of the vibratable diaphragm as a function of frequency has a minimum.
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The present invention relates to loudspeaker systems having multiple subchambers and passive radiators, such as ports and drone cones. These systems comprise an acoustic source so coupled to a series of higher order acoustic filters as to produce an acoustic output which is frequency band limited and whose acoustic power output in that band is generally constant as a function of frequency. The series of acoustic filters are typically embodied as acoustic compliances (enclosed volumes of air) and acoustic masses (passive radiators or ports). For background reference is made to Bose U.S. Patent No. 4,549,631 and the dual chamber systems described by Earl R. Geddes in his May 1989 article in the Journal of the Audio Engineering Society An introduction to Band-Pass Loudspeaker Systems, which discloses using components to achieve higher order rolloffs of high frequencies. All embodiments of the invention have the following advantages: 1. Relatively low average cone excursion in the bandpass region, i.e., relatively low distortion for large signal output for a given transducer size. 2. Relatively high output in this bandpass region for a given enclosure volume. 3. The use of common, practical, economically configured transducers as the drive units. 4. Relatively higher order rolloff of high frequencies. 5. Achieving the bandpass characteristic without external electrical elements, resulting in relatively low cost, relatively high performance and relatively high reliability. 6. A transient response which is delayed in time by up to or greater than 10 milliseconds. These embodiments may be used in any acoustic application where a bandpass output is desired, where low distortion is desired, where high output is desired, and/or where economically configured transducers are desired. Their uses include, but are not limited to, bass boxes for musical instruments, permanently installed sound systems for homes or auditoria, and for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. For any speaker system driven at high input electrical signal at a specified frequency, distortion components generated by the speaker system are generally higher in frequency than the specified frequency. If the specified frequency is in the bass region, these higher frequency distortion components make it easier for the listener to detect the speaker system location. In addition, most distortion has multiple frequency components resulting in a wideband distortion spectrum which gives multiple (positively interacting) clues to the listener as to the speaker system location. Because of the lower distortion generated by embodiments of this invention compared to prior art, these embodiments are more useful as nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. The higher order rolloff (≥ 18 dB/octave) of high frequencies for embodiments of this invention enhances its nonlocalizability. On complex signals (music or speech), the listener will receive significant directional cues only from the higher frequency components of the speaker system. Thus, these embodiments are more useful than prior art as nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Experiments performed by K. deBoer, Haas, Wallach, and others indicate that a listener's ability to correctly locate sources of sounds depends on the relative time difference of the sounds coming from those sources. If spectrally identical sounds are produced by two sources spaced a few meters apart, but one source produces the sound a few milliseconds later than the other, the listener will ignore the later source and identify the earlier source as the sole producer of both sounds (Precedence Effect). Embodiments of this invention produce a greater time delay than prior art and thus are more useful for providing nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Although all these exemplary configurations and volume and acoustic mass ratios describe embodiments whose acoustic power output is generally flat with frequency in the passband, this may not be the desired shape in certain applications, such as applications where the electrical input signal is equalized with frequency. For any desired frequency contour, a similar set of volume and acoustic mass ratios may be worked out for each configuration. In addition, as variations of the basic embodiments described herein, internal subchambers may be connected via passive radiator means not only to other subchambers but, in addition, to the region outside the enclosure. For a desired flat frequency response output, this may result in somewhat different volume and acoustic mass ratios for each configuration. In addition, as variations of the basic embodiments described herein, various internal subchambers may be connected by passive radiator means to only one other subchamber and not directly coupled to the region outside the enclosure. For a desired flat frequency response output, this may result in somewhat different volume and acoustic mass ratios for each configuration. For background reference is made to Bose U.S. Patent No. 4,549,631 incorporated herein by reference. This patent discloses an enclosure divided into ported subchambers by a baffle carrying a loudspeaker driver. FR-A-2145050 discloses a loudspeaker enclosure which is subdivided into subchambers by plugs having transfer tubes. According to the invention, there is provided a loudspeaker system comprising: a first electroacoustical transducer having a vibratable diaphragm for converting an input electrical signal into a corresponding acoustic output signal, an enclosure, the enclosure being divided into first, second and third subchambers by at least first and second dividing walls, and a first passive radiator intercoupling the first and third subchambers, characterised by: the first dividing wall supporting and coacting with the first electroacoustical transducer to bound the first and the second subchambers, a second passive radiator intercoupling at least one of the second and third subchambers with the region outside the enclosure, each of the passive radiators having an acoustic mass, each of the subchambers having an acoustic compliance, the acoustic masses and the acoustic compliances being selected to establish at least three spaced frequencies in the passband of the loudspeaker system at which the deflection characteristic of the vibratable diaphragm as a function of frequency has a minimum. Numerous other features, objects and advantages of the invention will become apparent from the following detailed description when read in connection with the accompanying drawings in which: FIG. 1 is a perspective pictorial representation of an exemplary embodiment of the invention; FIG. 2 is a simplified cross section of the embodiment of FIG. 1; FIG. 3 is an electrical circuit analog of the embodiment of FIGS. 1 and 2; FIG. 4 shows the radiated acoustic output power as a function of frequency of the embodiment of FIGS. 1-3 compared with other enclosures; FIG. 5 is a graphical representation of diaphragm excursion as a function of frequency of the embodiment of FIGS. 1-3 compared with that of an acoustic suspension enclosure; FIG. 6 is a graphical representation of the transient response of the embodiment of FIGS. 1-3 compared with that of an acoustic suspension enclosure; FIG. 7 is a pictorial perspective view of another embodiment of the invention; FIG. 8 is a simplified cross section of the embodiment of FIG. 7; FIG. 9 is a schematic electrical circuit analog diagram of the embodiment of FIGS. 7 and 8; FIG. 10 is the output power frequency response of the embodiment of FIGS. 7-9 compared with other enclosures; FIG. 11 shows diaphragm displacement as a function of frequency of the embodiment of FIGS. 7-9 compared with that of an acoustic suspension enclosure; FIG. 11A is a graphical representation of the transient response of the embodiment of FIGS. 7-9 compared with that of an acoustic suspension enclosure; FIG. 12 is a pictorial perspective view of another embodiment of the invention; FIG. 13 is a simplified cross section of the embodiment of FIG. 12; FIG. 14 is a schematic electrical circuit analog diagram of the embodiment of FIGS. 11-13; FIG. 15 is the output power frequency response of the embodiment of FIGS. 12-14 compared with the responses of other enclosures; FIG. 16 is a graphical representation of diaphram displacement as a function of frequency for the embodiment of FIGS. 12-14 compared with that of an acoustic suspension enclosure; FIG. 17 is a graphical representation of the transient response of the embodiment of FIGS. 12-14 compared with that of an acoustic suspension enclosure; FIG. 18 is a perspective pictorial view of another embodiment of the invention; FIG. 19 is a simplified cross section of the embodiment of FIG. 18; FIG. 20 is a schematic electrical circuit analog diagram of the embodiment of FIGS. 18 and 19; FIG. 21 is the output power frequency response of the embodiment of FIGS. 18-20 compared with other enclosures; FIG. 22 is a graphical representation of diaphram displacement as a function of frequency for the embodiment of FIGS. 18-20 compared with that of an acoustic suspension enclosure; FIG. 23 is a graphical representation of the transient response of the embodiment of FIGS. 18-20 compared with that of an acoustic suspension enclosure; FIG. 24 is a perspective pictorial view of another embodiment of the invention; FIG. 25 is a simplified cross section of the embodiment of FIG. 24; FIG. 26 is a schematic electrical circuit analog diagram of the embodiment of FIGS. 24 and 25; FIG. 27 is the output power frequency response of the embodiment of FIGS. 24-26 compared with that of other enclosures; FIG. 28 is a graphical representation of diaphram displacement of the embodiment of FIGS. 24-26 compared with an acoustic suspension enclosure; FIG. 29 is a graphical representation of the transient response of the embodiment of FIGS. 24-26 compared with that of an acoustic suspension enclosure; FIG. 30 is a perspective pictorial view of another embodiment of the invention; FIG. 31 is a simplified cross section of the embodiment of FIG. 30; FIG. 32 is a schematic electrical circuit analog diagram of the embodiment of FIGS. 30 and 31; FIG. 33 is the output power frequency response of the embodiment of FIGS. 30-32 compared with that of other enclosures; FIG. 34 is a graphical representation of diaphram displacement as a function of frequency for the embodiment of FIGS. 30-32 compared with that of an acoustic suspension enclosure; FIG. 35 is a graphical representation of the transient response of the embodiment of FIGS. 30-32 compared with that of an acoustic suspension enclosure; FIG. 36 is a perspective pictorial view of a commercial embodiment of the invention; FIG. 37 is a simplified cross section of the embodiment of FIG. 36; FIG. 38 is a graphical representation of the frequency response of the commercial embodiment of FIGS. 36 and 37; FIG. 39 is a pictorial representation of another embodiment of the invention comprising nesting cylindrical structures; and FIGS. 40A and 40B show shipping and use positions, respectively, of a variation of the embodiment of FIG. 39. With reference now to the drawings, the description of most embodiments includes: 1) a physical description of that embodiment; 2) a drawing of that embodiment; 3) an electrical circuit analog of that embodiment; 4) parameter values for a typical configuration of that embodiment; 5) performance parameters for the typical configuration of (4); e.g., radiated power and cone displacement as functions of frequency; 6) a description of the advantages of the embodiment; and 7) a range of volume and passive radiator acoustic mass ratios which produce a frequency power response which is generally constant with frequency over the band pass range of frequencies. Referring to FIGS. 1 and 2, there are shown a perspective pictorial view and a simplified cross section thereof, respectively, of an embodiment of the invention. In this embodiment, a second dividing wall 11 separates the first internal subchamber V1 from a third subchamber V3 and carries a passive radiator means P1 intercoupling the first internal V1 and third V3 subchambers. The second V2 and third V3 subchambers each has an exterior wall which carries a passive radiator or port means P2 and P3, respectively, for radiating acoustic energy to the region outside the enclosure. Woofer loudspeaker drivers 12 are mounted on first dividing wall 13 that separates the first internal subchamber V1 from the second subchamber V2. Referring to FIG. 3, there is shown an electrical circuit analog schematic diagram of the embodiment of FIGS. 1 and 2. There follows representative parameter values. 2.79 ohms= Rvc= resistance of the voice of the driving transducer 0.00107 henries= Lvc= inductance of the voice coil of the driving transducer 11.61 nt./amp.= BL= product of flux density in the voice coil gap and the length of voice coil wire in that gap 0.0532 kg= Cmmt= moving mass of the cone/voice coil 0.00027 M/nt.= Lcms= suspension compliance of the transducer 0.288 M/nt.-sec. = Rm = inverse of loss (mobility) of mechanical moving system, mechanical mhos. 0.0242 m²= So= area of electroacoustical transducer diaphragm 0.27 x 10⁻⁷m⁵/nt= Lv1= acoustic compliance of volume V1 (0.00378m³) 1.32 x 10⁻⁷m⁵/nt= Lv2= acoustic compliance of volume V2 (0.0185m³) 0.77 x 10⁻⁷m⁵/nt= Lv3= acoustic compliance of volume V3 (0.0108m³) 81 kg/m⁴= C₁= acoustic mass of port P1 144 kg/m⁴= C₂= acoustic mass of port P2 42.6 kg/m⁴= C₃= acoustic mass of port P3 0.0033 m⁵/nt sec.= R₁= acoustic mobility in port P1 0.01 m⁵/nt sec.= R₂= acoustic mobility in port P2 0.005 m⁵/nt sec.= R₃= acoustic mobility in port P3 12.8 x 10⁻⁶+ 1 / jω4.6= Zp3= radiation impedance seen by port P3 12.8 x 10⁻⁶+ 1 / jω4.6= Zp2= radiation impedance seen by port P2 Referring to FIG. 4, there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; a prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and the embodiment of FIGS. 1-3 by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. The embodiment of FIGS. 1-3 provides improved output in the bass region and a sharper cutoff at higher frequencies than the other enclosures. Referring to FIG. 5, there is shown a graphical representation of cone displacement as a function of frequency for a prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. A prior art ported system has one port resonance where the cone excursion is minimized. The two-subchamber system according to prior art (per Bose patent No. 4,541,631) has two passband resonances where the cone excursion can be minimized. Curve D shows that the three subchamber configuration according to this invention has three such resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for the embodiment of FIGS. 1-3 that may produce the flat response and benefits described above are: 1 ≤ V3V10.6 ≤ V2V1 + V30.5 ≤ C1C3 ≤ 4 0.5 ≤ C2C1 + C3 ≤ 4 Referring to FIG. 6, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIGS. 7 and 8, there are shown pictorial perspective and simplified cross-section views, respectively, of another embodiment of the invention. In this embodiment, a second dividing wall 11′ separates both the first V1′ and second V2′ internal subchambers from a third subchamber V3′ and carries two passive radiator means P1′ and P2′ each intercoupling the first internal and third subchambers and the second internal and third subchambers, respectively. The third subchamber V3′ has an exterior wall which carries a passive radiator or port means P3′ for radiating acoustic energy to the region outside the enclosure. Referring to FIG. 9, there is shown an electrical circuit analog schematic diagram of the embodiment of FIGS. 7 and 8. There follows typical parameter values for this embodiment. Referring to FIG. 10 there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and this configuration, by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. This configuration provides improved output in the bass region and a sharper cutoff at higher frequencies than any of the prior art enclosures. Referring to FIG. 11, there is shown a graphical representation of cone displacement as a function of frequency for a prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. Curve D shows that the three subchamber configuration according to this invention has three passband resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for this embodiment that may produce the flat response and benefits described above are: 1 ≤ V2V1 ≤ 5 0.25 ≤ V3V2 + V11.2 ≤ C2C12 ≤ C1 + C2C3Referring to FIG. 11A, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIGS. 12 and 13, there are shown pictorial perspective and simplified cross section views of another embodiment of the invention. In this embodiment, a second driving wall 11″ separates both the first internal subchamber V1″ from a third subchamber V3″ and carries a passive radiator means P1″ intercoupling the first internal and third subchambers. A third dividing wall 14″ separates the second internal subchamber from a fourth subchamber, and carries a passive radiator means intercoupling the second internal and fourth subchambers. The third and fourth subchambers each has an exterior wall which carries a passive radiator or port means P3″ and P4″, respectively, for radiating acoustic energy to the region outside the enclosure. Referring to FIG. 14, there is shown an electrical circuit analog schematic diagram of the embodiment of FIGS. 12 and 13. Exemplary parameter values follow: Advantages of this four-subchamber configuration are shown in FIGS. 15, 16 and 17. Referring to FIG. 15, there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and this configuration, by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. This configuration provides improved output in the bass region and a sharper cutoff at higher frequencies than any of these prior art enclosures. Referring to FIG. 16, there is shown a graphical representation of cone displacement as a function of frequency for prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. Curve D shows that the four-subchamber configuration according to this invention has four resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for this embodiment that may produce the flat response and benefits described above are: 1.5 ≤ V3V11.5 ≤ V4V21 ≤ V2 + V4V1 + V3 ≤ 4 0.8 ≤ C4C2C3C1 ≤ 1 0.8 ≤ C2 + C4C1 + C3Referring to FIG. 17, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIGS. 18 and 19, there are shown pictorial perspective and simplified cross-section views of another embodiment of the invention. In this embodiment, a second dividing wall 11′″ separates both the first V1′″ and second V2′″ internal subchambers from a third internal subchamber V3′″ and carries two passive radiator means P1′″ and P2′″ each intercoupling the first internal and third internal subchambers and the second internal and third internal subchambers, respectively. A third dividing wall 14 ' separates the third internal subchamber V3′″ from a fourth subchamber V4′″, and carries a passive radiator means P3′″ intercoupling the third internal and fourth subchambers. The fourth subchamber V4′″ has an exterior wall which carries a passive radiator or port means P4′″ for radiating acoustic energy to the region outside the enclosure. Referring to FIG. 20, there is shown an electrical circuit analog circuit diagram of the embodiment of FIGS. 18 and 19. Exemplary parameter values for this embodiment follow: Advantages of this four-subchamber configuration are shown in FIGS. 21-23. Referring to FIG. 21, there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and this configuration, by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. This configuration provides improved output in the bass region and a sharper cutoff at higher frequencies than any of these prior art enclosures. Referring to FIG. 22, there is shown a graphical representation of cone displacement as a function of frequency for a prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. Curve D shows that the four- subchamber configuration according to this invention has four resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for this embodiment that may produce the flat response and benefits described above: 1.5 ≤ V2V10.8 ≤ V4V3 ≤ 4 1.5 ≤ V3 + V4V1 + V22 ≤ C2C10.5 ≤ C4C3 ≤ 3 2 ≤ C1 + C2C3 + C4Referring to FIG. 23, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIGS. 24 and 25, there are shown perspective pictorial and simplified cross-section views of another embodiment of the invention. In this embodiment, a second dividing wall 11″″ separates the first internal subchamber V1″″ from a third internal subchamber V3″″ and carries a passive radiator means P1″″ intercoupling the first internal and third internal subchambers. A third dividing wall 14″″ separates the first V1″″, the second V2″″ and third V3″″ subchambers from a fourth subchamber V4″″, and carries two passive radiator means P2″″ and P3″″ intercoupling the second internal and fourth subchambers and the third internal and fourth subchambers, respectively. The fourth subchamber V4″″ has an exterior wall which carries a passive radiator or port means P4″″ for radiating acoustic energy to the region outside the enclosure. Referring to FIG. 26, there is shown an electrical circuit analog schematic circuit diagram of the embodiment of FIGS. 24 and 25. Exemplary parameter values follow: Referring to FIG. 27, there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and this configuration, by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. This configuration provides improved output in the bass region and a sharper cutoff at higher frequencies than any of these prior art enclosures. Referring to FIG. 28, there is shown a graphical representation of cone displacement as a function of frequency for a prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. Curve D shows that the four-subchamber configuration according to this invention has four resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for this embodiment that may produce the flat responses and benefits described above are: 1.5 ≤ V3V10.5 ≤ V2V1 + V3 ≤ 2 0.5 ≤ V4V1+V2+V3 ≤ 2 1.5 ≤ C1C3 ≤ 6 1 ≤ C2C1 + C3 ≤ 4 4 ≤ C1+C2+C3C4Referring to FIG. 29, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIGS. 30 and 31, there are shown pictorial perspective and simplified cross-section views of another embodiment of the invention. In this embodiment, second dividing wall 11v separates the first internal subchamber V1v from a third internal subchamber V3v and carries a passive radiator means P1v intercoupling the first internal and third internal subchambers. A third dividing wall 14v separates the third internal subchamber V3v from a fourth subchamber V4v and carries a passive radiator means P3v intercoupling the third internal and fourth subchambers. The second and fourth subchambers each has an exterior wall which carries a passive radiator or port means P2v and P4v, respectively, for radiating acousticenergy to the region outside the enclosure. Referring to FIG. 32, there is shown an electrical circuit analog schematic diagram of the embodiment of FIGS. 30 and 31. There follows exemplary parameter values for this embodiment. Advantages of this four-subchamber configuration are shown in FIGS. 33-35. Referring to FIG. 33, there is shown the acoustic power radiated by an acoustic suspension system as a function of frequency by curve A; a prior art ported system, by curve B; prior art (per Bose Patent No. 4,549,631) dual ported system, by curve C; and this configuration, by curve D. Each system has the same size woofer and the same total enclosure volume with the loudspeaker and port parameters having been appropriately optimized for each system by adjusting that system's elements to achieve flat frequency response. This configuration provides improved output in the bass region and a sharper cutoff at higher frequencies than any of these prior art enclosures. Referring to FIG. 34, there is shown a graphical representation of cone displacement as a function of frequency for a prior art acoustic suspension system, in curve A, and according to the invention, in curve D. Curve A shows that the cone excursion of the acoustic suspension speaker rises with decreasing frequency. Curve D shows that the four-subchamber configuration according to this invention has four resonances where the cone excursion is minimized. Thus, the overall cone excursion and thus, distortion, on bass frequency signals is lower in this configuration. The range of system enclosure parameters for this embodiment that may produce the flat response and benefits described above are: 1.5 ≤ V3V11.5 ≤ V4V30.5 ≤ V1+V3+V4V2 ≤ 3 0.8 ≤ C1C3 ≤ 4 0.8 ≤ C3C4 ≤ 4 0.5 ≤ C1+C3+C4C2 ≤ 3 Referring to FIG. 35, there is shown a graphical representation of impulse transient response of a prior art acoustic suspension system and the impulse transient response of the invention. The added time delay in the reproduction of the signal is particularly useful for nonlocalizable bass output components in multiple speaker configurations in which the desired sonic imaging is to be controlled by the higher frequency components of those multiple speaker configurations. Referring to FIG. 36, there is shown a pictorial perspective view of a commercial embodiment of the invention that is a variation of the embodiment of FIGS. 7-11A. This embodiment of the invention includes a pair of woofers 12 mounted on intermediate panel 13vi. Intermediate panels 11vi and 13vi bound intermediate subchamber V1 vi. Intermediate panels 13vi and 11vi bound end subchambers V3 vi and V2 vi, respectively. Passive radiator P1 vi intercouples end subchambers V2 vi and V3 vi. Passive radiator P2 vi intercouples intermediate subchamber V1 vi and end subchamber V3 vi. Flared port tube passive radiator P3 vi couples end subchamber V3 vi with the region outside the enclosure. Referring to FIG. 37, there is shown a simplified cross section of the embodiment of FIG. 36. This embodiment of the invention is embodied in the commercial ACOUSTIMASS®-5 series II bass module being manufactured and sold by the assignee of this application. This commercial embodiment has the following representative parameters: Volume of intermediate subchamber V1 vi .00413m³ Volume of end subchamber V2 vi .00657m³ Volume of end subchamber V3 vi .0119m³ Port tube passive radiator P1 vi .203m long by .044m in diameter. Port tubes passive radiator P2 vi each .057m long by .051m in diameter. Flared port tube passive radiator P3 vi .12m long by .12m in diameter at each end and .058m in diameter at the center bounded by the inside of a toroid of elliptical cross section. The ellipse has a major diameter substantially equal to the length of the tube. The woofers are 14cm diameter woofers. These parameters produce three deflection minima at 44 Hz, 80 Hz and 190 Hz and provide the frequency response characteristic shown in FIG. 38 having a relatively uniform response over the bass frequency range and a sharp cutoff at 30 db per octave above 200 Hz to sharply reduce the radiation of undesired harmonics through flared port P3 vi. The tapered cross section of flared port tube P3 vi helps avoid nonlaminar airflow to the region outside the enclosure that might produce audible noise when radiating at high pressure levels. In this specific embodiment the volumes of end subchambers V1 vi and V3 vi are unequal and greater than the volume of intermediate subchamber V2 vi. Port tubes P2 vi are symmetrical about port tube P₁ to provide equal acoustic loading to each of the two woofers. Having the end chambers coupled by the port tube through the intermediate subchamber facilitates manufacture and helps achieve a desired performance level with a thinner enclosure. Having one end of each port tube flush with a supporting intermediate wall increases the effective acoustic mass for a given port tube length. An advantage of the invention is that with at least three spaced deflection minima within the passband, diaphragm displacement to produce a prescribed sound level is reduced. This feature allows use of smaller woofers that may be supported upon a relatively small baffle parallel and perpendicular to enclosure sides in an enclosure of the same volume as a prior art enclosure having larger woofers mounted on a slanted baffle. Referring to FIG. 39, there is shown still another embodiment of the invention comprising cylindrical subchambers. A first cylindrical structure 101 defines subchambers 101A and 101B separated by an internal circular baffle 102 carrying woofer 103 with end port tubes 104 and 105. Cylindrical structure 101 may then be placed through the circular opening of port 112 in cylindrical structure 111 to define another subchamber formed by the region between cylindrical structure 101 and the contiguous cylindrical region of structure 111. Cylindrical structure 121 may then similarly accommodate nested structures 101 and 111 through port 122 to define still another subchamber surrounding cylindrical structures 101 and 111 and partially cylindrical. It is within the principles of the invention to form similar nesting structures of elliptical, triangular, square or other cross sections. Applying this nesting principle allows for implementing a modular building-block approach to forming enclosures, whereby a selected level of bass response may be achieved by adding completely passive subchambers to one or more basic drive units. Referring to FIGS. 40A and 40B, there are shown shipping and use positions, respectively, of a variation of the embodiment of FIG. 39. Applying this nesting principle allows for making a compact portable bass system, whereby the larger, outer subchamber collapsed serve as a carrying case during transport of shipment as shown in FIG. 40A, but can be extended to define a subchamber of larger volume for better bass reproduction as shown in FIG. 40B.
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A loudspeaker system comprising: a first electroacoustical transducer (12) having a vibratable diaphragm for converting an input electrical signal into a corresponding acoustic output signal, an enclosure, the enclosure being divided into first (V₁), second (V₂) and third (V₃) subchambers by at least first (13) and second (11) dividing walls, and a first passive radiator (P₁) intercoupling the first and third subchambers, characterised by: the first dividing wall (13) supporting and coacting with the first electroacoustical transducer (12) to bound the first (V₁) and the second (V₂) subchambers, a second passive radiator (P₂,P₃) intercoupling at least one of the second (V₂) and third (V₃) subchambers with the region outside the enclosure, each of the passive radiators (P₁,P₂,P₃) having an acoustic mass, each of the subchambers (V₁,V₂,V₃) having an acoustic compliance, the acoustic masses and the acoustic compliances being selected to establish at least three spaced frequencies in the passband of the loudspeaker system at which the deflection characteristic of the vibratable diaphragm as a function of frequency has a minimum. A loudspeaker system according to claim 1, wherein the second passive radiator (P₂) intercouples the second subchamber (V₂) with the region outside the enclosure, and further comprising a third passive radiator (P₃) intercoupling the third subchamber (V₃) with the region outside the enclosure. A loudspeaker system according to claim 1, further comprising a fourth subchamber (V₄ ) having an acoustic compliance and separated from at least one other of the subchambers by at least a third dividing wall (14 ), and a third passive radiator (P₂ ) having an acoustic mass and intercoupling the fourth subchamber (V₄ ) with at least one of the other subchambers, the acoustic masses and the acoustic compliances being selected to establish at least a fourth frequency spaced from the at least three spaced frequencies in the passband of the loudspeaker system at which the deflection characteristic of the vibratable diaphragm as a function of frequency has a minimum. A loudspeaker system according to claim 3, further comprising at least a fourth passive radiator (P₄ ) intercoupling the fourth subchamber (V₄ ) with the region outside the enclosure. A loudspeaker system according to claim 1, further comprising a third passive radiator (P₂') intercoupling the second and third subchambers (V₂',V₃'). A loudspeaker system according to claim 1, wherein the second and third subchambers are end subchambers and the second passive radiator is located in the third subchamber. A loudspeaker system according to claim 6, wherein the first passive radiator (P1 vi) passes through the first subchamber (V1 vi). A loudspeaker system according to claim 6 or claim 7, wherein the second passive radiator is a port tube (P3 vi) bounded by the inside surface of a toroid of substantially elliptical cross section. A loudspeaker system according to claim 8, wherein the elliptical cross section has a major diameter corresponding substantially to the length of said port tube (P3 vi). A loudspeaker system according to claim 1, wherein the second passive radiator (P₂') intercouples the second subchamber (V₂') with the region outside the enclosure, and further comprising a third passive radiator (P₁',P₂') intercoupling the first and second subchambers (V₁',V₂'). A loudspeaker system according to claim 3, wherein the third passive radiator (P₂''',P₃''') intercouples the second and fourth subchambers (V₂''',V₄'''), and further comprising a fourth passive radiator (P₁''',P₃''') intercoupling the first and fourth subchambers (V₁''',V₄'''). A loudspeaker system according to claim 3, wherein the third passive radiator (P₃ ) intercouples the fourth subchamber (V₄ ) with the third subchamber (V₃ ), and further comprising a fourth passive radiator (P₂) intercoupling the fourth subchamber (V₄ ) with the second subchamber (V₂ ). A loudspeaker system according to claim 3, wherein the first and third passive radiators (P1 V,P3 V) and the fourth subchamber (V4 V) intercouple the first and third subchambers (V1 V,V3 V), and further comprising a fourth passive radiator (P2 V) intercoupling the second subchamber (V2 V) and the region outside the enclosure. A loudspeaker system according to claim 1, wherein at least one of the subchambers (101) nests inside one of the other subchambers (111,121). A loudspeaker system according to claim 14, wherein said at least one and said other subchambers (101,111,121) are relatively movable between a transport-contracted position and a use-extended position.
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BOSE CORP; BOSE CORPORATION
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CARON GERALD F; GAWRONSKI BRIAN J; SCHREIBER WILLIAM P; CARON, GERALD F.; GAWRONSKI, BRIAN J.; SCHREIBER, WILLIAM P.; Caron, Gerald F., c/o Bose Corporation; Gawronski, Brian J., c/o Bose Corporation; Schreiber, William P., c/o Bose Corporation
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EP-0489553-B1
| 489,553 |
EP
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B1
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EN
| 19,970,528 | 1,992 | 20,100,220 |
new
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G03F7
| null |
G03F7
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G03F 7/033
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Photosensitive polymeric printing medium and water developable printing plates
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A photosensitive printing medium is compounded from a latex copolymer, a linear thermoplastic, elastomeric block copolymer, a basic nitrogen atom-containing compound, an ethylenically unsaturated compound, and a polymerization initiation system. The printing medium has a microstructure of distinct domains of the latex copolymer and the elastomeric block copolymer in a matrix of the other components. The printing medium is typically supported on a substrate to form a printing plate. The printing medium is photosensitive, and is imaged by exposure to actinic radiation through a photographic negative film. The unexposed portions are washed away in a water dispersive medium, without the use of organic solvents, producing a printing plate which, after drying and postexposure to UV light, is ready for printing.
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This invention relates to printing plates, and, more particularly, to a flexible photosensitive printing medium deposited upon a substrate to produce a printing plate. Flexographic printing is widely used in the production of newspapers and in the decorative printing of packaging media. In flexographic printing, a layer of a flexible printing medium is coated onto a flexible substrate such as a thin sheet of steel, aluminum or synthetic polymer, to form a printing plate. A relief pattern corresponding to the negative of the image to be printed is formed in the printing medium. The plate is then mounted on the printing press, and the printing commences. EP-A-84851 describes a process for preparing flexographic photopolymer elements by passing into the nip of a calendar a photopolymer composition mass comprising elastomeric binder, an ethylenically unsaturated compound having at least one terminal ethylenic group, and a photoinitiator or photoinitiator system, and calendering the photopolymerisable composition between a support and a multi-layer cover element to form a photopolymerisable layer therebetween, wherein the multi-layer cover element consists essentially of a flexible cover film, optionally a flexible polymeric film, and a layer of an elastomeric composition which is photosensitive or becomes photosensitive during or after calendering by contact with the photopolymerisable layer. One type of printing medium is natural or synthetic rubber. This printing medium has excellent mechanical properties, but the preparation of a printing plate with a rubber printing medium is labor intensive and slow. A pattern plate and a matrix board are prepared, and rubber plates are then hot press molded. Molded rubber printing media are not practical for printing applications with short deadlines, such as newspapers. Due to the nature of the medium and the imaging techniques described above, photosensitive printing plates produce printed images of a generally superior nature to those of molded rubber media. In another approach, the printing medium is formed of an elastomeric photopolymer composition. A layer of the photosensitive material is coated onto the substrate to form the printing plate. The coated side is exposed with light through a photographic negative of the image to be printed, causing photopolymerization of the exposed portion of the printing medium, which then becomes physically hardened and resistant to removal in a solvent. The unexposed and therefore unhardened portion of the printing medium is removed by washing in a solvent, leaving a relief pattern of the image to be printed. The printing plate is mounted on a press and printing is commenced. Photosensitive printing plates fall into two broad categories, liquid compositions and solid compositions. The liquid compositions require the actual manufacture of the relief printing surface from a viscous liquid calendared at the printing site on complex machinery designed for that purpose. Solid photopolymer printing plates have the significant advantage of being pre-manufactured and therefore simpler and more reliable to use. Flexographic printing using photosensitive solid printing media offers the desirable combination of fast, inexpensive processing and long press runs. There are several types of photosensitive, solid flexographic printing plates. Plates using modified thermoplastic elastomeric rubber or rubber-like printing media have excellent mechanical properties, but can be processed only in organic solvents. See, for example, US Patents 4,369,246 and 4,622,088. Plates using acrylic modified polyolefinic copolymer latex printing media are less elastic and flexible, but can be processed using water as the solvent. See, for example, US Patents 4,275,142 and 4,927,738. Plates using elastomeric copolymers with carboxyl groups in the printing medium have good mechanical properties but must be processed in aqueous alkaline mixtures of water and water-soluble organic compounds. These solvents suffer from many of the same disadvantages as fully organic solvents. The need to use organic solvents for processing photosensitive, solid printing plates other than the acrylic modified polyolefinic copolymer printing medium is a major obstacle in their utilization. Such solvents include, for example, methyl ethyl ketone, benzene, xylene, carbon tetrachloride, 1,1,1-trichloroethane, and trichloroethylene, alone or in combination with a cosolvent such as ethanol or isopropyl alcohol. The organic solvents present problems of adverse health effects to exposed workers, disposal without environmental damage, and risk of fires. The one type of printing medium that does not require washing in an organic-containing solvent, the acrylic modified polyolefinic copolymers, has insufficient elasticity and toughness for some printing applications such as flexible packaging. Japanese application number 63-131192 (JP-A-89300246) describes a photosensitive resin composition for flexible printing which consists of a partially internally cross linked copolymer; a linear macromolecule with a molecular weight of at least 5,000 that contains at least 30 mol% conjugated diene monomer units per molecule; a compound containing a basic nitrogen atom; a photopolymerisable ethylenically unsaturated monomer and a photopolymerisation initiator. The application does not disclose a photosensitive printing medium which has discrete domains of a latex copolymer and an elastomer bound together by a photopolymerisable interstitial phase. There exists a need for a photosensitive solid printing medium and plate that combines excellent physical properties with the ability to be washed in water without the use of alkaline additives or any organic solvents. The present invention fulfills this need, and further provides related advantages. SUMMARY OF THE INVENTIONThe present invention provides a photosensitive, solid printing medium that exhibits excellent physical properties such as elasticity and toughness, long press-run life, excellent image quality, and, significantly, is developable in tap water (as long as the tap water is soft water without excessive concentrations of calcium and magnesium ions that can interfere with processing). There is therefore greatly reduced risk of fire or health damage to workers who prepare the plates, and greatly reduced risk of environmental damage upon disposal of the processing solvents. Conventional processing procedures are used for exposure and printing. Moreover, the fully processed and hardened printing medium is not water soluble, so that water-based inks can be used in printing. The present invention provides a photosensitive printing medium having a composite structure, comprising: discrete domains of water-dispersible latex copolymer, said copolymer comprising the polymerization product of an aliphatic diene monomer, an α,β-ethylenically unsaturated carboxylic acid, and a polyfunctional α,β-ethylenically unsaturated vinyl monomer, discrete domains of a linear elastomeric block copolymer, and photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer copolymer together, said interstitial phase containing a photopolymerizable compound and a photoinitiator, said photopolymerizable compound being an ethylenically unsaturated compound containing at least one ethylenically unsaturated group. The elastomer may for example be a linear thermoplastic, elastomeric block copolymer having at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), where A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C. The medium may further comprise a basic nitrogen atom-containing compound; and the ethylenically unsaturated photopolymerizable compound may contain at least one terminal ethylenically unsaturated group, said compound being capable of forming a polymer by free-radical chain polymerization; and the polymerization initiator initiates, upon exposure to actinic radiation, free-radical chain polymerization of the ethylenically unsaturated compound. A monofunctional vinyl monomer is desirably included in the latex copolymer. The present invention also provides a flexible printing element, comprising a supporting substrate and a layer thereon of the above photosensitive printing medium. The present invention additionally provides a process for preparing a printing plate comprising exposing at least one part of a flexible printing element as defined above to actinic radiation to photopolymerize the exposed photosensitive printing medium, and washing the element with water to remove unexposed medium. The proper combination of a latex copolymer and a linear thermoplastic elastomeric block copolymer yields the unexpected result of a photosensitive printing medium that has excellent physical properties and is developable in water, without the use of alkaline additives or any organic solvents. These properties are related to the microstructure of the composite material. In accordance with this aspect of the invention, a photosensitive printing medium having a composite structure comprises discrete domains of water dispersible latex copolymer, discrete domains of an elastomer, and a photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer together, and contains a photopolymerizable compound and a photoinitiator. A key feature of this structure is the discrete domains of latex copolymer and elastomer bound together with the photopolymerizable interstitial phase. In some combinations of materials investigated but that are not within the scope of the Invention, the ingredients combined in a uniformly intermixed form, without discrete domains. These materials with a uniformly intermixed microstructure could not be processed with water as the sole solvent. The interstitial phase is a mixture of compounds that is disposed between the domains. The interstitial phase is photopolymerized in those areas exposed to actinic light, hardening the exposed areas and preventing the domains of latex copolymer and elastomer from being washed away in subsequent processing. The unexposed areas of the interstitial phase are not hardened, and are washed away in subsequent processing along with the domains of latex copolymer and elastomer material in the unexposed regions. The present approach therefore provides an important advance in the art of flexographic printing technology. Highly elastic, tough printing media, which are developable in water, are available through this approach. Other features and advantages of the invention will be apparent from the following more detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. BRIEF DESCRIPTION OF THE DRAWINGSFigure 1 is a perspective view of a printing plate; and Figure 2 is an electron photomicrograph of the structure of the printing medium of the invention labelled to show the various phases and domains. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSFigure 1 depicts a typical printing plate 20, formed of a supporting substrate 22 and a layer of a printing medium 24 fixed to the substrate 22. The substrate is typically a thin, flexible sheet of aluminum, steel, or synthetic polymer about 0.002 to about 0.010 inches thick. The printing medium 24 is prepared according to the invention and coated onto the substrate in a manner to be described. The printing medium 24 is typically from about 0.010 to about 0.250 inches thick, depending upon the specific printing application. The most preferred printing medium thickness is about 0.015 to about 0.125 inches. In accordance with a preferred embodiment of the invention, a photosensitive printing medium comprises from about 25 to about 75 percent by weight of a latex copolymer comprising from about 5 to about 95 mol percent of an aliphatic conjugated diene monomer, from about 1 to about 30 mol percent of an α, β -ethylenically unsaturated carboxylic acid monomer, from about 1 to about 30 mol percent of a polyfunctional α, β -ethylenically unsaturated vinyl monomer, and from about 0 to about 70 mol percent of a monofunctional vinyl monomer; from about 15 to about 50 percent by weight of a linear thermoplastic, elastomeric block copolymer having at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), wherein A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C; a basic nitrogen atom-containing compound present in an amount of from about 0.02 to about 2.5 mole per mole of acid groups on the latex copolymer; from about 10 to about 60 percent by weight of an ethylenically unsaturated compound containing at least one terminal ethylenically unsaturated group, the compound being capable of forming a polymer by free-radical chain polymerization; and from about 0.001 to about 10 percent by weight of a polymerization initiator which, upon exposure to actinic radiation, initiates free-radical chain polymerization of the ethylenically unsaturated compound. In the latex copolymer, the aliphatic conjugated diene monomer is preferably 1,3-butadiene, isoprene, dimethylbutadiene, or chloroprene. Most preferably, the conjugated diene monomer is 1,3-butadiene. The α, β -ethylenically unsaturated carboxylic acid is preferably (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, or crotonic acid. Most preferably, the α, β -ethylenically unsaturated carboxylic acid is (meth)acrylic acid. The polyfunctional vinyl monomer is preferably trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate. Most preferably, the polyfunctional vinyl monomers are divinyl benzene and ethylene glycol dimethacrylate. The latex copolymer optionally contains a monofunctional vinyl monomer. The monofunctional vinyl monomer is preferably styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Most preferably, the monofunctional vinyl monomer is either methyl methacrylate or styrene. The thermoplastic, elastomeric block copolymer has at least one unit of the general form (A-B-A), (A-B)n, or (A-B), where each A unit is a non-elastomeric polymeric block appended to an elastomeric polymer block B. The (A-B-A), (A-B)n, or (A-B) unit may describe the general formula of the block copolymer or additional (A-B-A), (A-B)n, or (A-B) units may be appended to it to form a repeating structure. It is possible to vary the nature of the A and B units, for example using two different terminal, non-elastomeric A blocks within the (A-B-A), (A-B)n, or (A-B) structure, or using two or more different elastomeric materials within the B block. Additionally, the repeating structure may be appended to another polymer. The non-elastomeric polymeric unit A is preferably the polymerization product of aromatic hydrocarbons containing vinyl unsaturation. Most preferably the non-elastomeric unit A is polystyrene. The elastomeric unit B is the polymerization product of aliphatic conjugated diolefinic compounds such as 1,3-butadiene and isoprene. Most preferably, the elastomeric unit B is polybutadiene or polyisoprene. A particularly preferred linear, thermoplastic block copolymer is a block copolymer of polystyrene attached to each end of a middle block of polybutadiene or polyisoprene. Such preferred forms include polystyrene-polybutadiene-polystyrene and polystyrene-polyisoprene-polystyrene, with the polyolefin block being 60-90 percent by weight of the block copolymer. Examples of useful thermoplastic elastomer block copolymers are manufactured by the Shell Chemical Company and sold under the trademark KratonR. The basic nitrogen-atom containing compound has a tertiary basic nitrogen atom and preferably includes a vinyl group capable of participating in free-radical polymerization during exposure to actinic radiation with the ethylenically unsaturated compound in the interstitial phase. The basic nitrogen-atom containing compound is preferably N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl-N'--(meth)acryloylcarbamate, N,N-dimethylaminoethoxyethanol, or N,N-dimethylaminoethoxyethoxyethanol. Most preferably, the basic nitrogen-atom containing compound is N,N-dimethylaminopropyl (meth)acrylamide. The ethylenically unsaturated compound may be any compound having ethylenic unsaturation. The ethylenically unsaturated compound is preferably an unsaturated carboxylic ester such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, diallyl itaconate, dibutyl fumarate, dibutyl maleate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,4-butanediol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate; an unsaturated amide such as methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, or 1,6-hexanediamine bis(meth)acrylamide; a divinyl ester such divinyl adipate or divinyl phthalate; an acrylated or methacrylated aliphatic or aromatic urethane derived from hydroxyalkyl (meth)acrylates and isocyanate compounds; and a di(meth)acrylicester of a diepoxypolyether derived from an aromatic compound with polyalcohols such as bisphenol or Novolac compounds. The proper choice of the ethylenically unsaturated compound permits realization of the greatest benefits of the invention. A primary consideration in the choice of ethylenically unsaturated compounds is their compatibility with the polymeric ingredients. In the present invention, compatibility is associated with the ability of the ethylenically unsaturated compounds to be absorbed by one or more of the polymeric ingredients and the clarity of the resulting photosensitive resin composition after all of the ingredients have been properly combined and formed into a sheet of the desired thickness, typically from about 0.010 inches to about 0.250 inches. It is found that inadequate compatibility of the ethylenically unsaturated compounds, as defined by absorption into one or more of the binder polymers, causes unusably low resin viscosities and severe cold flow properties. Excessive compatibility of the ethylenically unsaturated compounds, as defined by nearly complete absorption into one or more of the binder polymers, causes the photosensitive resin composition to have a flaking, dry consistency with poor film-forming properties. Such a composition can not be formed into a sheet for use as a printing medium. It is preferable in the present invention that the compounded photosensitive resin forms coherent films and has a Mooney viscosity in the range of about 40 to about 100 (ML1 + 4(45°C), ASTM D 1646-74). Poor compatibility of the ethylenically unsaturated compounds, as defined by the creation of hazy photosensitive resin compositions of poor clarity, causes scattering of actinic radiation when formed into sheets for use as a printing medium. A slight haze can be tolerated in many printing relief applications, but should be avoided when the desired relief image contains fine detail. The scattering of actinic radiation during exposure of the photosensitive resin composition through the photographic negative can cause the desired image to be obscured and therefore not realized. A combination of ethylenically unsaturated compounds is usually required to obtain all of the desired properties of the compounded photosensitive resin. The presently most preferred ethylenically unsaturated compound is a combination of (meth)acrylated aliphatic urethane oligomers and dibutyl fumarate. The polymerization initiation system is composed of compounds which, upon exposure to actinic radiation, homolytically decompose or otherwise react to produce free radicals which can initiate free-radical polymerization. The initiation system is preferably benzoin ethers such as benzoin isopropyl ether or benzoin isobutyl ether; benzophenones such as benzophenone or methyl o-benzoylbenzoate; xanthones such as xanthone, thioxanthone or 2-chlorothioxanthone; acetophenones such as acetophenone, 2,2,2-trichloroacetophenone, 2,2-diethoxyacetophenone, or 2,2-dimethoxy-2-phenyl- acetophenone; quinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, phenanthraquinone, or 1,2-benzanthraquinone; and acyl phosphine oxides such as methyl 2,6-dimethylbenzoyl phenylphosphinate, methyl 2,6-dimethoxybenzoyl phenylphosphinate, 2,6-dimethylbenzoyldiphenylphosphine oxide, or 2,4,6-trimethylbenzoylphenylphosphine oxide. Most preferably, the polymerization initiation system is either 2,2-dimethoxy-2-phenylacetophenone or 2-alkyl-anthraquinones. The photosensitive composition of the invention may optionally contain a small amount of a thermal polymerization inhibitor, for example hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p-t-butylcatechol, 2,6-di-t-butyl-p-cresol, or benzoquinone. Dyes such as eosin Y or rose bengal may be added. Plasticizers such as dialkyl phthalate, dialkyl sebacate, alkyl phosphate, polyethylene glycol, naphthionic oils, paraffinic oils, polyethylene glycol esters, polyethylene glycol ethers, phenoxy polyethylene glycols, alkylphenoxy polyethylene glycols, and glycerol may be added. Antiozonants such as microcrystalline wax, paraffin wax, dibutylthiourea and unsaturated vegetable oils may also be added. The latex copolymer is present in an amount of from about 25 to about 75 percent by weight of the total composition. If less than about 25 percent is present, the photoimaged printing medium cannot be developed in water. If more than about 75 percent is present, the physical properties such as elasticity and toughness of the photocured composition are inadequate. The linear, thermoplastic block copolymer is present in an amount of about 15 to about 50 percent by weight of the total composition. If less than about 15 percent is present, the physical properties such as elasticity and toughness are inadequate. If more than about 50 percent is present, the photoimaged printing medium cannot be developed in water. The basic nitrogen atom-containing compound is present in an amount of from about 0.02 to about 2.5 moles per mole of acid groups on the latex copolymer. The neutralization of the carboxyl groups of the latex copolymer by the tertiary amine group of the basic nitrogen atom-containing compound allows the latex to be dispersed in water or aqueous solvents. If less than about 0.02 moles per mole is present, the photoimaged printing medium cannot be developed in water. If more than about 2.5 moles per mole is present, there is excessive swelling of the cured, processed plate in water or water-based inks. The ethylenically unsaturated compound, preferably a mixture of such compounds, is present in an amount of from about 10 to about 60 percent by weight of the total composition. If less than about 10 percent is present, there is inadequate curing of the printing medium during UV exposure. Also, the compounded resin has an unworkable viscosity, with the compounded resin being flaky and dry. If more than about 60 percent is present, the viscosity of the resin is too low due to the presence of too much liquid in the mixture. The final cured film may also be too brittle due to excessive crosslinking of the interstitial phase and too little base polymer. The photoinitiator is present in an amount of from about 0.001 to about 10 percent by weight of the total composition. If less than about 0.001 percent is present, curing is slow or inadequate, or both. If more than about 10 percent of photoinitiator is present, light cannot penetrate the full thickness of the plate and there is insufficient through-cure due to excessive absorption of light on the top surface of the photosensitive printing medium. Curing of the composition at the resin-adhesive or resin-substrate interface often is needed for adequate adhesion, and too much photoinitiator may prevent curing at or near the interface. The photosensitive compositions are prepared by using conventional mixing and milling techniques well known in the art. The ingredients (latex copolymer, thermoplastic, elastomeric block copolymer, basic nitrogen-atom containing compound, ethylenically unsaturated compound, and polymerization initiation system, and optional ingredients) can be compounded using a mixer, kneader, or extruder. The components may be combined at the start of the compounding process, or alternatively, the latex copolymer and linear thermoplastic elastomeric block copolymer may be pre-kneaded. Alternatively, one or more of the liquid components may be preabsorbed into either of the polymeric phases. The resulting compositions can be formed into a photosensitive medium element by forming into a sheet by molding, calendaring, rolling, extruding, or a similar process. To form a printing plate, the photosensitive printing medium is laminated onto a suitable solid substrate or, an intermediate adhesive layer may be used. In accordance with this aspect of the invention, a flexible printing plate comprises a supporting substrate; and a layer of a photosensitive printing medium supported on the substrate, the printing medium having a composite structure comprising discrete domains of latex copolymer, discrete domains of an elastomer, and a photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer together, and contains a photopolymerizable compound and a photoinitiator. If desired, an antihalation layer may be used between the photosensitive sheet and the substrate. A variety of substrates may be used with the photosensitive compositions. The term substrate means any solid layer giving support and stability to the photosensitive medium. Particularly useful substrates are natural or synthetic materials that can be made into a rigid or flexible sheet form. Substrate materials include metals such as steel, copper or aluminum sheets, plates, or foils; paper; or films or sheets made from synthetic polymeric materials such as polyesters, polystyrene, polyolefins, or polyamides, used either alone or as laminates, and foam sheets. A cover sheet may be used on the surface of the photosensitive composition opposite that laminated to the substrate to protect the surface from contamination or damage during shipping, storage, and handling. Such cover sheets are well known in the art. See for example US Patents 4,323,637 and 2,369,246. It is often desirable to incorporate into the photosensitive element a layer between the cover sheet and the photosensitive composition that is soluble in the processing solvent and which remains on the surface of the photosensitive composition upon removal of the cover sheet. Such surface layers, well known in the art, can be useful to reduce the tackiness of the element's surface or to modify the photosensitive properties of the element, as by dyes or pigments. Printing plates are made by exposing selected portions of the photosensitive layer of the element to actinic radiation. In accordance with this aspect of the invention, a process for providing a printing plate ready for printing comprises the steps of providing a flexible printing plate comprising a substrate; and a layer of a photosensitive printing medium supported on the substrate, the printing medium having a composite structure comprising discrete domains of latex copolymer, discrete domains of an elastomer, and a photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer together, and contains a photopolymerizable compound and a photoinitiator; exposing portions of the printing medium with actinic light through a negative; and washing away the unexposed portions of the printing medium in a dispersive medium consisting essentially of water. The photosensitive medium is sometimes first generally exposed with actinic light, from its backside through the supporting substrate prior to exposure from the frontside through the negative, to partially harden the photosensitive medium material at and near the interface with the substrate. This back-exposure technique improves the bonding between the printing medium and the substrate, and also creates a subsurface hardened layer which acts as a floor after subsequent exposure and washout of the front side of the printing medium through the negative. Selective exposure of the photosensitive medium is achieved by the use of an image-bearing transparency such as a negative film on the surface of the photosensitive layer, through the front side of the photosensitive medium. Areas of the transparency opaque to the actinic radiation prevent the initiation of free-radical polymerization within the photosensitive layer directly underneath them. Transparent areas of the image-bearing element will allow the penetration of actinic radiation into the photosensitive layer, initiating free-radical polymerization, rendering those areas insoluble in the processing solvent, in this case water. The unexposed portions of the photosensitive layer are then selectively removed by washing in water. The washing may be performed by a variety of processes, including brushing, spraying, or immersion. Brushing is usually preferred as it aids in the removal of soluble portions and reduces the washing time required. The resulting surface has a relief pattern that reproduces the image to be printed, the relief portions extending above the pre-hardened floor layer (if any) produced by the back-exposure processing. Raised portions carry ink to the surface being printed during the printing operation. The resulting image-bearing printing plate can optionally be further prepared prior to use. After processing, the wet printing plate is dried, as with a forced hot air dryer or a convection oven. Exposure of the entire cured, processed photosensitive layer to actinic radiation for several minutes is often desirable to increase toughness and reduce surface tack. The surface may be treated with an oxidizing solution such as aqueous acidic hypochlorite or aqueous bromine solutions to reduce surface tack. Such surface treatments are well known in the art. See for example, US Patents 4,400,459 and 4,400,460. In the printing plate and printing medium of the present invention, selective removal of the unreacted photosensitive composition layer is achieved by brushing or spraying the element with water heated to about 25-75°C for about 5-30 minutes. Increased water temperature generally decreases the time required to remove the desired portions. It is important to use soft water, that is, water from which metallic cations such as Ca+2, Mg+2, and Fe+2 have been removed, during the washing process. The presence of these inorganic cations impedes the dispersion of unpolymerized areas. Commonly available water softening systems (such as ion exchange systems) are suitable for pre-treating the water used to remove the unreacted photosensitive composition. The processed plate is dried in an oven at about 50-80°C for about 5-15 minutes. The processed plate is then postexposed to ultraviolet (UV) light for about 15 seconds to 10 minutes to further toughen the plate. These last two steps are utilized in the processing of other types of photosensitive printing plates, but the required times are much longer for those other types of plate. Generally, no further surface treatments such as oxidation, which are necessary for some other photosensitive printing plates, are needed before the plate is used. The photosensitive medium material of the present invention utilizes a combination of a hydrophilic copolymer latex and a hydrophobic linear thermoplastic elastomer block copolymer. The hydrophilic copolymer latex contains carboxyl groups, which when neutralized with the basic nitrogen atom-containing compound, impart to the latex water dispersibility. The copolymer latex is internally crosslinked and therefore maintains its spherical latex microstructure after compounding with the other ingredients used to produce the photosensitive composition. These compositions rely on the photoinitiated polymerization during exposure to actinic radiation of reactive compounds present between and absorbed into the latex particles for the formation of a strong, cohesive film. Such microstructures often do not possess physical properties such as good elasticity, toughness, and abrasion resistance. The linear thermoplastic elastomer block copolymers possess long homopolymer blocks of aromatic and aliphatic comonomers which cause the formation of discrete phases. The aromatic phases impart good toughness and thermoplastic properties while the aliphatic domains impart good elasticity. These linear thermoplastic block copolymers are hydrophobic by nature and are not solubilized by water. Figure 2 depicts the microstructure of the photosensitive printing medium of the invention. The photomicrograph of Figure 2 was obtained by sectioning a specimen of the printing medium made in accordance with the invention, and shadowing it with OsO4. The structure contains discrete domains 30 of the latex copolymer and discrete domains 32 of the elastomeric block copolymer. (A domain of each type has been outlined on the photomicrograph so that they can be readily discerned.) The domains are generally roughly equiaxed and range from about 0.1 to about 0.5 micrometers in size. An interstitial phase between the domains 30 and 32 binds the domains together. The discrete domains of the latex copolymer occupy from about 25 to about 75 percent by volume of the medium, and the discrete domains of the elastomer occupy from about 15 to about 50 percent by volume of the medium. This structure is significant in permitting achieving improved properties while maintaining water processibility. Water can penetrate the unreacted portions, solubilizing the unreacted interstitial phase 36 and dispersing the hydrophilic latex particle domains 32. The voids thus formed cannot support the hydrophobic elastomer domains 34 exposed to the water, which are removed by the processing action. Alternatively, had the microstructure been a single homogeneous mass without the domain structure of discrete domains of latex copolymer and elastomer block copolymer, water processibility would not have been possible. Although domain structures for latex block copolymer-based printing media are known, it is surprising that a substantial amount of the elastomeric block copolymer can be added without loss of the discrete domain structure or transition to a homogeneous mass microstructure. The use of the two types of copolymers in combination imparts to the photosensitive resin composition excellent physical properties such as elasticity, toughness, and abrasion resistance. Significantly, from about 15-50 percent by weight of the hydrophobic block copolymer does not prevent the development of the composition in pure water. Thin strands of linear copolymer often connect the elastomer domains. The presence of rubbery hydrophilic latex domains imparts the property of water processability. The presence of hydrophobic elastomer domains imparts the improved physical properties. The following examples are intended to illustrate aspects of the invention, and should not be taken as limiting of the invention in any respect. Example 1--Preferred CompositionA latex copolymer was provided having a composition in weight percent of 70 percent 1,3-butadiene, 20 percent styrene, 6 percent methacrylic acid, and 4 percent divinyl benzene. To 30.7 grams of this latex copolymer was added a mixture of the following: 7.3 grams of N,N-dimethylaminopropyl methacrylamide, 4.9 grams difunctional aliphatic urethane oligomer (Sartomer C-9504), 25.6 grams dibutyl fumarate, 0.3 grams 2-t-butylanthraquinone, and 0.5 grams 2,6-di-t-butyl-p-cresol. The latex copolymer was allowed to absorb the mixture for 12 hours and was then compounded with 30.7 grams of styrene-isoprene-styrene (86 weight percent isoprene) block copolymer (Shell KratonR D-1107) using a two-roll mill at 70°C until clear and uniform in appearance, which required about 1 hour. The resulting compound was a non-tacky solid. This compound was placed between two sheets of polyester terephthalate (duPont MylarR) and pressed into a sheet 0.060 inches thick. The photosensitive composition was removed from the polyester film and was laminated onto a 0.005 inch thick sheet of polyester terephthalate which had been previously coated with a film about 2 micrometers thick of a commercial polyurethane adhesive. The photosensitive composition was back-exposed through the polyester substrate for 30 seconds to ultraviolet radiation from a bank of Sylvania 115W Blacklight fluorescent lamps at a distance of about 2 inches. The substrate was then turned away from the light source and a photographic negative with the desired image was contacted with the photosensitive resin composition. The composition was exposed for 4 minutes through the negative. After removing the negative, the unexposed, non-image area was washed away in a brush-type processor using water heated to 40°C, for 4 minutes. The resulting printing plate had floor and relief layers each about 0.030 inches thick. The processed printing plate was dried at 80°C for 5 minutes and postexposed using the same light source for 3 minutes. The resulting printing plate exhibited good toughness and flexibility, and was non-tacky. Physical properties of specimens of the printing media were measured with the following results: Shore A hardness, 32; resilence, 53 percent; tensile strength, 19 kilograms per square centimeter; 234 percent elongation; and no cracking when bent, after exposure and processing, completely back upon itself. (In the last test, a sample of the exposed and processed printing medium material is bent around rods of decreasing diameter, until cracking is observed. In the test of the preferred material, no cracking was observed in the test even when no rod was used, and the resin was bent back upon itself.) The printing plate was mounted on a flexographic printing press and printed with a variety of inks, including water-based, alcohol-based, and organic solvent-based types. The printing plate showed good reproduction of the original image and long run life. Example 2--Less Preferred Composition Within the Scope of the InventionA latex copolymer was prepared having a composition, in weight percent, of 70 percent 1,3-butadiene, 20 percent methyl methacrylate, 6 percent methacrylic acid, and 4 percent ethylene glycol dimethacrylate. To 40.0 grams of the latex copolymer was added a mixture of the following: 7.3 grams of N,N-dimethylaminopropyl methacrylamide, 4.9 grams difunctional aliphatic urethane oligomer (Sartomer C-9504), 25.5 grams dibutyl fumarate, 0.3 grams 2-t-butylanthraquinone, and 0.5 grams 2,6-di-t-butyl-p-cresol. After absorption as described in Example 1, the ingredients were compounded with 21.5 grams of styrene-isoprenestyrene (86 weight percent isoprene) (KratonR D-1107) block copolymer as described in Example 1. A printing plate was made from the resulting photosensitive compound and exposed and processed as described in Example 1, except that the washing time was 8 minutes. The resulting cured composition had the following physical properties: Shore A hardness, 37; resilence, 57 percent; tensile strength, 12 kilograms per square centimeter; 168 percent elongation; and no cracking when bent completely back upon itself. Example 3--Insufficient Linear, Thermoplastic, Elastomeric Block CopolymerA latex copolymer was prepared having a composition in weight percent of 69 percent 1,3-butadiene, 20 percent methyl methacrylate, 6 percent methacrylic acid, and 2 percent divinyl benzene. To 49.2 grams of the latex copolymer was added a mixture of the following: 5.0 grams of ethoxy bisphenol A diacrylate, 4.9 grams of 1,6-hexane diol dimethacrylate, 5.5 grams of lauryl methacrylate, 15.0 grams of dibutyl fumarate, 0.3 grams 2-ethylanthraquinone, and 0.5 grams 2,6-di-t-butyl-p-cresol. After absorption as described in Example 1, the ingredients were compounded with 12.3 grams of styrene-isoprene (90 weight percent isoprene) block copolymer (KratonR 1320), as described in Example 1. The photosensitive resin was formed, cured, and processed as in Example 1, except that a washing time of 4 minutes was used. The resulting cured compound was harder and had elasticity and toughness inferior to those of the compounds of Examples 1 and 2. The cured composition had the following physical properties: Shore A hardness, 60; resilence, 37 percent; tensile strength, 25 kilograms per square centimeter; 64 percent elongation; and cracked when bent around a rod of 2 millimeters diameter. Example 4--Non-block-type CopolymerA latex copolymer was prepared having a composition in weight percent of 69 percent 1,3-butadiene, 20 percent methyl methacrylate, 9 percent methacrylic acid, and 2 percent divinyl benzene. To 36.9 grams of the latex copolymer was added a mixture of the following: 24.6 grams of butadiene-acrylonitrile copolymer (BF Goodrich ProteusR 9500, a non-block copolymer), 7.3 grams N,N-dimethylaminopropyl methacrylamide, 5.0 grams difunctional aliphatic urethane oligomer (Sartomer C-9504), 4.9 grams 1,6-hexane diol dimethacrylate, 5.5 grams lauryl methacrylate, 15.0 grams dibutyl fumarate, 0.3 grams 2-ethylanthraquinone, and 0.5 grams 2,6-di-t-butyl-p-cresol. The mixture was compounded on a two-roll mill as described in Example 1. The photosensitive resin was formed, cured, and processed as in Example 1, except that it was found that the composition could not be washed in water to remove unexposed resin. The compound had the following physical properties: Shore A hardness, 57; resilence, 35 percent; tensile strength, 25 kilograms per square centimeter; 87 percent elongation; and no cracking was observed when the exposed and processed printing medium was bent completely back upon itself. Example 5--No Latex CopolymerA mixture of 11.5 grams N,N-dimethylaminopropyl methacrylamide, 7.9 grams ethoxylated bisphenol A diacrylate, 7.7 grams 1,6-hexane diol diacrylate, 8.7 grams lauryl methacrylate, 23.8 grams dibutyl fumarate, 0.5 grams 2-ethylanthraquinone, and 0.9 grams 2,6-di-t-butyl-p-cresol was combined with 39.0 grams of styrene-isoprene-styrene (86 weight percent isoprene) block copolymer (KratonR D-1107). The combined ingredients were allowed to stand for 20 hours, at which time little of the liquid was absorbed into the block copolymer. Compounding with a two-roll mill at 70°C for several hours resulted in a soft, sticky resin that exhibited cold flow characteristics. It was not possible to form a sheet of sufficient quality to measure the same physical properties measured in the other examples. A cure sheet of the resin could not be processed in water. Example 6--No Block CopolymerA latex copolymer was prepared having a composition in weight percent of 70 percent 1,3-butadiene, 20 percent methyl methacrylate, 6 percent methacrylic acid, and 4 percent ethylene glycol dimethacrylate. To 59.4 grams of the latex copolymer was added a mixture of the following: 5.8 grams of N,N-dimethylaminopropyl methacrylamide, 5.4 grams polyethoxy phenol, 5.4 grams polyethoxy nonylphenol, 10.8 grams lauryl methacrylate, 5.5 grams diethylene glycol dimethacrylate, 5.5 grams polyethylene glycol (400) diacrylate, 1.8 grams 2,2-dimethoxy-2-phenyl-acetophenone, and 0.4 grams 2,6-di-t-butyl-p-cresol. The ingredients were compounded using a two-roll mill as described In Example 1 and processed as in Example 1 to a printing plate, except that the exposure time through the negative film was reduced to 80 seconds and the washing time in water was 3 minutes. The cured film had the following physical properties, which are not suitable for use as a flexographic printing plate: Shore A hardness, 72; resilence, 30 percent; tensile strength, 18 kilograms per square centimeter; 39 percent elongation; and cracking was observed when the printing medium was bent around a rod having a diameter of 6 millimeters. When printed on a flexographic printing press, wearing of the relief layer was quickly observed, resulting in poor reproduction quality. Example 7--Determination of Dependence of Properties on Amount of Thermoplastic, Elastomeric Block CopolymerA photosensitive resin composition was prepared as described in Example 6. Styrene-isoprene-styrene block copolymer (KratonR D-1107) at varying weight-percent levels was added to portions of the composition by compounding on a two-roll mill. The resulting compounds were formed into sheets 0.060 inches thick and laminated onto a substrate as described in Example 1. These printing plates were processed as described in Example 1 until about 0.030 inches of the unexposed resin composition was removed. The required processing times for unreacted polymer washout in tap water were as shown in the following table Block Copolymer (Weight Percent) Processing Time (Minutes) 103 205 308 4018 50more than 60 The processing time is a key consideration in a production operation. Acceptable processing times are obtained with block copolymer percentages of up to 50 percent. However, the lesser block copolymer contents below about 15 weight percent produce unacceptable mechanical properties, see Example 3 where the block copolymer content is 12.3 percent. It is therefore concluded that the block copolymer should be present in an amount of from about 15 to about 50 percent. Above about 25 percent, the processing times begin to lengthen to unacceptably high values. Very short processing times are also not desirable, because the processing may be difficult to control precisely. A preferred block copolymer content is about 25 percent. Such a resin composition has a combination of good mechanical properties and good processability in a commercial printing operation. Examples 8-23--Use of Other CompositionsA series of specimens using various ingredients was prepared and mechanically tested in the manner discussed previously. The following table reports the compositions and results: These results establish that a wide range of components may be used in the compositions of the invention, and that substantial deviations from the established ranges result in diminished properties.
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Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, GR, IT, LI, LU, NL, SEA photosensitive printing medium having a composite structure, comprising: discrete domains of water-dispersible latex copolymer, said copolymer comprising the polymerization product of an aliphatic diene monomer, an α,β-ethylenically unsaturated carboxylic acid, and a polyfunctional α,β-ethylenically unsaturated vinyl monomer, discrete domains of a linear elastomeric block copolymer, and photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer copolymer together, said interstitial phase containing a photopolymerizable compound and a photoinitiator, said photopolymerizable compound being an ethylenically unsaturated compound containing at least one ethylenically unsaturated group. The printing medium of claim 1, wherein the domains have a maximum dimension of from about 0.1 to about 0.5 micrometers. The printing medium of claim 1 or 2, wherein the elastomer is a polymer having at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), where A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature of below about 10°C. The printing medium of any one of claims 1 to 3, wherein the discrete domains of the latex copolymer occupy from about 25 to about 75 percent by volume of the medium. The printing medium of any one of claims 1 to 4, wherein the discrete domains of the elastomer occupy from about 15 to about 50 percent by volume of the medium. A photosensitive printing medium as claimed in claim 1 which further comprises a basic nitrogen atom-containing compound; and wherein: the linear thermoplastic, elastomeric block copolymer has at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), wherein A is a non-elastomeric polymer block having a number average molecule weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C; the ethylenically unsaturated photopolymerizable compound contains at least one terminal ethylenically unsaturated group, said compound being capable of forming a polymer by free-radical chain polymerization; and and the polymerization initiator initiates, upon exposure to actinic radiation, free-radical chain polymerization of the ethylenically unsaturated compound. The printing medium of claim 6, wherein the aliphatic conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isopropene, dimethylbutadiene, and chloroprene. The printing medium of claim 6 or 7, wherein the α,β-ethylenically unsaturated carboxylic acid is selected from the group consisting of (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, and crotonic acid. The printing medium of claim 6, 7 or 8, wherein the polyfunctional vinyl monomer is selected from the group consisting of trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,4-butane diol di(meth)acrylate, and 1,6-hexane diol di(meth)acrylate. The printing medium of any one of claims 6 to 9, wherein the latex copolymer further contains a monofunctional vinyl monomer. The printing medium of claim 10, wherein the monofunctional vinyl monomer is selected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. The printing medium of any one of claims 6 to 11, wherein the non-elastomeric unit A is the polymerization product of aromatic hydrocarbons containing vinyl unsaturation. The printing medium of claim 12, wherein the non-elastomeric unit A is polystyrene. The printing medium of any one of claims 6 to 13, wherein the elastomeric unit B is the polymerization product of aliphatic conjugated diolefinic compounds. The printing medium of any one of claims 6 to 13, wherein the elastomeric unit B is selected from the group consisting of polybutadiene, polyisoprene, and the combination of ethylene and butylene. The printing medium of any one of claims 6 to 15, wherein the basic nitrogen atom-containing compound is selected from the group consisting of N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl (meth) crylamide, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl-N'-(meth)acryl-olycarbamate, N,N-dimethylaminoethoxyethanol, and N,N-dimethylaminoethoxyethoxyethanol. The printing medium of any one of claims 6 to 16, wherein the ethylenically unsaturated compound is selected from the group consisting of an unsaturated carboxylic a divinyl ester, an acrylated urethane, a methacrylated urethane, and a di(meth)acrylic ester of a diepoxypolyether derived from an aromatic compound with polyalcohols. A photosensitive printing medium comprising, from about 25 to about 75 percent by weight of a latex copolymer comprising from about 5 to about 95 mol percent of an aliphatic conjugated diene monomer, from about 1 to about 30 mol percent of an α,β-ethylenically unsaturated carboxylic acid, from about 1 to about 30 mol percent of a polyfunctional α,,β-ethylenically unsaturated vinyl monomer, and from about 0 to about 70 mol percent of a monofunctional vinyl monomer; from about 15 to about 50 percent by weight of a linear thermoplastic, elastomeric block copolymer having at least one unit of a general formula selected from the block Copolymer group consisting of (A-B-A), (A-B)n, and (A-B), wherein A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C; a basic nitrogen atom-containing compound present in an amount of from about 0.02 to about 2.5 mole per mole of acid groups in the latex copolymer; from about 10 to about 60 percent by weight of an ethylenically unsaturated compound containing at least one ethylenically unsaturated group, the compound being capable of forming a polymer by free-radical chain polymerization; and from about 0.001 to about 10 percent by weight of a polymerization initiator which, upon exposure to actinic radiation, initiates free-radical chain polymerization of the ethylenically unsaturated compound. A flexible printing element, comprising a supporting substrate and a layer thereon of the photosensitive printing medium of any one of claims 1 to 18. A process for preparing a printing plate comprising exposing at least one part of a flexible printing element as claimed in claim 19 to actinic radiation to photopolymerize the exposed photosensitive printing medium, and washing the element with water to remove unexposed medium. Claims for the following Contracting State : ESA process for preparing a photosensitive printing medium having a composite structure, comprising: discrete domains of water-dispersible latex copolymer, said copolymer comprising the polymerization product of an aliphatic diene monomer, an α,β-ethylenically unsaturated carboxylic acid, and a polyfunctional α,β-ethylenically unsaturated vinyl monomer, discrete domains of a linear elastomeric block copolymer, and a photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer copolymer together, said interstitial phase containing a photopolymerizable compound and a photoinitiator, said photopolymerizable compound being an ethylenically unsaturated compound containing at least one ethylenically unsaturated group, said process comprising admixing the latex copolymer, elastomeric block copolymer, photopolymerizable compound and photoinitiator. The process of claim 1, wherein the domains of the linear elastomeric block copolymer have a maximum dimension of from about 0.1 to about 0.5 micrometers. The process of claim 1 or 2, wherein the elastomer is a polymer having at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), where A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature of below about 10°C. The process of any one of claims 1 to 3, wherein the discrete domains of the latex copolymer occupy from about 25 to about 75 percent by volume of the medium. The process of any one of claims 1 to 4, wherein the discrete domains of the elastomer occupy from about 15 to about 50 percent by volume of the medium. A process as claimed in claim 1, in which the photosensitive printing medium further comprises a basic nitrogen atom-containing compound; and wherein: the linear thermoplastic, elastomeric block copolymer has at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), wherein A is a non-elastomeric polymer block having a number average molecular weight of 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C; the ethylenically unsaturated photopolymerizable compound contains at least one terminal ethylenically unsaturated group, said compound being capable of forming a polymer by free-radical chain polymerization; and the polymerization initiator initiates, upon exposure to actinic radiation, free-radical chain polymerization of the ethylenically unsaturated compound. The process of claim 6, wherein the aliphatic conjugated diene monomer is selected from the group consisting of 1,3-butadiene, isoproprene, dimethylbutadiene, and chloroprene. The process of claim 6 or 7, wherein the α,β-ethylenically unsaturated carboxylic acid is selected from the group consisting of (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, and crotonic acid. The process of claim 6, 7 or 8, wherein the polyfunctional vinyl monomer is selected from the group consisting of trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,4-butane diol di(meth)acrylate, and 1,6-hexane diol di(meth)acrylate. The process of any one of claims 6 to 9, wherein the latex copolymer further contains a monofunctional vinyl monomer, The process of claim 10, wherein the monofunctional vinyl monomer is selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. The process of any one of claims 6 to 11, wherein the non-elastomeric unit A is the polymerization product of aromatic hydrocarbons containing vinyl unsaturation. The process of claim 12, wherein the non-elastomeric unit A is polystyrene. The process of any one of claims 6 to 13, wherein the elastomeric unit B is the polymerization product of aliphatic conjugated diolefinic compounds. The process of any one of claims 6 to 13, wherein the elastomeric unit B is selected from the group consisting of polybutadiene, polyisoprene, and the combination of ethylene and butylene. The process of any one of claims 6 to 15, wherein the basic nitrogen atom-containing compound is selected from the group consisting of N,N-dimethylaminoethyl (meth) acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl-N'-(meth)acryl-olycarbamate, N,N-dimethylaminoethoxyethanol, and N,N-dimethylaminoethoxyethoxyethanol. The process of any one of claims 6 to 16, wherein the ethylenically unsaturated compound is selected from the group consisting of an unsaturated carboxylic ester, a divinyl ester, an acrylated urethane, a methacrylated urethane, and a di(meth)acrylic ester of a diepoxypolyether derived from an aromatic compound with polyalcohols. A process as claimed in claim 1, for preparing a photosensitive printing medium comprising: from about 25 to about 75 percent by weight of a latex copolymer comprising from about 5 to about 95 mol percent of an aliphatic conjugated diene monomer, from about 1 to about 30 mol percent of an α,β-ethylenically unsaturated carboxylic acid, from about 1 to about 30 mol percent of a polyfunctional α,β-ethylenically unsaturated vinyl monomer, and from about 0 to about 70 mol percent of a monofunctional vinyl monomer; from about 15 to about 50 percent by weight of a linear thermoplastic, elastomeric block copolymer having at least one unit of a general formula selected from the block copolymer group consisting of (A-B-A), (A-B)n, and (A-B), wherein A is a non-elastomeric polymer block having a number average molecular weight of above 2,000 to 100,000 and a glass transition temperature of above about 25°C, and B is an elastomeric polymer block having a number average molecular weight of 25,000 to 1,000,000 and a glass transition temperature below about 10°C; a basic nitrogen atom-containing compound present in an amount of from about 0.02 to about 2.5 mole per mole of acid groups in the latex copolymer; from about 10 to about 60 percent by weight of an ethylenically unsaturated compound containing at least one ethylenically unsaturated group, the compound being capable of forming a polymer by free-radical chain polymerization; and from about 0.001 to about 10 percent by weight of a polymerization initiator which, upon exposure to actinic radiation, initiates free-radical chain polymerization of the ethylenically unsaturated compound. A flexible printing element, comprising a supporting substrate and a layer thereon of the photosensitive printing medium produced by the process of any one of claims 1 to 18. A process for preparing a printing plate comprising exposing at least one part of a flexible printing element as claimed in claim 19 to actinic radiation to photopolymerize the exposed photosensitive printing medium, and washing the element with water to remove unexposed medium. A photosensitive printing medium having a composite structure, comprising: discrete domains of water-dispersible latex copolymer, said copolymer comprising the polymerization product of an aliphatic diene monomer, an α,β-ethylenically unsaturated carboxylic acid, and a polyfunctional α,β-ethylenically unsaturated vinyl monomer, discrete domains of a linear elastomeric block copolymer, and photopolymerizable interstitial phase that binds the domains of latex copolymer and elastomer copolymer together, said interstitial phase containing a photopolymerizable compound and a photoinitiator, said photopolymerizable compound being an ethylenically unsaturated compound containing at least one ethylenically unsaturated group.
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NAPP SYSTEMS INC; NAPP SYSTEMS INC.
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WAGNER WILLIAM R; WAGNER, WILLIAM R.
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EP-0489554-B1
| 489,554 |
EP
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B1
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EN
| 19,960,515 | 1,992 | 20,100,220 |
new
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B65B29
| null |
B31B1, B65B29
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B65B 29/04
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Method and apparatus for production of tagged articles
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A method and apparatus are described for tag and thread assembly for tagged infusion packets. Spaced tags (8) from a strip (40) of tags and a length of thread (10) are laid over each other on the periphery of a first assembly wheel (58) and the thread is drawn out in loops (12) between successive tags. The spaced tags and looped thread are transferred to a second assembly wheel (108) where they are connected to a web (30a) of sheet material that is to form the infusion packets. The web is subsequently formed into a series of compartments in which infusion material is contained. The compartments are severed from the web for forming the individual packets and the thread is simultaneously severed between the packets.
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This invention relates to tagged articles and to a method and apparatus for producing such articles. The invention finds particular, but not exclusive, use in the production of infusion packets containing infusible material, such as tagged tea bags. Tea bags consist of doses of dried and shredded tea leaves, sealed in compartments made of a readily permeable web material, generally referred to as paper although it may have a significant plastics content and may even be constituted by a perforated or permeable plastics material. Tea bags and other infusion bags are often provided with a tag, attached to the bag itself through a thread, to make it more convenient for the user to handle the bag. Examples of such tagged bags can be found in GB-A-2052428, GB-A-2202819, US-A-2925171 and US-A-2335159. In the first of these, the thread is pre-packed within the tag and the tag is then inserted into a pocket in the bag itself. The arrangement is intended to avoid entangling the threads in a package of bags such as might happen if all the tags hung freely from their threads. The solution to that problem offered by the disclosure is, however very elaborate and increases costs very considerably. In GB-A-2202819 double-compartment bags have the attaching thread loosely looped around them and adhesive tabs overlie both the tags and the thread to secure them to each other and to the bags. The length of thread must be limited if it is to stay in place. If it is not closely related to the bag length, the loop can slip too easily off the bag as it becomes looser, so there is a risk of entanglement with other bags if each bag is not individually packaged. US-A-2925171 provides examples of infusion bags with freely hanging tags. The thread attaching the tag to its bag may be knotted onto the end of the bag, so also closing the bag but incidentally also restricting the volume of the bag when its contents swell during infusion. Alternatively, the thread must be attached to the bag by a staple or clip. In the case of US-A-2335159 one or more threads are laid between the two web layers that form the compartments of a series of bags and the compartments are separated from each other by seals across the webs in the regions where the threads cross the web. This form of product is difficult to manufacture - for example the threads must be correctly located between the webs before the infusible material can be sealed in place - and may not be particularly convenient since the length of the thread is set by the size of the bag. Another method of producing tagged tea-bags is disclosed in US-A-2556383 in which a thread is drawn onto a periphery of a rotating wheel on which there are a series of spaced tag seats. Tags having pre-punched flaps are then slid sideways into the seats over which the thread already runs, the thread being engaged by the flaps as the tags are inserted. The flaps are next pressed down onto the thread to secure the tags and thread together, and following this the thread between each adjacent pair of tags is drawn into a recess in the wheel to form a loop. The thread between successive tags is next cut as the tags are carried round to the bottom of the wheel. Here the loops of thread depend below the wheel and are attached to respective tea-bags which are conveyed below the wheel in synchronism with its rotation. Such an arrangement provides a continuous production process but has many disadvantages. In particular, the tags cannot be very securely attached to the thread because they rely on the purely mechanical connection offered by the flaps, which must also allow the thread to be drawn through them when the loops are formed. There is also the difficulty of ensuring alignment between the loosely hanging loops and the bags passing beneath the wheel, which makes it impossible to achieve fast and reliable production. It is an object of the invention to provide an alternative method of assembling tags to a thread, and/or assembling the tags to infusion packets with a thread between each tag and its packet. More generally, the invention is applicable to the attachments of tags by a thread (which term may include any filament-like element) to sheet materials of various forms. According to one aspect of the invention, there is provided a method of attaching a thread to tags in which a length of the thread is brought together with a series of spaced tags and the thread between the tags is drawn out to a length greater than the spacing between the tags, said drawn-out lengths of thread being formed into loops to lie against respective Tags and the thread between the loops being attached adhesively to the tags. In an alternative aspect of the invention there is provided a method of attaching tags and thread to a sheet material wherein a web of the sheet material is assembled with a series of tags spaced along its length, said thread being given a length between successive tags greater than the spacing between the tags, the web being brought together with said tags and thread with at least a part of said length of said thread being gathered between the tags and said web of sheet material. Preferably the attachment of each tag to the thread is made only after retaining the thread between tag and web. According to another aspect of the present invention there is provided a tag-thread assembly apparatus having a circulatory working surface comprising a plurality of tag seats arranged to retain successive tags, means for laying a thread onto said surface coincident with the tags, loop formers between successive tag seats for drawing the thread in a loop between each successive pair of seats, means for attaching the thread to the tags after said loop-drawing step, and means for locating the thread loops against the tags. In one embodiment the working surface is provided on the circumference of a wheel, around which are spaced a series of tag seats provided with suction retaining means for the tags. Slots between the tag seats accommodate loop formers which reciprocate into and out of the slots, so as to draw into the slots a thread that extends freely over the tags on the working surface, thereby to form looped lengths of the thread between successive tag seats before the thread is attached to the tags. The apparatus of the present invention may further include means for attaching the tags and looped thread to a web of sheet material. This may be effected by a second circulatory working surface, to which the tags and looped thread are transferred and onto which the sheet web material is introduced to lie against the tags and web, there being means associated with said second surface for attaching the web, tags-and thread together. In the assembly of tags and looped thread with the web of sheet material on the second working surface it is preferably arranged that at least part of the looped lengths of thread are gathered between their respective tags and the web. Preferably the thread extends unbroken between successive tags during these assembly steps. The web will typically be divided subsequently, at intervals along its length, to form separate packets each with a tag, after some further treatment, for example to produce sealed compartments in the web bags, and the thread can be severed simultaneously with the severing of the compartments from the web. The invention will now be described by way of example and with reference to the accompanying drawings, wherein: Fig. 1 is an oblique view of a tea bag carrying a tag and looped thread assembly produced using the present invention; Fig. 2 is a simplified oblique view of a tag and thread assembly apparatus according to one embodiment of the present invention; Figs. 2a and 2b are, respectively, detail views of the application of the web to the tags and thread on the second assembly wheel and the combined web tags and thread leaving said wheel; Fig. 3 is a schematic illustration of the assembly process using the apparatus of Fig. 3; Fig. 4 is a diagrammatic sectional view of the first assembly wheel in the apparatus of Fig. 2; and Fig. 5 is a detail illustration of tag seats on the first assembly wheel. Fig. 1 shows a tea-bag 2 which comprises first and second compartments 4,6, each containing a dose of tea. A tag 8 is attached to the tea-bag and a thread 10, comprising a length gathered in a loop 12 held under the tag, is secured at one end to the tag by a glue spot 14 and at the other to the head or top of the tea bag by a glue spot 16. The tag is held releasably in place on the tea-bag by a pair of tacking heat seals 18 and a third such tacking seal 20 may be made to retain the thread loop in place. The compartments 4,6 have each been produced from a web of sheet material folded lengthwise to form an elongate tube about the tea doses. The material has a fusible component for heat sealing and overlapping edges of the tube are closed together by a butt or lap seal 22. The seals 22 run along the opposed or inner faces of the two compartments of the tea-bag. The head and tail of each compartment are closed by profiled heat seals 24,26 respectively. These profiled seals are complementary to each other, the head seal 24 being convex and the tail seal 26 being concave. The heads of the two compartments are sealed together by the seal 24 which extends right across the width of the tea-bag. The thread 10 is secured at one end to this head seal. The concave heat seals 26 close the tails of the two compartments and form tapered side pieces at the tail of each compartment. The end tips of the side pieces of the two compartments are sealed together by further heat seals 26a juxtaposed on the seals 26 in this region and the joined side pieces are folded inwards so that in side view the tea-bag shows a W-fold 28 at the tail. A continuous process may be operated to form the webs into double-compartment tea bags of this form, using the machine illustrated in our published European patent application A-448325, the contents of which are incorporated herein by reference. As is described in more detail in that earlier application, and as is shown in Fig. 2, a suitably permeable paper web 30 having heat sealing properties, for example a 15.5gsm double-sided heat-sealable filter paper made by Messrs J R Crompton of Bury, Lancashire and known as Single Phase Superseal , is drawn from roll 32 into a buffer reservoir 33. Leaving the reservoir the web 30 is slit lengthwise into two webs 30a,30b as it passes through a pair of scissors rolls 34. The two webs are subsequently formed into respective series of sealed compartments containing doses of tea, and are brought together to give the double-compartment tea bags. Details of this process are given in the earlier application EP-A-448325, but the present application is primarily concerned with the assembling of the tags 8 and thread 10 with the web 30a before the web is dosed with tea and compartmented. As shown in Figs. 2 and 3, a tag strip 40 is drawn from a roll 42 through a reservoir 44 by a tag drive roller 46 to be fed to a tag cutter rotor 48 having a series of radial blades which operate against a counter-rotating pressure roller 50 to sever individual tags 8 from the strip 40. Sensing means 48a detect a pattern repeat printed on the tag strip to ensure the cuts of the cutter rotor are correctly located in relation to the pattern repeat. The pressure roller 50 is provided with suction slots which are not shown but which are arranged and operated similarly to the suction slots in rotating assembly wheel 58 to which the pressure roller transfers the tags. As each tag 8 is severed from the strip 40 it is retained by suction on the roller 50 which carries the tag to the periphery of the assembly wheel 58 which has on its periphery a series of spaced seats 60 for individual tags 8. Suction slots 62 (Fig. 5) open onto the face of each seat to hold the tags in place. The assembly wheel 58 runs faster than the pressure roller 50 so that the tags 8 are spaced from each other as they are delivered to the seats 60 on the wheel periphery. As each tag reaches a seat 60, the suction source switches from its sector on the roller 50 to the slots in that seat so that the tag is transferred from the roller to the assembly wheel seat. At the same time, the thread 10 is drawn from a bobbin 64 onto the periphery of the wheel 58, to lie centrally on top of the tags 8. Between adjacent suction seats 60 the wheel 58 has radial slots 66 to permit the loops 12 to be formed in the thread between the tags. To form the loops, on one side of the assembly wheel 58 an end flange 68 (Fig. 4) carries a series of pivot mountings 70 the axes of which are normal to the wheel axis. A series of arms 72 are supported in the pivot mountings 70 and each arm is aligned with a respective slot 66 to reciprocate about its pivot 70 into the slot so as to draw out the thread into a loop. In Fig. 4 respective arms 72 are illustrated at the opposite end positions of their reciprocating motion. The operating mechanism to generate this motion comprises a fixed cam plate 74 supported on an arbour 76 on which the assembly wheel 58 is rotatably supported through bearings 76a. On one end of each arm 72, a rolling follower 78 is mounted. Each follower 78 has a spherical sector outer surface that runs in a cam groove 80 extending continuously around the face of the cam plate 74. As the assembly wheel 58 rotates, therefore, the followers 78 track around the cam groove to reciprocate the other ends of their arms 72 into and out of the slots 66 in a pattern of movement determined by the fixed cam plate 74. Fig. 4 also illustrates the suction supply to the seats 60 on the assembly wheel. Suction supply pipe 82 is connected to a junction piece 84 mounted in a fixed wall 86 on which the arbour 76 is supported. A manifold plate 88 is sealingly connected to the junction piece and has a suction channel 90 extending in an arc concentric to the assembly wheel. The manifold plate 88 bears on a sliding seal plate 92 carried by the assembly wheel 58, the plate having a series of ports 94 aligned with conduits 96 which extend to the suction slots 62 in the tag seats 60. When the assembly wheel rotates, therefore, the slots 62 are subjected to suction as their respective ports 94 come into communication with the arcuate channel 90. Also shown in Fig. 4 is a similar arrangement, circumferentially spaced from the manifold 88, comprising an inlet 98 for connection to a pressure source (not shown) when it is required to blow through the conduits 96 and slots 62 to expel foreign matter. In the sequence of operation, immediately after being transferred to the assembly wheel 58, each tag 8 passes under an idler roller 102 around which the thread 10 is guided onto the middle of the wheel. Over the sector of the assembly wheel in which the tags and thread are placed onto its periphery, the arms 72 are held in their outermost positions, clear of the slots 66 and the seats 60. When they reach the point at which the thread is laid onto the assembly wheel each arm 72 begins to swing radially inwards to catch the thread in its notched end 72a and draw a loop of thread into the associated slot 66. Central notches 60a at the opposite ends of each tag seat 60 help to keep the thread centred on the assembly wheel. The loops have been fully formed by the time their respective slots 66 approach the periphery of a second assembly wheel 108 which is provided with analogous suction seats (not shown) to those on the first assembly wheel 58. The tags and thread are transferred to the second wheel 108 as the tag seats of the respective wheels come into register with each other, the suction effect then being switched from the tag seat on the wheel 58 to the tag seat on the wheel 108. As a result of the transfer the thread finds itself held between the tags and their seats where it is trapped with the loops formed between the tags hanging loosely. To prevent the thread loops being trapped in the slots 66 during transfer to the second wheel the arms 72 rise from that lowermost position as they approach the second wheel but move out of the slots 66 only after they have passed the contact point with the second wheel. In fact, by keeping the arms in the slots during the approach to the second wheel and after the drawing out of the loops and the approach to the second wheel for a minimum number of slots, eg. 6 slots, it can be ensured that the previously looped thread is held frictionally against return movement as each new loop is formed. While on the second wheel the tags and thread are brought together with the web 30a. As they come towards the web, the loops are constrained to lie approximately centrally on the wheel periphery by suction means, eg. in the formof converging guide plate 112 having perforations (not shown) along its length connected to the suction source. Alternatively it may be arranged that a guide member such as the plate 112 exerts sufficient friction to draw the loops to near their full length. Once the tags, thread and web have been brought together on the wheel 108, welding elements on a tacking roller 114 form the weak heat seals 18,20 between the tags and the web. The seals 18 are made by a pair of small heated elements bearing on the tag on each side of the central thread the elements having a grid-like surface so that high local pressures are applied without creating large forces, and the fusible component of the web material is reliably softened or melted to adhere to the tag. A further heated element on the tacking roller is in the form of a narrow heated bar to make the tack seat 20 between the thread loop to the web. After leaving the second wheel, the assembly is drawn onwards by a further nip drive roller 118 which runs at a slightly higher speed to maintain a slight tension in the web between the second wheel 108 and the drive 118. The tension ensures that the tags can be kept in register as the assembly passes through a shielded section 120 over a pair of hot melt jetting guns 122 which produce the spot seals 14,16 securing the thread to the tag and to the web respectively. It is also possible to use a heat-sealable thread to make the thread-web and/or thread-tag connections. As described previously, although the assembly of the threaded tags to the web is now completed, the thread is left in a continuous length as the web is processed further. The thread is severed only at the final stage when the tea bags have been fully formed, simultaneously with the severing of the bags from each other. For further illustration of that step reference may be made to EP-A-448325 referred to above. Fig. 2 also shows, in broken lines, reserve spools 32a,42a,64a of web, tag and thread materials for ensuring continuity of operation.
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A method of attaching thread to tags in which a length of the thread is brought together with a series of spaced tags and the thread between the tags is drawn out to a length greater than the spacing between the tags, characterised in that said drawn-out lengths of thread are formed into loops to lie against respective tags and that the thread between said loops is attached adhesively to the tags. A method according to claim 1 wherein the thread is laid upon the spaced tags before each portion of thread between successive tags is drawn out to said greater length. A method according to claim 1 or claim 2 wherein, after said drawing out of the thread, a web of sheet material is applied against the tags and thread, and the tags and thread are attached adhesively to said web. A method according to claim 3 wherein the tags and the thread are separately attached to the web. A method according to claim 3 or claim 4 wherein at least a part of each said of thread loop is trapped between a respective tag and said web of sheet material. A method according to any one of the preceding claims wherein the thread is attached to the web initially by a relatively weak adhesive connection and a permanent connection between the thread and web is made while the web is held under tension. A method of attaching a series of tags and thread to a sheet material wherein a web of the sheet material is assembled with a series of tags spaced along its length, and said thread is given a length between successive tags greater than the spacing of said tags, characterised in that the web is brought together with said assembly of tags and thread to locate the series of spaced tags along its length with at least a part of said length of thread between tags gathered between the tags and said web of sheet material. A method according to claim 7 wherein the attachment of the tags to the thread is made after the thread has been placed between the tags and the web. A tag-thread assembly apparatus having a circulatory working surface comprising a plurality of tag seats (60) arranged to retain successive tags (8), loop formers (72) between successive tag seats for drawing a thread (10) in a loop between each successive pair of seats, characterised in that means (102) are provided for laying the thread onto said surface coincident with the tags and that the apparatus further comprises means (122) for attaching the thread to the tags after said loop-drawing step and means for locating the thread loops against the tags. Apparatus according to claim 9 wherein the circulatory working surface is provided on the circumference of a wheel (58) around which are spaced a series of said tag seats (60) provided with suction retaining means (62) for the tags. Apparatus according to claims 9 or 10 further comprising means (108,114,122) for attaching the tags and looped thread to a web of sheet material (30a). Apparatus according to claim 11 wherein said further means comprises a second circulatory working surface (108) to which the tags and the looped thread are transferred from the first said working surface and onto which the web of sheet material is introduced to lie against the tags and thread, there being means (114) associated with said second surface for at least temporarily attaching the assembly of web, tags and thread together. Apparatus according to claim 11 wherein the means (122) for attaching the thread to the tags are arranged to act on each tag and its thread after the action of means (114) for temporarily attaching the assembly of web, tags and thread together.
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UNILEVER NV; UNILEVER PLC; UNILEVER N.V.
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CLEALL ANDREW JOHN; GOODWIN JAMES; VERNON GEOFFREY WILLIAM; CLEALL, ANDREW JOHN; GOODWIN, JAMES; VERNON, GEOFFREY WILLIAM
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EP-0489555-B1
| 489,555 |
EP
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B1
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EN
| 19,980,114 | 1,992 | 20,100,220 |
new
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B01D53
| null |
C01B3, B01D53
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B01D 53/047, C01B 3/56, L01D259:40M12N2, L01D256:20, L01D259:40M18B, L01D257:702A, L01D256:16, L01D259:40M16H, L01D259:40H, L01D259:410, L01D253:108, L01D257:504, L01D259:40M18D, L01D259:404
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Hydrogen and carbon monoxide production by pressure swing adsorption purification
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The present invention is directed to a method for producing hydrogen and carbon monoxide from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane, which comprises the steps of (a) passing the feed mixture through a first pressure swing adsorption system comprising an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen to separate hydrogen as a non-adsorbed product and carbon dioxide, methane, and carbon monoxide as an adsorbed fraction, (b) desorbing carbon monoxide, (c) desorbing carbon dioxide and methane, (d) passing the carbon monoxide to a second pressure swing adsorption system comprising an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane to separate carbon monoxide as an adsorbed fraction and hydrogen, carbon dioxide, and methane as a non-adsorbed fraction, and (e) desorbing carbon monoxide. In a second embodiment, the invention is directed to a method which comprises the steps of (a) providing a pressure swing adsorption system having a first stage comprising an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane, and a second stage comprising an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen, (b) passing the feed mixture through the first stage to separate carbon monoxide as an adsorbed fraction and hydrogen, carbon dioxide, and methane as a non-adsorbed fraction, (c) passing the non-adsorbed fraction through the second stage to separate carbon dioxide and methane as an adsorbed fraction and hydrogen as a non-adsorbed pure product, (d) desorbing carbon dioxide and methane, and (e) desorbing carbon monoxide.
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The present invention is directed to a method of producing merchant grade hydrogen and carbon monoxide from a steam reformed hydrocarbon feed mixture. More particularly, the present invention is directed to a method of producing hydrogen and carbon monoxide from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane.Various methods are known for separating gaseous mixtures produced by the steam reforming of hydrocarbons. Steam reforming to produce hydrogen consists of treating a hydrocarbon feed mixture with steam in a catalytic steam reactor (reformer) which consists of a number of tubes placed in a furnace at a temperature in the range from about 676.7°C (1250°F) to about 926.7°C (1700°F). The reversible reforming reactions which occur when methane is used as the hydrocarbon feed mixture are set out below. CH4 + H2O = CO + 3H2CH4 + 2H2O = CO2 + 4H2CO + H2O = CO2 + H2Carbon monoxide and carbon dioxide are generally removed by shift conversion (reaction of carbon monoxide with steam to form additional hydrogen and carbon dioxide), absorption in amines or other alkaline solvents (carbon dioxide removal), and methanation (conversion of trace carbon monoxide and carbon dioxide to methane). When carbon monoxide is a desired product, the shift conversion and methanation steps are not employed.The hydrogen-rich gas mixture exiting the steam reformer consists of an equilibrium mixture of hydrogen, carbon monoxide, carbon dioxide, water vapor, and unreacted methane. The reforming reactions are endothermic and therefore hydrocarbons and process waste gases are burned in the reformer furnace to provide the endothermic heat. Hydrocarbon steam reforming reactions and hydrogen separation processes are disclosed in more detail in Ammonia and Synthesis Gas: Recent and Energy Saving Processes , Edited by F.J. Brykowski, Chemical Technology Review No. 193, Energy Technology Review No. 68, Published by Noyes Data Corporation, Park Ridge, New Jersey, 1981.Conventional methods for recovering hydrogen and carbon monoxide from a hydrocarbon steam reformed feed mixture have generally focused on cryogenic distillation processes to separate and purify hydrogen and carbon monoxide in the mixture after carbon dioxide is removed. Cryogenic separation processes tend to have a high capital cost especially when more than one pure product is required.Methods for separating hydrogen and carbon monoxide by pressure swing adsorption processes are disclosed in EP-A-0 317 235 which relates to a method for forming hydrogen and carbon monoxide from a feed mixture exiting a hydrocarbon steam reformer comprising hydrogen, carbon monoxide, and carbon dioxide. The method comprises the steps of passing the feed mixture through a sorptive separation to separate a hydrogen product, a carbon monoxide-rich product, and a carbon dioxide-rich product. The carbon monoxide-rich product is further purified in a two stage pressure swing adsorption system. The first stage comprises an activated carbon adsorbent which removes carbon monoxide and methane as the strongly adsorbed waste stream. The second stage comprises a zeolite adsorbent and produces a pure carbon monoxide stream as an adsorbed product.US-A-4,917,711, discloses an adsorbent for carbon monoxide and unsaturated hydrocarbons which comprises a high surface area support, such as a zeolite, alumina, silica gel, aluminosilicate, or aluminophosphate, and cuprous or cupric compound. The adsorbent may be used to separate carbon monoxide and unsaturated hydrocarbons from a gaseous mixture containing hydrogen, nitrogen, argon, helium, methane, ethane, propane, and carbon dioxide by passing the mixture through the adsorbent and releasing the adsorbed carbon monoxide by heating, or lowering the pressure of, the adsorbent.Japanese patent JP01203019 discloses a four column pressure swing adsorption system for separating carbon monoxide from a gaseous mixture. The columns contain an adsorbent containing copper to adsorb carbon monoxide gas. The term adsorption bed refers either to a single bed or a serial arrangement of two beds. The inlet end of a single bed system is the inlet end of the single bed while the inlet end of the two bed system (arranged in series) is the inlet end of the first bed in the system. The outlet end of a single bed system is the outlet end of the single bed and the outlet end of the two bed system (arranged in series) is the outlet end of the second bed in the system. By using two adsorption beds in parallel in a system and by cycling (alternating) between the adsorption beds, product gas can be obtained continuously. An aim of the present invention is to provide an improved method of producing hydrogen and carbon monoxide from a hydrocarbon steam reformed feed mixture employing a novel combination of pressure swing adsorption methods which minimizes capital cost requirements and increases the recovery of carbon monoxide. According to the present invention there is provided a method of producing by pressure swing adsorption hydrogen and carbon monoxide products from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane, characterised by repeating the steps of: (a) providing a pressure swing adsorption system (M) having a first stage and a second stage, wherein the first stage contains an adsorption bed comprising an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane, the second stage contains an adsorption bed comprising an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen, and the first and second stages are connected in series and each stage contains an inlet end and an outlet end;(b) passing the feed mixture through the inlet end of the first stage of the pressure swing adsorption system (M) to separate carbon monoxide as an adsorbed fraction and hydrogen, carbon dioxide, and methane as a non-adsorbed fraction;(c) passing the non-adsorbed fraction from step (b) through the second stage of the pressure swing adsorption system (M) to separate carbon dioxide and methane as an adsorbed fraction and hydrogen as a non-adsorbed substantially pure product;(d) stopping the flow of feed mixture into the inlet end of the first stage;(e) desorbing carbon dioxide and methane from a location intermediate the first and second stages of the pressure swing adsorption system (M) to form a carbon dioxide-rich fraction;(f) desorbing the carbon dioxide and methane by purging the second stage with hydrogen gas in a countercurrent direction and purging the first stage with carbon monoxide gas in a cocurrent direction and withdrawing the purge effluent gases from a location intermediate the first and second stages of the pressure swing adsorption system (M); and (g) desorbing carbon monoxide from the first stage of the pressure swing adsorption system (M) to form a substantially pure carbon monoxide product.Embodiments of the invention will now be described, by way of example, reference being made to the Figures of the accompanying diagrammatic drawings in which:- FIGURE 1 is a schematic process flow diagram illustrating a novel two stage pressure swing adsorption system according to the present invention to separate hydrogen and carbon monoxide from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane; andFIGURE 2 is a schematic process flow diagram illustrating a first stage of a pressure swing adsorption system for separating carbon monoxide as an adsorbed product and a second stage of a pressure swing adsorption system for separating carbon dioxide as an adsorbed fraction and hydrogen as a non-adsorbed product, according to the present invention.In the embodiment illustrated in the drawings, a novel two stage pressure swing adsorption system is utilized which efficiently and economically yields enriched hydrogen and carbon monoxide. The first stage of the pressure swing adsorption system separates carbon monoxide as an adsorbed fraction and hydrogen, carbon dioxide, and methane as a non-adsorbed fraction. The second stage of the pressure swing adsorption system separates carbon dioxide and methane as an adsorbed fraction and hydrogen as a non-adsorbed pure product.The novel combination of pressure swing adsorption separation methods of the present invention provides significant savings in capital and operating expense over completely cryogenic methods. The steps in the present method may be integrated into steps in the hydrocarbon steam reformer method to enhance the reforming process. For example, the carbon dioxide-rich fraction from the second stage in the second embodiment may be recycled and used as fuel in the hydrocarbon steam reformer, further increasing the concentration of carbon monoxide in the feed mixture. The feed mixture (exhaust gas, effluent gas, exit gas, feed gas) in the present invention is a mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane. Preferably, the feed mixture is an effluent gas from a hydrocarbon steam reformer. The feed mixture will in general comprise hydrogen in an amount up to about 80%, carbon monoxide in an amount up to about 20%, carbon dioxide in an amount up to about 30%, and methane in an amount up to about 3%.The feed mixture is typically available in a saturated state and may be dried by passing the mixture through a condenser (drier) containing a desiccant such as alumina, silica, or zeolite. Desorption of the water from the desiccant may be accomplished by purging the desiccant with a dry waste purge gas (such as the carbon dioxide-rich fraction or nitrogen gas). Any water remaining in the feed mixture is removed with the strongly adsorbed stream (carbon dioxide-rich fraction). After being dried, the feed mixture may be compressed prior to passage of the mixture into the pressure swing adsorption system.The feed mixture from the hydrocarbon steam reformer will first be passed through a process cooler to cool the gas and condense and remove water vapor. To maximize the carbon monoxide concentration and minimize the carbon dioxide concentration in the feed mixture, the hydrocarbon steam reformed feed mixture will by-pass the shift converter.The adsorbent material in the adsorbent bed in the second stage is an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen. The adsorbent material may be a molecular sieve or activated carbon, and preferably is a combination of molecular sieves and activated carbon. Both calcium and sodium aluminosilicate zeolites may be employed. Carbon molecular sieves and silica molecular sieves are also useful. Suitable zeolite sieves include, but are not limited to, the type 5A, 10X, 13X zeolite molecular sieves, and mordenites. Preferred zeolite sieves are the type 5A zeolite sieves and molecular sieves with comparable pore size and molecular attraction.The adsorbent material in the adsorbent bed in the first stage is an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane. In general, suitable adsorbent materials are copper exchanged substrates such as those selected from the group consisting of copper exchanged Y-type aluminosilicate zeolite molecular sieves, copper exchanged alumina, and copper exchanged activated carbon, and mixtures thereof. In a preferred embodiment, the adsorbent material is copper aluminosilicate zeolite molecular sieve material, available under the tradename NKK type adsorbent in a package from Nippon Kokan K. K., Tokyo, Japan. Copper aluminosilicate zeolite molecular sieves can be prepared by exchanging sodium in sodium aluminosilicate zeolite molecular sieves with copper (2+) followed by a heating and reducing treatment to enhance the affinity of the adsorbent for carbon monoxide and reduce the affinity of the adsorbent for carbon dioxide. see, for example, US-A-4,917,711, US-A-4,914,076, US-A-4,783,433,, and US-A-4,743,276. In accord with the present invention, a hydrogen gas product can be prepared having a purity of greater than about 99%, preferably greater than about 99.99%, and more preferably greater than about 99.999%. A carbon monoxide gas product can be prepared having a purity of greater than about 98%, preferably greater than about 99%, and more preferably greater than about 99.85%. Referring to FIGURE 1, gaseous feed mixture is fed through feed conduit 70 to two stage pressure swing adsorption system M to separate the mixture. Typically the feed mixture from the hydrocarbon steam reformer will enter two stage pressure swing adsorption system M at a pressure in the range from about 1.034 MPa (150 psia) to about 4.136 MPa (600 psia), preferably from about 1.034 MPa (150 psia) to about 2.758 MPa (400 psia), and more preferably from about 1.034 Mpa (150 psia) to about 2.068 MPa (300 psia). After being cooled, the feed mixture entering pressure swing adsorption system M will be at ambient temperature.During the hydrogen product production step, feed mixture is fed into and hydrogen product is withdrawn from two stage pressure swing adsorption system M. Hydrogen product is separated as a pure non-adsorbed product and carbon monoxide, carbon dioxide, methane, and water vapor is separated as an adsorbed fraction. Hydrogen product (merchant grade, less than about 10 vpm impurities) is withdrawn from two stage pressure swing adsorption system M through feed conduit 71 and passed to hydrogen reservoir B. After the hydrogen product production step, pressure swing adsorption system M undergoes a pressure equalization step, an intermediate depressurization step, and a second stage purge/first stage purge step (carbon dioxide-rich fraction production steps). During the intermediate depressurization step, carbon dioxide-rich gas is collected as secondary product, compressed, and recycled to the reformer feed gas. During the second stage purge/first stage purge step, the second stage is purged with hydrogen from another stage and the first stage is purged with carbon monoxide product gas from the reservoir Q. The depressurization and purge effluent gases are passed to carbon dioxide reservoir N and collected as secondary product via feed conduit 72. The gases are then passed to compressor 0 via feed conduit 73 and compressed and recycled to the reformer feed gas via feed conduit 74. In general, carbon dioxide compressor 0 will compress the carbon dioxide-rich fraction to a pressure in the range from about 1.034 MPa (150 psia) to about 4.136 MPa (600 psia), preferably from about 1.034 MPa (150 psia) to about 3.102 MPa (450 psia), and more preferably from about 1.034 MPa (150 psia) to about 2.413 MPa (350 psia). After the carbon dioxide-rich fraction production steps, pressure swing adsorption system M undergoes a second stage purge/first stage evacuation step (carbon monoxide production step). In the second stage purge/first stage evacuation step, the second stage is purged with hydrogen gas and the first stage is evacuated using vacuum pump P to remove carbon monoxide product gas. The carbon monoxide product gas is withdrawn through feed conduits 77 and 78 and passed to carbon monoxide reservoir Q.After the carbon monoxide production step, pressure swing adsorption system M undergoes a pressure equalization step (repressurization). During the pressure equalization step, the bed is repressurized by pressure equalization with another bed. The bed is then repressurized to adsorption pressure using hydrogen gas from the pressure swing adsorption system. The carbon monoxide product (merchant grade, less than about 1500 vpm impurities) is passed through feed conduits 77, 78, and 75 to carbon monoxide reservoir Q. FIGURE 2 illustrates a two stage pressure swing adsorption method for separating carbon monoxide and hydrogen from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane in accord with the second embodiment of the present invention. As set out in FIGURE 4, the feed mixture from the hydrocarbon steam reformer is passed through feed conduit 70 to pressure swing adsorption system M.In FIGURE 2, the two stage pressure swing adsorption system M comprises adsorption beds A1'', A2''; B1'', B2''; C1'', C2''; and D1'', D2'', carbon monoxide storage vessel Q, carbon dioxide-rich gas buffer vessel N, hydrogen product reservoir B, hydrogen product pressure control valve PCV1, carbon monoxide-rich product gas pressure control valve PCV2, carbon dioxide product pressure control valve PCV3, repressurization flow control valve FCV1, hydrogen product purge gas flow control valve FCV2, stop valves 221 to 248 and 251 to 259, and non-return valves 249 and 250.Adsorption beds A'' through D'' are connected in parallel. Each of the adsorption beds, A'' through D'', is physically divided into two stages, a first (bottom) stage and a second (top) stage, A1''/A2'', B1''/B2'', C1''/C2'', and D1''/D2'', respectively, which are connected in series. Each stage contains an inlet (feed) end and a outlet (discharge) end. The first stage and second stage of each bed are isolated by two stop valves for sequential depressurization and carbon monoxide production steps (i.e., first stage A1'' and second stage A2'' are isolated by stop valves 252 and 256). The two part stages facilitate removal of a carbon dioxide stream from an intermediate position in the bed. The carbon dioxide stream is drawn at an intermediate pressure, for example at about 0.172 Mpa (25 psia), and passed to carbon dioxide storage vessel N. The first adsorption bed stage (for example, first stage A1'') comprises an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane and may be selected from the group consisting of copper exchanged Y-type aluminosilicate zeolite molecular sieves, copper exchanged alumina, and copper exchanged activated carbon. The second adsorption bed stage (for example, second stage A2'') comprises an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen and may be a molecular sieve or activated carbon, and preferably is a combination of molecular sieves and activated carbon. The two stage pressure swing adsorption system is operated in accordance with the full cycle sequence shown in Table 1. The sequence is described below in detail using stages A1''/A2''. Stages B1''/B2'', C1''/C2'', and D1''/D2'' are employed in the same sequence but at an offset as shown in Table 1. All stop valves may be controlled automatically on a predetermined schedule. Four Bed Two Stage Pressure Swing Adsorption Cycle Sequence Step NoBed A''Bed B''Bed C''Bed D''Valves Open1Feed gas Product gasEq.Press. (repress.)Top Purge Bottom PurgeEq.Press. (depress.)221,237,252,256, 242,248,253,257, 255,259,251,244, 258,254,235,2282Feed gas Product gasRepressurize H2 Product gasTop Purge CO ProductionTop/Bottom Depressurize221,237,252,256, 242,257,253,251, 244,258,235,229, 259,255,2363Eq.Press. (depress.)Feed gas Product gasEq.Press. (repress.)Top Purge Bottom Purge224,240,253,257, 239,245, 252,256, 258,254,251,247, 259,236,231,2554Top/Bottom DepressurizeFeed gas Product gasRepressurize H2 Product gasTop Purge CO Production224,240,253,257, 256,252,233,245, 258,254,251,247, 259,236,2325Top Purge Bottom PurgeEq.Press. (depress.)Feed gas Product gasEq.Press. (repress.)227,243,254,258, 251,238, 256,233, 222,252,242,248, 253,257,259,2556Top Purge CO ProductionTop/Bottom DepressurizeFeed gas Product gasRepressurize H2 Product gas227,243,254,258, 251,238,256,233, 223,257,253,234, 248,259,2557Eq.Press. (repress.)Top Purge Bottom PurgeEq.Press. (depress.)Feed gas Product gas230,246,255,259, 239,245, 252,256, 251,241,258,254, 257,234,225,2538Repressurize H2 Product gasTop Purge CO ProductionTop/Bottom DepressurizeFeed gas Product gas230,246,255,259, 239,256,252,251, 241,257,234,226, 258,254,235Feed gas/Product gas Feed gas admitted to bottom of bed. Product gas released from top of bed. Eq.Press. (depress.) Bed pressure equalized to another bed at lower pressure through top ends of beds. Top/Bottom Depressurize Top and bottom beds depressurized from intermediate location. Depressurized gas recycled to reformer feed gas. Top Purge/Bottom Purge Top bed purged with hydrogen. Bottom bed purged with carbon monoxide. Purge effluent removed from intermediate location. Top Purge/CO Production Top bed purged with hydrogen. Bottom bed evacuated to remove carbon monoxide product gas. Eq.Press. (repress.) Bed pressure equalized with another bed at higher pressure through top ends of beds. Repressurize H2 Product gas Repressurization of bed to adsorption pressure using hydrogen product gas from pressure swing adsorption system.At the start of the pressure swing adsorption cycle, first stage A1'' and second stage A2'' are in the hydrogen production step. Feed mixture from the hydrocarbon steam reformer is passed to the inlet end of first stage A1'' via open stop valve 221 at a pressure typically in the range from about 1.034 MPa (150 psia) to about 4.136 MPa (600 psia). The feed mixture passes from the outlet end of the first stage A1'' through stop valves 252 and 256 to the inlet end of the second stage A2''. The feed mixture is adsorbed in first stage A1'' and second stage A2'' to selectively sieve hydrogen as an non-adsorbed fraction and carbon dioxide, carbon monoxide, and methane as adsorbed products. Non-adsorbed hydrogen product gas is withdrawn from the outlet end of second stage A2'' via open stop valve 237 and passed to hydrogen product reservoir B via non-return valve 249 and hydrogen product pressure control valve PCV1. The hydrogen product gas typically contains less than about 10 vpm impurities.During the hydrogen production step, the copper exchanged substrate in first stage A1'' preferentially adsorbs carbon monoxide. The activated carbon/molecular sieve adsorbent material in second stage A2'' preferentially adsorbs carbon dioxide, water vapor, and methane more strongly than hydrogen. As the feed mixture flows through the adsorbent stages, carbon monoxide becomes concentrated in first stage A1'', carbon dioxide, water vapor, and methane become concentrated in second stage A2'', and the mixture exiting the bed stages becomes enriched in hydrogen. The zeolite molecular sieve adsorbent removes all but traces of other gases and yields a hydrogen product substantially free of impurities. The flow of feed mixture into the inlet end of the first stage and flow of product gas from the outlet end of the second stage are stopped just before the breakthrough point of non-hydrogen components from the outlet end of the second stage. A typical feed and production cycle is conducted for a period of about two to about six minutes.When the non-hydrogen components (i.e., methane) in the feed mixture advance close to the outlet end of second stage A2'', the hydrogen production step in first stage A1''/A2'' is stopped. Stop valves 221 and 237 are closed stopping the production of hydrogen. First stage A1'' and second stage A2'' are then depressurized (treated as one bed with stop valves 252 and 256 open) and stage C1''/C2'' is repressurized (treated as one bed with stop valves 254 and 258 open) by pressure equalization of the beds through the outlet (top, discharge) ends of the beds. Stop valves 239 and 245 are opened and void gas is passed from the outlet end (top) of second stage A2'' to the outlet end (top) of bed C2'' to substantially equalize the pressures in beds A1''/A2'' and beds C1''/C2''. This pressure equalization step typically is conducted for a period of about twenty to about forty seconds.During the pressure equalization step, void gas containing carbon dioxide and methane is passed to the repressurized bed and the pressure in first stage A1''/A2'' decreases. Optionally, first stage A1''/A2'' may be pressure equalized with an equalization tank through the outlet end of second stage A2''. The gas collected in the equalization tank is subsequently used to repressurize a bed in the pressure swing adsorption system.Ater the pressure equalization step is complete, first stage A1''/A2'' begins the intermediate depressurization step (a first carbon dioxide-rich fraction production step). During the intermediate depressurization step, first stage A1'' and second stage A2'' are depressurized from an intermediate location to withdraw and produce a carbon dioxide-rich fraction. Stop valves 239 and 245 are closed and stop valves 233, 252, and 256 are opened to withdraw the carbon dioxide-rich fraction from a position intermediate between first stage A1'' and second stage A2''. The carbon dioxide-rich fraction is drawn at an intermediate pressure, for example at about 0.172 MPa (25 psia), and passed to carbon dioxide storage vessel N. The carbon dioxide-rich fraction from carbon dioxide storage vessel N is then passed to the reformer feed gas via compressor 0.During the intermediate depressurization step, void gas in second stage A2'' which is predominantly carbon dioxide, is withdrawn from the inlet (bottom) end of the bed. Withdrawal of carbon dioxide-rich void gas from the outlet (top) end of first stage A1'' causes the carbon monoxide, adsorbed near the bottom of the bed, to be desorbed displacing additional void gas. Withdrawal of carbon dioxide from a location intermediate between first stage A1'' and second stage A2'' minimizes retention of carbon dioxide in the top region of second stage A2'' which could contaminate a subsequent carbon monoxide production step. The time for the intermediate depressurization step is typically about two minutes.When the intermediate depressurization carbon monoxide production step is complete, first stage A1''/A2'' undergoes a second stage purge/first stage purge step (a second carbon dioxide-rich fraction production step). During the second stage purge/first stage purge step, second stage A2''is purged with hydrogen gas and first stage A1'' is purged with carbon monoxide product gas from carbon monoxide reservoir Q. During the purge of second stage A2'' with hydrogen gas, stop valves 251, 238, and 233 are opened. Hydrogen from hydrogen reservoir B is then passed through open flow control valve FCV2, open non-return valve 250, and open stop valves 251 and 238, through second stage A2'', and open stop valves 256 and 233 to carbon dioxide reservoir N. During the purge of first stage A1'' with carbon monoxide gas, stop valves 222, 252, 233 are opened. Carbon monoxide from carbon monoxide reservoir Q is then passed through open flow control valve FCV3, open stop valve 222, through first stage A1'', and open stop valves 252 and 233 to carbon dioxide reservoir N. The flow of hydrogen through second stage A2'' is in a direction countercurrent and the flow of carbon monoxide is in a direction cocurrent to the flow of the feed mixture during the hydrogen production step. Generally, the purge steps are carried out simultaneously and are conducted for a period of one to two minutes. The resulting carbon dioxide-rich fraction generally contains at least about 50% by volume carbon dioxide and less than 10% by volume carbon monoxide, and small amounts of methane, with the balance being hydrogen.When the second stage purge/first stage purge step is complete, stages A1'' and A2'' undergo a second stage purge/first stage evacuation step (carbon monoxide production step). During the second stage purge/first stage evacuation step, second stage A2''is purged with hydrogen gas and first stage A1'' is evacuated using vacuum pump R to withdraw carbon monoxide product gas from the inlet end of first stage A1'' for passage to carbon monoxide reservoir Q. During the production of carbon monoxide, stop valves 252 and 222 are closed. Carbon monoxide is then passed from first stage A1'' through open stop valve 223 to carbon monoxide reservoir Q. Generally, the purge and production steps are carried out simultaneously and are conducted for a period of one to two minutes.The resulting carbon monoxide-rich fraction, which is produced at a pressure at about 0.17 MPa (about 25 psi), generally contains carbon monoxide having a purity exceeding 98%.After the carbon monoxide production step is complete, first stage A1'' and second stage A2'' is repressurized and bed C1''/C2'' is depressurized by pressure equalization of the beds. Stop valves 223, 233, and 251 are closed and stop valve 252 is opened. Void gas is passed from the outlet end of second stage C2'' to the outlet end of second stage A2'' to substantially equalize the pressure of bed A1''/A2'' and bed C1''/C2''.After the pressure equalization step (repressurization step) is complete, first stage A1'' and second stage A2'' are backfilled with hydrogen product gas. Stop valves 238 and 244 are closed and bed A1''/A2'' is repressurized by backfill with product gas. Product gas from producing bed D1''/D2'' is passed through open repressurization flow control valve FCV1 and into the outlet end of second stage A2'' to backfill bed A1''/A2'' through open stop valve 239.When the backfill step is complete, first stage A1'' and second stage A2'' are ready to again begin the hydrogen production step. Repressurization flow control valve FCV1 and stop valve 239 are closed and stop valves 221 and 237 are opened to admit feed mixture to the inlet end of first stage A1''. The hydrogen production step in bed A1''/A2'' is begun and the cycle is repeated. Beds A1''/A2'', B1''/B2'', C1''/C2'', and D1''/D2'' operate in the sequence set out in Table 3. In general, the time to complete a cycle (cycle time) is in the range from about 60 seconds to about 1500 seconds, preferably from about 180 seconds to about 960 seconds, and more preferably from about 240 seconds to about 720 seconds. The selectivity of the adsorbent material in the bed of the pressure swing adsorption system for a gaseous component is generally governed by the volume of the pore size and the distribution of that pore size in the adsorbent. Gaseous molecules with a kinetic diameter less than, or equal to, the pore size of the adsorbent are adsorbed and retained in the adsorbent while gaseous molecules with a diameter larger than the pore size of the adsorbent pass through the adsorbent. The adsorbent thus sieves the gaseous molecules according to their molecular size, The adsorbent may also separate molecules according to their different rates of diffusion in the pores of the adsorbent.Zeolite molecular adsorbents adsorb gaseous molecules with some dependence upon crystalline size. In general, adsorption into zeolite is fast and equilibrium is reached typically in a few seconds. The sieving action of zeolite is generally dependent upon the difference in the equilibrium adsorption of the different components of the gaseous mixture. When air is separated by a zeolite adsorbent, nitrogen is preferentially adsorbed over oxygen and the pressure swing adsorption method may be employed to produce an oxygen enriched product. When hydrogen, carbon monoxide, carbon dioxide, and methane are separated by a zeolite adsorbent, carbon dioxide, carbon monoxide, and methane are the adsorbed components, in the order indicated, and hydrogen is the unadsorbed component.During the carbon monoxide pressure swing adsorption separation, carbon dioxide, hydrogen, and methane are removed from the feed mixture as vent gas during the pressure equalization step. A certain amount of carbon monoxide is lost with the vent gas. This loss of carbon monoxide results from carbon monoxide not adsorbed in the sieves at the pressure swing adsorption operation pressure, and carbon monoxide present in the bed voids and discharged during the pressure equalization step. This vent gas containing carbon monoxide is recycled to the pressure swing adsorption system as feed gas during the carbon monoxide cocurrent purge step.
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A method of producing by pressure swing adsorption hydrogen and carbon monoxide products from a feed mixture comprising hydrogen, carbon monoxide, carbon dioxide, and methane, characterised by repeating the steps of: (a) providing a pressure swing adsorption system (M) having a first stage and a second stage, wherein the first stage contains an adsorption bed comprising an adsorbent having a greater affinity for carbon monoxide than for hydrogen, carbon dioxide, and methane, the second stage contains an adsorption bed comprising an adsorbent having a greater affinity for carbon dioxide, methane, and carbon monoxide than for hydrogen, and the first and second stages are connected in series and each stage contains an inlet end and an outlet end;(b) passing the feed mixture through the inlet end of the first stage of the pressure swing adsorption system (M) to separate carbon monoxide as an adsorbed fraction and hydrogen, carbon dioxide, and methane as a non-adsorbed fraction;(c) passing the non-adsorbed fraction from step (b) through the second stage of the pressure swing adsorption system (M) to separate carbon dioxide and methane as an adsorbed fraction and hydrogen as a non-adsorbed substantially pure product;(d) stopping the flow of feed mixture into the inlet end of the first stage ;(e) desorbing carbon dioxide and methane from a location intermediate the first and second stages of the pressure swing adsorption system (M) to form a carbon dioxide-rich fraction;(f) desorbing the carbon dioxide and methane by purging the second stage with hydrogen gas in a countercurrent direction and purging the first stage with carbon monoxide gas in a cocurrent direction and withdrawing the purge effluent gases from a location intermediate the first and second stages of the pressure swing adsorption system (M); and (g) desorbing carbon monoxide from the first stage of the pressure swing adsorption system (M) to form a substantially pure carbon monoxide product.The method according to claim 1, characterised in that the adsorbent in the adsorption bed in the first stage (A1'') of the pressure swing adsorption system (M) in step (b) is selected from the group consisting of copper exchanged Y-type aluminosilicate zeolite molecular sieves, copper supported on alumina, and copper supported on activated carbon, and mixtures thereof.The method according to claim 1, characterised in that the adsorbent is copper exchanged Y-type aluminosilicate zeolite molecular sieves.The method according any one of to claims 1 to 3, characterised in that the adsorbent in the adsorption bed in the second stage (A2'') of the pressure swing adsorption system in step (c) comprises activated carbon and zeolite molecular sieves.The method according to claim 4, characterised in that the zeolite molecular sieves are an aluminosilicate zeolite selected from the group consisting of type 5A, 10X, 13X zeolite molecular sieves, and mordenites.
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BOC GROUP INC; THE BOC GROUP, INC.
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KRISHNAMURTHY RAMACHANDRAN; KRISHNAMURTHY, RAMACHANDRAN
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EP-0489556-B1
| 489,556 |
EP
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B1
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EN
| 19,950,802 | 1,992 | 20,100,220 |
new
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G06F12
| null |
G06F15, G06F13, G06F12
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G06F 12/08B4P4B
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Consistency protocols for shared memory multiprocessors
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A shared memory multiprocessor having a packet switched bus, together with write back caches for connecting individual processors to that bus, employs a consitency protocol that permits the caches to store multiple copies of read/write data at identical physical addresses for use as neded by the respective processors. The protocol causes the hardware to automatically and transparently maintain the consistency of this data. To that end, the caches detect when a datum becomes shared by monitoring the traffic on the bus, thereby enabling them to broadcast an updating write on the bus whenever their respective processors issue a write to a shared address. If desired, this protocol may be extended to include an advisory invalidate for reducing the amount of address sharing that occurs, thereby enhancing the efficiency of the protocol. The protocol maintains a consistent view of memory for the processors, while permitting I/O devices to have direct access to the memory system.
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This invention relates to shared memory multiprocessors that have packet switched memory busses. A key goal in designing computer memory busses is to maximize their usable bandwidth. A short bus cycle time is required to achieve this, but that alone does not ensure that the usable bandwidth of the bus will be comparable to its electrical bandwidth because the bus must also have a high efficiency (conventionally defined as the ratio of the usable bus bandwidth to its electrical bandwidth) to achieve that goal. Indeed, a short bus cycle time is of relatively little value for increasing the usable bandwidth of a conventional circuit switched bus because the circuit switching of the bus serializes the request/reply pairs for successive transactions on a transaction-by-transaction basis. As is known, a cache memory system can be employed for reducing the number and frequency of the main memory transactions a computer system is required to perform, but in high performance systems the traffic on the memory bus usually still is a dominant performance limiting factor. Unfortunately, the access time of economically practical main memory typically is several times longer than the minimum realizable bus cycle time, so the usable bandwidth of a circuit switched bus tends to be limited by the main memory access time. In systems having cache memory, the wasted wait cycles of a circuit switched bus (i. e., its wasted bandwidth) may be reduced by increasing the size of the main memory/cache memory data transport unit, thereby amortizing the bus wait cycles over larger blocks of data. However, this approach tends to increase the bandwidth load that is placed on the bus by the processor or processors, which at least partially negates the benefit of the larger data transfer unit. Others have recognized that the bandwidth penalty caused by idle bus cycles can be avoided by employing a packet switched bus (sometimes also referred to as a split cycle bus, or a pending bus). Packet switching of the bus dissociates the requests and the replies of bus transactions from each other, thereby permitting requests and replies for multiple transactions to be interleaved on the bus. As a general rule, idle bus cycles can be avoided simply by dissociating the requests and replies of the transactions in which main memory participates (i.e., the main memory transactions ). However, it has been found that it is advantageous to dissociate the requests and replies of all bus transactions, so that a variable number of bus cycles (in excess of the implementionally dependent minimum number of cycles) may intervene between any request and its corresponding reply, subject only to the possible expiration or abortion of a request to which no reply is received within a predetermined timeout period. This essentially complete dissociation of all requests and replies helps eliminate bus deadlocks, while making it easier to interface the bus with non-synchronized devices, such as with the memory busses of dissimilar or foreign computer systems, including industrial standard systems. Furthermore, it facilitates the use of interleaved main memory modules, and simplifies the solution to the cache consistency problem for multiprocessors having multilevel, hierarchical cache memory systems. Usable bus bandwidth and cache consistency are related but separable issues. As will be appreciated, cache consistency is a more detailed consideration because it is a specific requirement for busses which provide access to multiple cached copies of shared data while permitting different ones of the cached data copies to be updated under the control of different processors, such as in multiprocessors. There are several known solutions to the cache consistency problem for circuit switched busses. However, the known techniques for maintaining cache consistency are not directly applicable to packet switched busses See, Andrew W. Wilson, Jr., Hierarchical Cache/Bus Architecture for Shared Memory Multiprocessors, Computer Architecture Conference (IEEE/ACM), 1987, pp 244-252. US-A-4843542 discloses a method for maintaining the cache consistency in a multiprocessing system, said method employing a bus protocol which uses flags associated with the data in the caches for indicating the status of the data (shared, owned). In accordance with the present invention, a shared memory multiprocessor having a packet switched bus, together with write back caches for connecting individual processors to that bus, employs a consitency protocol that permits the caches to store multiple copies of read/write data at identical physical addresses for use as neded by the respective processors. The protocol causes the hardware to automatically and transparently maintain the consistency of this data. To that end, the caches detect when a datum becomes shared by monitoring the traffic on the bus, thereby enabling them to broadcast an updating write on the bus whenever their respective processors issue a write to a shared address. If desired, this protocol may be extended to include an advisory invalidate for reducing the amount of address sharing that occurs, thereby enhancing the efficiency of the protocol. The protocol maintains a consistent view of memory for the processors, while permitting I/O devices to have direct access to the memory system. More specifically, the present invention provides a method for a shared memory multiprocessor comprising a main memory for storing a complete, non-overlapping data cover for all of said physical addresses; a packet switched bus coupled to said main memory; a plurality of data processing means for manipulating data at respective, potentially overlapping sets of said addresses; and a corresponding plurality of cache memories coupled between said bus and respective ones of said data processing means for giving the respective data processing means read and write access to cached versions of the data stored at a respective sets of said addresses: said cache memories being snoopy, write back cache memories for initiating, responding to, and participating in transactions on said bus for reading copies of the data at selected addresses into any given one of said cache memories in reply to a read request made by said given cache memory, and for broadcasting data updates for any selected address from any given one of said cache memories to all of the other of said cache memories in reply to a write request that is made by the given cache memory whenever it is determined that such an update is directed to an address that is shared by a plurality of said cache memories: each of said transactions including a request packet that is issued by the cache memory requesting the transaction and a time dissociated reply packet that is issued by a responder; said request and reply packets uniquely identifying the cache memory requesting the transaction, the requested transaction type, and the address to which the transaction is directed; the reply packet for each read transaction further including a copy of the data at the address to which the read transaction is directed in a data transport unit containing a predetermined number of contiguous addresses that are read into and cached by the cache requesting the transaction as a data block; and the reply packet for each write transaction further including the data update for the address to which the write transaction is directed, such that said update is written into all cached copies of said address in response to the reply packet: wherein data consistency for all physical addresses used by the multiprocessor is preserved by: maintaining, for each of said cache memories, a shared state and an owner state for each data block cached therein; maintaining, for each of said cache memories, a pending state for each data block cached therein that is subject to a pending transaction of the respective cache memory; monitoring all bus transactions for setting the shared state for any given data block within any given one of said cache memories to a true state whenever it is determined that the given data block is shared by at least one other of said cache memories; setting a reply shared flag in the reply packet for said read or write request to a true state if the request packet is addressed to shared data; checking the shared status within any given cache memory that receives a write from its respective data processing means to determine whether said write is directed to a shared data block and, if so, causing said given cache memory to issue a corresponding write request on said bus for broadcasting said write to all other caches containing said data block; setting the owner state for a given data block to a true state within a given cache memory whenever its respective data processing means is responsible for providing a latest update for said given data block; transferring data block ownership of shared data blocks from cache memory to cache memory upon receiving the reply packets for the write transactions by which said data blocks are updated, whereby the owner state for a given data block is set to a true state in, at most, one of said caches at any given time; checking, on each request, to determine whether any of said cache memories assert ownership of the address to which said read request is directed; reading the data for the reply packet for such a read request from a cache memory owner of the data block containing the address to which the read request is directed or from said main memory, depending on whether ownership is asserted or not, respectively, in response to said read request; updating the pending state for each pending read and write transaction of said cache memories to reflect any changes in the shared status of the address to which said transaction is directed that occur while the transaction is pending; and logically ORing the pending state for each pending read transaction of each cache memory with the reply shared flag in the reply packet for such transaction, so that the shared state for the data block that is loaded into said cache memory in response to said reply packet is set to a true sate if said data block becomes shared at any time prior to the receipt of said reply packet. By way of example only, embodiments of this invention will be described with reference to the attached drawings, in which: Fig. 1 is a simplified block diagram of a shared memory multiprocessor having a hierarchical cache memory system; Fig. 2 is a simplified schematic diagram of the internal logic of a standard bus/client interface for the multiprocesor shown in Fig. 1; Fig . 3A is a schematic diagram of a pipelined memory bus for a monoboard computer; Fig . 3B is a schematic diagram of a pipelined memory bus for a multiboard computer; Fig. 3C is a schematic diagram of a pipelined memory bus for a multiboard, multimodule computer; Fig. 4 is a functional diagram for identifying the various signal ports of the bus/client interface that is shown in Fig. 2; Fig. 5 is a functional block diagram of an arbiter for arbitrating a memory bus of the foregoing type in time overlapping relationship with the transmission of packets on the bus; Fig. 6 is a timing diagram that illustrates the time overlap between the arbitration of the pipelined bus shown in Fig. 3B and the transmission of packets thereon; Fig. 7 is a bit-level diagram of the header cycle of a request packet for a bus transaction in a format selected for an initial embodiment of this invention; Fig. 8 is a bit-level diagram of the header cycle of a correspondingly formatted reply packet; Fig. 9 illustrates the cyclical reordering of a data block transport unit on a bus for causing the addressed quantum of the data block to be contained within the first data cycle of the transport unit; Fig. 10 is a simplified schematic diagram of a single level shared memory multiprocessor that is useful for illustrating the basic principles of the data consistency protocol that has been provided for the initial embodiment of this invention; Fig. 11 is a bit-level diagram of the header cycle format for the request packets of the bus transactions that are performed by an enhanced embodiment of this invention; Fig. 12 is a bit-level diagram of the header cycle format for the reply packets of the bus transactions that are carried out by the enhanced embodiment of this invention; Fig. 13 is a functional diagram for identifying the various signal ports of the standard device-bus interface for the enhanced embodiment of this invention; Fig. 14 is a simplified schematic diagram of the internal logic of the device-bus interface shown in Fig. 13: Fig. 15 is a timing diagram for illustrating the relative timing of certain of the signals that the enhanced embodiment of the invention relies upon for the arbitration and transmission two cycle long request and reply packets. There are several important features of the memory systems that are disclosed herein, so the disclosure is organized as follows to assist in locating material relating to the different features: I. An Initial Embodiment A. System Architecture 1. Bus and Memory Hierarchy a. Multilevel Bus System B. Bus Logical Terminology C. Bus physical Terminology D. Device-Bus Interface 1. Signals 2. Arbitration Interface 3. Data/Control Interface 4. Consistency Port E. Transactions 1. Memory Related Transactions 2. I/O Transactions 3. Miscellaneous Transactions F. Data Consistency 1. Data Consistency in Single Level Systems 2. Data Consistency in Multilevel Systems II. An Enhanced Embodiment A. System Architecture B. Device-Bus Interface 1. Signals 2. Arbitration Interface 3. Data/Control Interface 4. Consistency port C. Transactions 1. Memory Related Transactions 2. I/O Transactions 3. Miscellaneous Transactions D. Data Consistency I. An Initial EmbodimentTurning now to the drawings, and at this point especially to Fig. 1, there is a multiprocessor 11 having a plurality of processors 12aa-12ij and a shared main memory 13. Although the main memory 13 is depicted as being centralized, it will be understood that it may be distributed to provide a disjoint (i. e., mutually exclusive and exhaustive) cover of the used subset of the physical address space. A. System Architecture1. Bus and Memory HierarchyThe processors 12aa-12ij are organized in one or more clusters 14a-14i, each of which has an arbitrated, packet switched, local bus 15a-15i, respectively. In the illustrated embodiment each of the clusters 14a-14i includes one or more of the processors 12aa-12ij, although that is not mandatory. For instance, if desired, one of the clusters could be dedicated to performing I/O for the multiprocessor 11. It is, however, important that each of the processors 12aa-12ij is coupled to its cluster or local host bus 15a..., or 15i by a first level cache memory 16aa-16ij, respectively (it being understood that the processors themselves may be include one or more even lower levels of cache memory, not shown) because the processors 12aa-12ij communicate with their host busses via their cache memories 16a-16ij. The local busses 15a-15i, in turn, link the caches 16aa-16ij to the shared resources within the clusters 14a-14i, respectively. For example, the local bus 15a of the cluster 14a interconnects the first level caches 16aa-16aj for the processors 12aa-12aj, respectively, with an optional map cache 17a, and with an intermediate level or second level cache memory 19a. As shown, the second level cache 19a is composed of a random access memory (RAM) module 20a and a controller 21a. a. Multilevel Bus ArchitectureThe illustrated multiprocessor 11 has a hierarchical architecture, so like reference numerals are employed to identify like components at the different levels of the hierarchy. Moreover, alphabetic suffixes have been appended to the reference numerals to aid in identifying the hierarchical dependency of the components (see the first character of the dual character suffixes) and to distinguish between like components having a common dependency (see the second character of the dual character suffixes). If desired, any one of the clusters 14a-14i could be configured to operate as a fully functional, monoprocessor or multiprocessor computer system. The bus protocol of the present invention provides sufficient usable bus bandwidth to support several processors on a single bus, which is a system configuration that would provide ample computing power for most existing desktop workstation applications and for many existing print server and file server applications. However, the tree-like, hierarchical architecture of the multiprocessor 11 effectively isolates the local cluster bus transactions from most transactions on the global bus 26, such as the global main memory transactions. Consequently, the bus traffic and the electrical loading of the busses are distributed, thereby permitting the construction of even larger and more powerful multi processors. Indeed, while only two levels of hierarchy are illustrated, it will be understood that the tree-like architecture of the multiprocessor 11 is extensible through the use of additional layers of cache memory (not shown) for interconnecting two or more busses at any given level of the hierarchy with a bus at the next higher level. As will be seen, the cache memory 16aa-16ij and 19a-19i is organized as a cache memory tree, with the storage capacities of the caches typically decreasing with increasing depth in the tree. The same bus protocol is employed at all levels of the hierarchy, so the system designer has substantial freedom to reconfigure the multiprocessor 11 to better tailor it to the specific requirements of a particular application. Main memory 13 is connected to the top level, global bus 26 via a suitable controlled 25, but processors and I/O devices may be connected to busses at any level of the hierarchy. The bus hierarchy is completely transparent to all bus clients (i. e., the caches 16aa-16ij for the processors 12aa-12ij, respectively; the cache 60 through which an I/O bridge 18i communicates with its host bus 15i; the controllers 28i and 29i through which a local area network (LAN) 30i and a display or printer device 31i, respectively communicate with their host bus 15i; the second level caches 19a-19i through which the clusters 14a-14i, respectively, communicate with the global bus 26, and the controller 25 through which main memory 13 communicates with the global bus 26), so the clients do not need to be customized for any of the possible system configurations. As described more fully hereinbelow in Section I.D., the bus-client interface is independent of the system configuration. B. Bus Logical TerminologyThe bus protocol of the present invention involves bus operation at three distinct levels-viz., the electrical level of the bus cycles, the logical level of the packets, and the functional level of the transactions. As a matter of definition, a bus cycle is one complete period of the clock on any given bus, so it is the unit of time for electrical information transfer via a single bus. A packet, in turn, is a contiguous sequence of successive bus cycles for logical information transfer. And, a transaction is composed of a request packet and a corresponding reply packet for performing a logical function, such as a data fetch operation (i.e., a data read from a specified memory address location) or a data store operation (i. e., a data write to a specified memory address location). As previously pointed out, all request/reply pairs are dissociated, so the request and reply for any transaction may be separated by an arbitrary number of bus cycles, up to a limit determined by a preselected timeout period for a pending request (i. e., a request that is awaiting a reply). Characteristically, the first cycle or so-called header of each packet carries address and control information, while subsequent cycles carry data if they are required to do so by the definition of the transaction. Each of the busses 15a-15i and 26 is synchronous, but they are not necessarily synchronized with each other because all bus-to-bus information transfer is fully buffered by caches, such as the second level caches 19a-19i. Furthermore, as more fully described hereinbelow, each of the busses 15a-15i and 26 is independently arbitrated by arbiters 35a, 35b, 35i and 36. Every client device on a packet switched bus (as a matter of definition, a client device - sometimes also referred to as a bus client - is a device that transmits and/or receives packets via a host bus 14a-14i or 26) must be able to function both as a bus master and as a bus slave. However, the transaction level interaction of the client devices is somewhat easier to understand if the client that issues a request packet for initiating a given transaction is defined as being a requestor and if any device that issues a reply packet in response to such a request is defined as being a responder. As will be seen, there is no more than one responder to any given request. In operation, an arbiter grants the bus to a requestor in response to an arbitration request that is made by the requestor. The requestor becomes the bus master when it is granted the bus, so that it then issues its request packet. All of the other bus clients examine the address and the command that are carried by this packet to determine whether they are required to take any action or not. The client or clients that are required to take action function as slaves to perform the required action, but the bus is released by the requestor as soon as it is finished issuing its request packet. Thus, the responder must make its own independent arbitration request to acquire bus mastership from the arbiter before it can return its reply packet to the requestor. This reply packet is addressed to the requestor, so the requestor operates in a slave mode to receive it. C. Bus physical Terminology Any given bus (e.g., any of the local busses 15a-15i or the global bus 26) may be composed of multiple segments, but there preferably is no more than one bidirectional bus segment within any single bus to avoid degrading the bus performance. Thus, referring to Figs 3A-3C, it will be seen that the segments of each bus are connected via synchronously clocked pipeline registers 37, regardless of whether the computer system is configured as a monoboard computer as in Fig. 3A, a multiboard computer as in Fig. 3B, or a multiboard/multimodule computer as in Fig. 3C. Pipelining is not essential to the bus protocol of this invention or for maintaining the cache consistency which the protocol assures, but it facilitates the optimization of the electrical characteristics of the bus or busses. It should be understood, however, that pipelining is a feasible option because each of the busses is packet switched. More particularly, the systems depicted in Figs 3A-3C have two, three and four levels of pipelining, respectively, Preferably, the pipelined bus segments are short and are of generally equal length to minimize and more or less equalize electrical signal propagation delay times. Moreover, in practice some or all of the bus segments may be terminated by balanced resistive terminations or the like (not shown) to suppress unwanted signal reflections. It is to be noted, however, that the electrical characteristics of the bus and the bus protocol are essentially independent of each other. D. Device-Bus InterfaceAs will be recalled, standardized bus interfaces, such as shown in Fig. 2 at 41, are provided for electrically interconnecting the busses 14a-14i and 26 with their respective client devices. preferably, these bus clients have open drain CMOS drivers and receivers (see EP-A-0 450 871) for applying output signals to the bus and for receiving input signals from the bus, respectively. The advantage of using such drivers and receivers on the client side of the interface 41 is that their power consumption is sufficiently low to permit this invention to be implemented using currently available VLSl technology. 1. Signals As shown in Fig. 4, the bus interface 41 has a control port, an arbitration port, a receive port, a send port, and a consistency port. The host bus applies a clock signal to the control port of the interface 41 for controlling the timing of all interactions between the interface 41 and its associated bus client device and for providing a reference from which any other clocks that may be needed by the client device can be derived. The control port also includes an output for a synchronous stop output signal (SStopOut) and an input for a corresponding synchronous stop input signal (SStopln), whereby the associated client device may assert SStopOut whenever it wants to bring the system to a synchronous stop. The assertion of SStopOut by any bus client causes a true SStopln signal to be applied to all of the clients on the bus and to the arbiter for the bus, thereby halting all activity on the bus, until the client deasserts SStopOut. 2. Arbitration Interface The arbiters 35a-35i and 36, time multiplex the busses 14a-14i and 26, respectively, among the client devices that are contending for them at any given time, thereby ensuring that each client has fair, bounded time access to its host bus. The client devices are coupled to the arbiter for their host bus by one or more dedicated request lines and by one or more dedicated grant lines. In operation, a client device transmits a bus request to the arbiter for its host bus via its dedicated request line or lines in anticipation of outputting a request or a reply packet on its bus. In most cases, the arbitration request is transmitted after the client has fully assembled the request or reply packet on behalf of which the arbitration request is being made, but in some cases the arbitration request is registered with the arbiter while the client is still assembling the packet in order to reduce the client latency. For example, to reduce the latency of main memory 13, the memory controller 25 preferably registers its arbitration request for a ReadBlock reply (described in more detail hereinbelow) while it is retrieving the data that is to be included in the reply from the main memory 13. As will be seen, each arbiter receives arbitration requests that have different priorities and that are made to acquire the bus for the transmission of packets of different lengths (e.g., an implementation of this initial embodiment utilizes 2 and 5 cycle long packets). Consequently, multiple arbitration request lines are favored (see Fig. 2 and 4) because they permit the client devices to encode their arbitration requests in just a few clock cycles (one cycle and two cycle arbitration requests are described hereinbelow with reference to this initial embodiment and to an enhanced embodiment, respectively), using an encoding that enables the arbiter to discriminate between arbitration requests of different priority and arbitration requests for the transmission of packets of different lengths. Any of the client device may have multiple arbitration requests pending with its bus arbiter at any instant in time. The arbiter, in turn, applies preselected arbitration rules for prioritizing the pending arbitration requests of the contending client devices and sequentially grants those requests in priority order by returning bus grant signals to one after another of the contending client devices via their dedicated bus grant line or lines. For example, the arbitration rules that govern whenever any one or more of the client devices have registered arbitration requests of different priorities with the arbiter for their host bus typically cause the arbiter to grant those requests in declining order of priority. On the other hand, multiple pending arbitration requests of the same priority from one or more of the client devices suitably are handled by employing a round-robin rule to arbitrate among the contending clients and a FIFO (first in/first out) rule to arbitrate between multiple requests of any given client. More particularly, as shown in Fig. 4, each client device has two arbitration request lines 38, and one grant line 39. The two request lines 38 enable the client to encode up to four different arbitration requests for decoding by the arbiter, as at 40 and 41 in Fig. 5. The arbitration requirements of all bus clients, except main memory controllers, can be satisfied by assigning the following meanings to those encodings: All main memory arbitration requests are of the same priority, so the arbitration requests from main memory controllers suitably are interpreted as follows: In practice, the foregoing interpretations of the arbitration requests are programmed into the arbitration ports of the arbiter during system initialization (by means not shown). Specifically, arbitration ports, such as the port 43, that are connected to memory controllers are programmed to function as so-called memory ports, which means that they utilize a single FIFO request register and are assigned memory priority for both short and long reply packets (the only higher priority is cache reply priority ). The other arbitration ports 42 are programmed to function as so-called normal ports, which means that they utilize separate counters or registers for registering low and high priority requests. Thus, each of these normal arbitration ports 42 is further programmed with the length of the packets for which the associated client device makes its low and high priority arbitration requests. A typical assignment of priorities to the arbitration requests that an arbiter may receive from the different types of client devices that it may be required to service is (in declining order of priority): As a general rule, a display controller (see 28i in Fig. 1) utilizes its low arbitration priority to satisfy its request, so the display ordinarily is driven by data that is transferred to its controller during bus cycles that otherwise would be idle. If, however, the data queue for the display drops to a near empty level, the display controller employs its high priority request level for a few request packets to refill its data queue. The two highest arbitration priorities are assigned to replies to reduce the number of pending replies. This is an important flow control mechanism for avoiding bus deadlock. It also reduces transaction execution delays (i. e., the time between the issuance of a request and the receipt of a responsive reply). However, the high priority that is given to replies increases the likelihood of a client device accumulating a sufficient number of transaction requests to put its transaction request register 34 (Fig. 2) at risk of overflowing. Therefore, to prevent such congestion, there is a second flow control mechanism that may be invoked by any client device to demand a system-wide hold of the arbiter. A demand for a system-wide hold temporarily disables the arbiter from granting the bus for the transmission of request packets, thereby causing the arbiter to dedicate the bus to the clients that are making arbitration requests for the transmission of reply packets. Once demanded, such a system-wide hold remains in effect until it is released by the client that demanded it. This enables the congested client to confirm that its pending request queue has dropped to a sufficiently low level to relieve the congestion before normal operation is resumed. As will be understood from the foregoing, different client devices may have different levels of priority, but the allocation of the host bus is non-preemptive. As a result, a client device that has been granted its host bus is the bus master for a sufficient period of time to enable it to place a complete request or reply packet on the bus. However, it is to be understood that one of the important advantages of the encoding of the arbitration requests is that it enables the arbiter to determine predictively, for any given arbitration request from any given client, the length of the packet that the given client will be issuing when it is granted the bus in response to its given arbitration request. This permits the arbiter to limit the length of time that it grants the bus to any given client device to the exact number of bus cycles that the client requires for issuing its packet. Even more significantly, as shown in Fig. 6, it enables the arbiter to control the timing of successive grants, such as Grant₁ and Grant₂, so that the second grant (Grant₂) is issued just after the current bus master client evaluates its grant (Grant₁) for the final bus cycle of the packet A that it is issuing. This early grant notification affords the client that will become the next bus master adequate time to enable it to bring its bus drivers up to a suitably high voltage level for driving the bus with the header cycle for its packet B during the very first bus cycle following the final cycle of the immediately preceding packet A. Thus, it will be evident that the arbiter not only performs the bus arbitration in time overlapping relationship with the transmission of packets on the bus, but also permits the clients to fill all of the available bus cycles with packets. Busses that are composed of a plurality of pipelined bus segments, such as shown in Figs. 3A, 3B and 3C, must be designed with some care if it is desired to utilize predictive, overlapping arbitration of the foregoing type for permitting their clients to fill all of their available bus cycles with packets. Specifically, successive packets A and B can be packed into consecutive bus cycles on the middle or so-called backpanel segment of such a bus if and only if the backpanel segment is the only bidirectional segment of the bus. Otherwise, any attempt to pack the packets A and B into consecutive bus cycles will be defeated by the prohibition against time overlap between those two packets on any given bus segment. As shown in Figs 3A, 3B and 3C, the solution is to use unidirectional bus segments for all segments of such a bus, except for its backpanel segment. The efficacy of this solution is illustrated in Fig. 6, which tracks the packets A and B from the unidirectional output segments A₁ and A₂, respectively, of the bus shown in Fig. 3B, across its backpanel segment B, and then to its unidirectional input segments C₁ and C₂, respectively. As shown, there are two additional wires, 51 and 52, that connect each arbiter to all of the client devices that it is responsible for servicing. In the cycle just preceding the grant of the bus to a given client device, the logic level of the signal on the so-called HIPGrant line 51 enables the client devices to determine whether the next grant will correspond to a high priority request or not, and the logic level of the signal on the so-called LongGrant line 52 enables the clients to determine whether the next grant will be for a long packet or not. These two signals, therefore, enable the clients to discriminate between grants for pending arbitration requests of different priority and between grants provided to permit the transmission of packets of different lengths. 3. Data/Control InterfaceReturning for a moment to Fig. 1, the global bus 26 and each of the cluster busses, such as 14a-14i, are configured to provide a power of 2, denoted as 2n, bit-wide multiplexed data/address path. To connect client devices to unidirectional bus segments, the standard interface 41 (Fig. 4) has a send port and a receive port, each of which comprises a 2n bit wide data/address path (in a typical implementation of this invention, the data/address path of each bus is 64 bits wide). However, the send port of the interface 41 can be operated in a bidirectional mode, so it is utilized as a send/receive (transceive) port for connecting client devices to bidirectional bus segments. As shown, the send and receive port also include a wire for a header cycle bit, and a wire for a parity bit. In this embodiment, a HeaderCycle logical true ( 1 ) signal is asserted during the first cycle of each packet by the bus master (i. e., the client issuing the packet) to identify the header cycle of the packet. Parity, on the other hand, is computed at the data source from the data that is carried by the associated packet to enable the receiver to detect data transmission errors. This parity checking is entirely conventional, so it suffices to note that even parity is employed because the bus idle logic level in this particular implementation is low ( 0 ). 4. Consistency portTo maintain data consistency across all cached copies of each of the memory addresses that is cached within any two or more of the cache memory clients on any given bus at any given time, the bus-device interface 41 has inputs 61 and 62 for receiving Sharedln and Ownerln signals, respectively, from memory controllers (including controllers for intermediate or higher level caches), together with outputs 62 and 63 for transmitting SharedOut and OwnerOut signals, respectively, from cache memories. A true (logical 1 ) SharedOut signal state is asserted, after a fixed delay, by a cache whenever it already contains an address to which a cache requestor on the same bus issues a memory request (e.g.,WriteSingle, ConditionalWriteSingle or ReadBlockRequest in this implementation). Sharedln, on the other hand, is a suitably delayed logical OR of the SharedOut signals from all of the caches on the bus. The delay caused by this logical OR operation also is fixed, so the responder evaluates the Sharedln signal level a predetermined time after it receives such a request packet to determine whether the address specified by the requestor was shared by any of the other caches on its bus when they received the request. As will be seen, this Sharedln signal value is returned to the requestor when the responder issues its reply by a so-called replyShared bit in the header cycle of the reply packet, thereby informing the requestor whether the data to which its request was directed was shared or not when it made its request. A true (logical 1 ) OwnerOut signal state is asserted, after a fixed delay, by a cache whenever it is the owner of the data block residing at the address specified in a read request (e.g., a ReadBlockRequest) that it receives from another cache. As described in more detail hereinbelow, a cache becomes the owner of a data block whenever it writes data into that particular data block. This means that the ownership, if any, belongs to the cache that last wrote into the data block, so there is no more than one owner at a time of any given data block. Nevertheless, to simplify the timing, the Ownerln signal preferably is a similarly delayed logical OR of the OwnerOut signals from the caches on the bus, so that the uppermost client on the bus (i. e., the memory controller or a higher level cache) can evaluate Ownerln at the same time that it is evaluating Sharedln to determine whether it should issue the reply or defer in favor of having the reply come from a lower level cache owner of the data. As will be appreciated, the ORing of the OwnerOut signals from the caches is not essential because no more than one Cache can assert OwnerOut, but it results in uniform treatment of the Sharedln and Ownerln values. It is noteworthy that the Sharedln and Ownerln signal values are computed by logical ORs, rather than by wire-ORing. This permits pipelining of Sharedln and Ownerln, while avoiding electrical constraints on their timing and interpretation. It also permits parity checking of the SharedOut/Sharedln and OwnerOut/Ownerln signal values if desired (see the discussion of this option in the following description of the enhanced embodiment). E. TransactionsTransactions are the uppermost layer of the bus protocol. Each transaction is composed of a request packet and a reply packet, which are independently arbitrated. A transaction begins when the requestor registers an arbitration request with the arbiter for its bus, but the request packet is stored by the requestor in its request register 28 until the arbiter grants it the bus. When that occurs, the requestor issues its request packet one cycle at a time during consecutive bus cycles. The first cycle of a request packet, which is called the header cycle, contains all of the information that is needed to identify the requestor and the transaction the requestor is initiating. It also includes sufficient information for selecting the client device or devices that need to participate in the transaction to bring it to a successful conclusion. Subsequent cycles of the request packet generally contain data that is dependent on the transaction that is to be performed. All client devices (including the requestor) receive the request packet, and each of them examines its header cycle to determine whether it is required to participate in the transaction or not. As a general rule, a substantial number of the bits of the header cycle of each request packet are reserved for an address that is issued by the requestor to select a memory location or an I/O device register. Although the mechanism by which devices are selected to participate in a transaction may differ for different transactions, most transactions utilize the address that is contained in the header cycle as the selection mechanism. More particularly, referring to Fig. 7, in this embodiment forty-seven bits of the header cycle of each request packet are allocated to an address field (this implementation currently employs only thirty-two of these bits, so the other fifteen bits are available for future extensions, which means that these unused bits must be checked when reading the address field to confirm that they are all 0 ). Ten of the other bits are reserved for carrying a so-called DevicelD, which is a unique identifier that each client device is assigned (suitably, these DeviceIDs are assigned during system initialization by means not shown). Furthermore, five of the remaining bits of the request header cycle are used for encoding transaction commands. And still one more bit is used for protective mode checking by the client devices (this mode checking enables the client devices to determine whether the requestor is authorized to initiate the specified transaction, but such mode checking is beyond the scope of this invention). Accordingly, in this particular implementation, the request header cycle has only one unallocated bit. No more than one client device replies to any given request, although more than one client may change its internal state upon receiving the request packet. The responder first partially or completely assembles the reply and then registers a bus arbitration request with the arbiter for its bus. Thereafter, upon being granted the bus, the responder sends its reply packet one cycle at a time during consecutive bus cycles, starting again with a header cycle which is followed by one or more data cycles. For example, a 64 bit-wide bus supports a data transfer unit of eight octets (eight bit bytes) on each data cycle. These bytes, in turn, may be organized into words of various lengths to implement a variety of different word-based software architectures. As shown in Fig. 8, the header cycle of each reply packet replicates the transaction identifying bits of the encoded command that was received from the requestor, the address specified by the requestor, and the DevicelD of the requestor. Typically, the responder simply strips this information from the header cycle of the request packet and then stores it for use in constructing the header cycle of the reply packet. This information not only uniquely identifies the transaction to which the reply packet relates, but also unambiguously links the reply packet to the transaction requestor. Considering the header cycle of a typical reply packet in some additional detail, it will be observed that it suitably is bit-by-bit identical to the header cycle of the corresponding request packet, with the following exceptions: (1) a request/reply flag bit is inverted to indicate that the packet is a reply; (2) the mode bit of the request header is used as a fault bit in the reply header to indicate whether the responder encountered a fault or not while assembling the reply; and (3) the unused bit of the request header is employed as a replyShared bit to indicate whether the datum at the address specified for the transaction was shared by multiple caches or not at the time that the responder received the request packet for the transaction. The function of the replyShared bit is described more fully hereinbelow. However, it is appropriate to note at this point that the responder drives the fault bit to a true ( 1 ) logic level state only when it encounters a fault, so this bit effectively notifies the requestor whenever such a fault occurs, thereby causing the requestor to prepare itself to receive a fault code (which suitably is transmitted in the thirty-two lower order bits of the second cycle of the reply packet). Fault detection and fault code generation are outside the scope of this invention. As before, all client devices examine the header cycle of the reply packet to determine whether any action is required of them. In operation, the DeviceIDs are relied on to disambiguate the replies amongst the different client devices. Some clients, however, may have multiple outstanding or pending requests. Thus, replies suitably are further disambiguated within each of those clients, either by assigning multiple DevicelDs to the clients or by making some other suitable provision for enabling them to disambiguate the replies to their outstanding requests. A transaction is complete when the requestor receives a reply. In most cases, the bus protocol of the present invention results in a one-to-one correspondence between requests and replies. However, some request packets may not have a corresponding reply packet and vice versa, either because of the implementation of the bus protocol or because of errors and the like. Thus, the protocol does not depend on the request/reply pairing as being an invariant. Instead, it merely requires that all client devices on any given bus service the request packets that require action from them in arrival order. As will be seen, this requirement is central to maintaining data consistency. A table summarizing the command encodings and the packet lengths of the request/reply pairs for the transactions that have been defined for this initial embodiment is set forth below: As will be seen, there are three general types of transactions: (a) memory transactions for performing memory access operations while maintaining cached data consistency, (b) I/O transactions for performing programmed I/O operations, and (c) miscellaneous transactions for implementing still other functions. As will be appreciated, the extremely compact and efficient encoding of the transactional commands is practical because the logic level ( 0 or 1 ) of the request/reply flag bit (i. e., the fifth bit of the command field as shown in the foregoing table) is sufficient to indicate whether any given packet is a request or a reply. Up to sixteen different commands can be encoded using this command field format, so it will be understood that the above-defined transactions only partially exhaust the command field capacity. Of course, the excess capacity of the command field may be utilized, if desired, to define further transactions for implementing additional features. 1. Memory Related TransactionsMemory transactions are employed for transferring data back and forth between processors and memory, as well as between I/O devices and memory. More particularly, ReadBlock is invoked by a cache requestor to read a data block from the main memory 13 or from another cache, depending on whether a version of the desired data block is cached elsewhere in the memory system and, if so, on whether the cached version is owned or not. FlushBlock can be invoked by a cache requestor for writing a owned data block (i. e., a block of data that has been modified most recently by a locally initiated write- i. e., a write initiated by a processor in the same branch of the memory tree) back to the main memory 13. And, WriteBlock is available for enabling secondary data sources (i. e., data producers that are external to the memory system) to write data blocks directly into the main memory 13, as well as into any intermediate level caches caches 19a-19i and any first level caches 16aa-16aj (see Fig. 1) that match on the address specified for the transaction. In other words, this WriteBlock transaction permits new data to be introduced into the primary memory system of the multiprocessor 11, without having to route such data through a cache. All of these block transactions span a plurality of contiguous words, such as four 64-bit words which are serially aligned in physical address space so the address of the first individually addressable quantum within any such data block is 0 mod N, where N is the number of individually addressable quanta contained within each data block. Advantageously, all block data transfers on each bus are organized so that the addressed quantum appears in the first data cycle on the bus, followed by the remaining quanta of the data block in cyclical order. See Fig. 9. This minimizes the memory latency for retrieving the datum from the specified address, which is especially desirable in the event of a cache miss. WriteSingle is a transaction which is invoked by a cache requestor for updating multiple cached copies of shared data, without necessarily affecting the main memory 13. This transaction can be invoked only by a cache that contains a copy of the affected data block. ConditionalWriteSingle is a closely related, optional transaction that a cache requestor can invoke for performing atomic read-modify-writes to such shared data. 2. I/O TransactionsI/O transactions allow processors to transfer data to and from I/O devices, such as the LAN controller 29i in Fig. 1. The address space employed for these I/O transactions (i. e., I/O space ) is totally disjoint from the address space used for memory transactions (i. e., memory space ), so a given valid address is either in memory space or in I/O space, but not in both. As will be seen, I/O transactions have no bearing on data consistency, and the data consitency protocol has no bearing on the I/O transactions. IORead, IOWrite and BlOWrite transactions have been defined in this embodiment for performing I/O operations. Each I/O device is allocated a unique portion of a common address space, and these transactions are issued to that address space. Thus, the I/O devices, such as the controller 29i in Fig. 1, are free to interpret the I/O commands that are addressed to them as required to enable them to effectively participate in the desired transaction. The lORead and the lOWrite transactions are initiated by cache requestors to read and write addressable quanta from and to, respectively, specified I/O addresses. BlOWrite also is a cache initiated transaction for writing a single addressable quantum to I/O address space, but it differs from the I/OWrite transaction because it permits the data to be written simultaneously into multiple instances of a given device type. Thus, while BlOWrite is not an unrestricted global broadcast transaction, it is a broadcast to all devices of a given type. The definition of device type is system dependent and is beyond the scope of this invention. Turning for a moment to the I/O bridge that is shown at 18i in Fig. 1, it is to be understood that it is a hybrid device insofar as the memory system is concerned. More particularly, this I/O bridge device 18i is useful for giving an aysnchronous I/O device, such as the memory bus of a foreign computer system, direct access to the memory system of the multiprocessor 11 via a cache 60 that is functionally similar to the caches 16aa-16ij. To that end, the bridge 18i includes provision (not shown) for buffering memory reads and writes issued by such an I/O device and for translating those reads and writes into defined memory transactions However, it also responds to I/O transactions within a portion of the I/O space, which means that the processors 12aa- 12ij can access the internal resources of the I/O bridge 18i and the registers of the I/O devices to which the bridge 18i is connected. The allocation of I/O address space is non-trivial only because the I/O address space size requirements of the different I/O devices that may be connected to one or another of the busses of the multiprocessor 11 differ substantially. Therefore, as a practical matter, these differences should be taken into account while allocating the I/O address space to ensure that the I/O address space allocation for each I/O device is a reasonable approximation of the address space the device is likely to need. 3. Miscellaneous TransactionsMap and DeMap are cache invoked transactions for carrying out high speed virtual-to-physical address space mapping in the virtual memory environment of the multiprocessor 11. To that end, Map permits a cache requestor to read a virtual page-to-physical page mapping entry from a map cache, such as at 17a in Fig. 1. DeMap, on the other hand, enables a cache requestor to invalidate a cache resident virtual-to-physical address map for any specified page of virtual address space. F. Data ConsistencyIt is essential in a shared memory multiprocessor environment for all bus clients to have access to the same sequence of data values for any given address in the memory space. This is referred to as data consistency . The use of separate cache memories for the individual processors of such a multiprocessor complicates the problem of maintaining this data consistency, especially in larger systems where the potential number of copies of a given address that may exist within the caches at any given time is large. However, an especially efficient data consistency protocol can be implemented by employing so-called write back caches (i. e., caches that update cached data in accordance with data writes issued by processors, without immediately updating main memory) for initiating and executing the memory transactions that are required by the processors 12aa-12ij and by the I/O bridge 18i (Fig. 1). These caches may fetch and store data as needed from all addresses in the memory space, because the external consistency of multiple copies of the data at any given address within the memory space is maintained automatically and transparently by the hardware through the use of certain of the above-described transactions. Moreover, I/O devices are permitted direct access to the memory space, while preserving a consistent view of memory for the processors 12aa-12ij and for the I/O bridge 18i. More particularly, as explained in even further detail hereinbelow, the caches 12aa-12ij, 19a-19i and 60 detect when a datum becomes shared by directly or indirectly monitoring the traffic on their respective host busses, and they perform a broadcast write whenever any processor (or the I/O bridge 18i) updates a shared datum value in the memory space. All of the caches 12aa-12ij and 60 are snoopy caches, which means that they monitor all of the traffic on their busses. 1. Data Consistency in Single-Level SystemsAs previously pointed out, a single level system is composed of one or more processors, such as the processors 12aa-12aj in Fig. 1, which are connected to their memory bus 15a through respective caches 16aa-16aj, together with a shared main memory. Being that the processors 12aa-12aj access main memory through their caches 16aa-16aj, respectively, it will become evident that it is sufficient to maintain data consistency between all cached copies of any given address. This means that the main memory copy of an address that is cached can be stale with respect to the cached copy or copies, without risk of computational errors being caused by this stale main memory data. To maintain data consistency, the consistency protocol relies upon each cache keeping two status bits, shared and owner, for each data block that it is caching, together with a pendingState for any data block that is subject to a transaction that is pending on the bus at the request of that particular cache. In addition, the caches 16aa-16aj conventionally maintain a Valid state bit for each of their data blocks to distinguish between currently cached data blocks and deleted or empty data blocks that can be overwritten. The state of the shared bit indicates whether there possibly are multiple cached copies of the associated data block or not. This is a conservative indication because the shared bit is affirmatively set to a true ( 1 ) state if there are multiple cached copies, but is not necessarily reset to a false ( 0 ) state if there is only one cached copy. The owner bit for a data block, in turn, is set to a true ( 1 ) state in a given cache if and only if the processor or other device that communicates with the bus through the given cache was responsible for performing the most recent (i. e., last) write into that particular data block. This means that there is no more than one cache owner of a given data block at any instant in time on any given bus, even if one or more of the other caches on the bus also contain a copy of that same data block. Additionally, the pendingState that a cache maintains for each transaction that it has pending on the bus enables the cache to correctly compute the value for its shared bit for the data block to which the transaction pertains when it receives the reply, even if the number of cached copies of that data block changes while the transaction is still pending. This pendingState information also enables the cache to identify intervening transactions that can modify the value of the datum at the address specified by its pending transaction, so that the cache can take appropriate action to obtain the correct datum value for that transaction, as more fully discussed hereinbelow. As a general rule, a first level cache initiates a ReadBlockRequest whenever its associated processor issues a fetch or store command to an address that causes a cache miss to occur (i. e., whenever the address to which such a command is issued is not in the cache). If necessary, the cache may also initiate a FlushBlock for writing data from the cache to main memory, thereby freeing storage space within the cache for storing new data (as will be recalled, only data blocks that have their owner bit set are written out by FlushBlock to avoid writing stale data into main memory). Furthermore, a cache initiates a WriteSingle transaction (this is the aforementioned write that distinguishes the consistency protocol from the minimum set of operations that would be needed if data consistency could be ignored) whenever its associated processor writes into a data block that has its shared bit set ( 1 ). All caches, including the requestor, attempt to match the addresses specified in the header cycles of any RBRqst, WSRqst, WSRply, CWSRqst, CWSRply, and WBRqst packets (i. e., the packets that may affect the value and/or the not-shared status of the datum at the specified address). The pendingState that the requestor maintains for each of its pending transactions includes the address of the data that is subject to the transaction for enabling the requestor to detect intervening packets of the foregoing type that specify the same address, together with a shared status that is cleared to a false ( 0 ) state when the requestor receives its own request packet. This enables the requestor to set its shared status for any data block that is subject to one of its pending transactions to a true ( 1 ) state if that particular data block becomes shared while the transaction is pending. Furthermore, as described in some additional detail hereinbelow it also enables the requestor to take suitable corrective action if the value of the datum that is subject to the pending transaction is changed while the transaction is pending. All caches, other than the requestor, simply match the addresses specified in the header cycles of the above-enumerated packets against the addresses of the data blocks they are caching to determine whether they contain the specified address or not. No such matching is required for either a FBRqst packet or a FBRply packet, because the FlushBlock transaction is used only for writing data blocks from the caches to main memory, without requiring notification of the other caches that such action is being taken. Likewise, no address matching is necessary for a WBRply packet because it simply provides an acknowledgement that memory has processed the corresponding WBRqst packet. Furthermore, a RBRply is relevant only to the requestor, so the other caches may ignore such a packet. Each cache, except the requestor, that successfully matches the address specified in the header cycle of a RBRqst, a WSRqst, or a CWSRqst packet asserts SharedOut at the consistency port of its bus interface 41 (Fig. 4), thereby signaling that the data block at that particular address is shared. Such a cache also sets the shared bit for its copy of the specified data block to a true ( 1 ) state, if it has not previously been so set. As will be recalled, headers of all request and reply packets carry DeviceIDs (see Figs. 7 and 8) that enable the bus clients to determine whether they are the requestor or not for any given packet. As will be appreciated, the assertion of SharedOut by any of the caches on the bus is sufficient to cause the replyShared bit to be set to a true ( 1 ) state in the header cycle of the corresponding reply packet, regardless of whether the reply is supplied by a cache owner of the data block or by main memory 13(in the absence of a cache owner). This follows from the fact that the SharedOut signals from the caches are logically ORed (by means not shown) to compute the value of the Sharedln signal that is applied to the consistency ports of all of the bus client interfaces 41 via a shared line 61 (Fig. 10). The requestor, on the other hand, ORs the replyShared bit that it receives in the header cycle of the reply to its pending transaction with the shared bit that it maintains in its pendingState for the transaction. Thus, the requestor's shared bit for its copy of the specified data block is set to a true ( 1 ) when it receives its reply either if the data block existed in another cache when the requestor issued its request packet or if the data block was copied into another cache while the requestor was awaiting its reply. A requestor that issues a WSRqst or a CWSRqst sets or resets its shared bit for its copy of the data block to which the transaction pertains depending on the state of the replyShared bit in the header cycle of the corresponding reply packet (see Fig. 8) that it receives and the shared status of its pendingState when that reply is received. If both the replyShared bit in the header of the reply is false ( 0 ) state and the shared status in its pendingState for the transaction is false ( 0 ), the requestor has confirmation that no other cache contains a copy of the data block into which it is writing. Accordingly, the requestor then resets its shared bit for the specified data block to a false ( 0 ) state, thereby ensuring that the shared bit is eventually cleared when the status of a data block changes from a shared to a not shared state. The manipulation of the owner bits that the caches maintain for the data blocks they are storing is even more straightforward. Briefly, a cache sets its owner bit for a data block whenever it writes into the data block on behalf of its processor. Conversely, a cache clears or resets its owner bit for a data block whenever the data block contains an address that causes the cache to successfully match on the address specified in a WSRply or a CWSRply for a WriteSingle or a ConditionalWriteSingle transaction requested by any other cache. WriteSingle and ConditionalWriteSingle are fully equivalent insofar as the data consistency protocol is concerned, so it will be understood that the following description of the effect of a WriteSingle transaction on the shared and owner bits applies equally well to a ConditionalWriteSingle. As previously pointed out, the processors store data in the shared memory system by writing data into the data blocks that are residing in their respective caches. If a processor issues a store command for storing a given datum value in a word or other addressable quantum of one of the data blocks that is residing within its associated cache while the shared bit for that data block is reset to a false ( 0 ) logic level, the processor immediately updates the appropriate portion (e.g., word) of the cached data block and simultaneously sets the owner bit for that data block. On the other hand, if the shared bit for the data block to which processor store command is directed is set to a true ( 1 ) logic level, the cache suspends the execution of the store command and issues a WSRqst packet which (a) identifies the physical address to which the processor has directed its store command (this physical address typically is determined by translation of the virtual address provided by the processor), and (b) contains the datum value that the processor has provided. All WSRply packets come from the memory controller in a single-level system. Moreover, a WSRply packet replicates both the physical address and the datum value of the corresponding WSRqst packet. Thus, upon receiving its WSRply packet, the cache requestor not only executes the data store for its processor, but also sets its owner bit for the data block into which the processor data is written to a true ( 1 ) state. Any of the other caches that match on the address specified in the header cycle of this WSRply packet (a) update their copies of the datum to which the reply packet is addressed based on the datum value that is provided by the reply packet, and (b) reset their owner bits for the data block that has been updated to a false ( 0 ) state. As will be appreciated, this ensures that no more than one cache will assert ownership of any given data block during any given bus cycle. It also means that there is no assertion of ownership by any of the caches for any cached data block that has not been written into since it was read from main memory. In view of the foregoing, it will be understood that when a cache requestor issues a RBRqst packet on its bus for a data block at a specified address, the data block may or may not be owned by another cache on the bus. If, however, one of the other caches owns the specified data block, the owner (and possibly one or more of the other caches) will match on its address, thereby causing each of them to assert SharedOut. Furthermore, the owner also will assert OwnerOut, thereby causing the logical OR's of the OwnerOut signals to drive the Ownerln line 62 (Fig. 10) to a true ( 1 ) state. The true ( 1 ) state of the Ownerln signal prevents the main memory from responding to the RBRqst, so the responsibility for supplying the corresponding RBRply packet is transferred to the cache owner of the specified data block. On the other hand, if none of the caches asserts ownership of the specified data block (i. e., if the Ownerln signal is false ( 0 ), main memory supplies the RBRply, even if the data block is shared. As previously mentioned, the packet switching of the bus creates a risk that the ownership of a data block will change after a requestor has issued a RBRqst, but before it has received the corresponding RBRply. For example, a cache may issue a RBRqst for a data block that is owned by main memory at the time that the request is issued. However, a short time earlier, some other cache may have issued a WSRqst to write new data into that very same data block. The risk then is that the WSRply packet will be issued by the memory controller prior to the RBRply packet because the memory services request packets in arrival order. If that occurs, the cache that initiated the Write Single transaction will become the owner of the data block Notwithstanding this intervening change in the ownership of the data block, main memory 13 (Fig. 1) still will supply the RBRply when it is ready to do so, because the cache owner was not prepared to assert its ownership of the specified data block when it received the RBRqst. This means that the data provided by this RBRply packet is stale. Therefore, to avoid taking stale data, the ReadBlock requestor uses its pendingState for its RBRqst to either compute the correct value for the requested data block or to initiate a retry of the ReadBlock after it receives the RBRply to its original RBRqst. The packets that a ReadBlock requestor needs to take into account while its request is pending to avoid utilizing stale data are those that modify the data (WSRply, CWSRply, and WBRqst) to which its RBRqst packet is addressed. WriteBlock transactions are similar, but not identical, to FlushBlock transactions insofar as the memory system is concerned. Caches ignore FBRqsts, but not WBRqsts. Instead, any cache that matches on the address specified by a WBRqst, overwrites its address matching data block with the data contained by the WBRqst packet and resets or clears its owner bit for that data block to a false ( 0 ) state. A brief example will add some useful perspective to the foregoing description of the single-level consistency protocol. As will be seen, the example that follows describes a sequence of events for a specified memory location (address 73), starting from the state where none of the five caches 82a-82e in the shared memory system 83 shown in Fig. 10 has the data block containing that address. For convenience, the reference numerals that are used in this example correspond to the reference numerals that are used in Fig. 10: 1. a. Processor 81 a reads add ress 73. b. Cache 82a misses and does a ReadBlock on the bus 85. c. Main memory 86 provides the requested data. d. The state bits for the cached copy of the data block are: Shared82a = 0 and Owner82a = 0. 2. a. Processor 81 b reads address 73. b. Cache 82b misses and does a ReadBlock on the bus 85. c. Cache 82a sets its Shared bit for the data block containing address 73 to a true ( 1 ) state and also asserts SharedOut, so the Sharedln line 61 is driven to a true ( 1 ) state after a predetermined delay. d. Memory 86 still provides the data. e. The state bits for the cached copies of the data block are: Shared82a = Shared82b = 1; Owner82a = Owner82b = 0. 3. a. Processor 81c reads address 73. b. Cache 82c misses and does a ReadBlock on the bus 85. c. Cache 82a and cache 82b assert SharedOut, thereby again causing the Sharedln line 61 to be driven high ( 1 ). d. Memory 86 still provides the data. e. The state bits for the cached copies of the data block now are: Shared82a = Shared82b = Shared82c = 1; Owner82a = Owner82b = Owner82c = 0. 4. a. Processor 81 b writes address 73. b. Because the data is shared, cache 82b does a WriteSingle on the bus 85. c. Cache 82a and cache 82c assert SharedOut, so the Sharedln line 61 is driven high. d. Cache 82a, cache 82b, and cache 82c update their values at address 73, but memory 86 does not. e. Cache 82b becomes owner of the data block containing address 73 (Owner82b = 1), but the shared and owner state bits for the cached copies of the data block otherwise are unchanged. 5. a. Processor 81d reads address 73. b. Cache 82d misses and does a ReadBlock on the bus 85. c. Cache 82a, cache 82b, and cache 82c assert SharedOut to signal Sharedln on line 61. d. Cache 82b asserts OwnerOut, thereby causing the Ownerln line 62 to be driven to a true ( 1 ) state after a predetermined delay. This inhibits main memory 86 from responding. Instead, the data block is provided by its owner cache 82b. e. Cache 82d marks its copy of the data block as Shared82d = 1, Owner82d = 0. The shared and owner state bits for the cached copies of the data block otherwise are unchanged. 6. a. Processor 81 d now writes address 73. b. Because the data is shared, cache 82d does a WriteSingle on the bus 85. c. Cache 82a, cache 82b and cache 82c assert SharedOut, so the Sharedln line 61 is again driven high ( 1 ). d. Ownership of the data block containing address 73 changes from cache 82b to cache 82d (Owner82b = 0, Owner82d = 1). The shared and owner state bits for the cached copies of the data block otherwise are unchanged 7. a. Processor 81e writes address 73. b. Cache 82e misses and does a ReadBlock on the bus 85. c. Cache 82a, cache 82b, cache 82c and cache 82d assert SharedOut, thereby causing the Sharedln line 61 to be driven to a true ( 1 ) state after the aforementioned delay. d. Cache 82d, the current owner of the data block containing address 73, asserts OwnerOut, so it causes the Ownerln line 62 to be driven high ( 1 ) to inhibit memory 86 from supplying the data in favor of doing so itself. e. Cache 82e marks its state bits for its copy of the data block as Shared82e = 1, Owner82e = 0. f. Cache 82e then does a WriteSingle to address 73 because the data is shared. g. Cache 82a, cache 82b, cache 82c, and cache 82e assert SharedOut, thereby driving the Sharedln line 61 to cause the replyShared bit in the WSRply header to be set to a true ( 1 ) state. h. Ownership of the data block containing address 73 switches from cache 82d to cache 82e (Owner82d = 0, Owner82e = 1). Otherwise, the shared and owner state bits for the cached copies of the data block remain unchanged. 2. Data Consistency in Multilevel SystemsAs will be recalled, a two-level memory system is composed of a plurality of one-level memory systems 14a-14i (Fig. 1), called clusters, which are connected to a main or global bus 26 via second-level caches 19a-19i, respectively. In other words, each cluster contains a single second-level cache that connects the cluster to the global bus 26, together with a private bus that connects the second-level cache to the first-level caches in the cluster. This private cluster bus is electrically and logically distinct from the other cluster busses and from the global bus. Main memory 13 is connected to the global bus 26. At the cluster bus level of such a memory system, the second-level cache has the functional attributes of main memory. On the other hand, at the global bus level, the second-level caches function in essentially the same way as the caches within a single-level system. As will be seen, the design of the bus protocol and the data consistency protocol operate to prevent the first-level caches from discovering whether they are operating in a one-level or a multilevel memory system. In other words, the responses that the first-level caches receive from their environment are the same in both cases. Thus, it suffices to note that the foregoing description of the data consistency protocol for a one-level memory system aptly describes the consistency protocol as applied to each of the clusters of a multilevel system. The extension of the data consistency protocol to multilevel systems requires the higher level caches 19a-19i to keep all of the state bits (shared, owner, and pendingState) a first level cache maintains, plus so-called existsBelow bits. More particularly, each of the higher level caches maintains one existsBelow state bit for each data block that it is caching. This existsBelow bit is set to a true( 1 ) state for any given data block within a higher level cache if and only if one or more of the next lower level caches in the same branch of the memory tree also has a copy of the that particular data block. Thus, for example, in a two-level system of Fig. 1, the existsBelow bits enable the second level caches 19a-19i to filter packets that appear on the global bus 26, so that the only global bus traffic that produces traffic on a given cluster bus 15a,... or 15i is the global traffic that is relevant to one or more of the cluster bus client devices. As will be appreciated, without such filtration, all of the traffic on the global bus 26 would appear on every cluster bus 15a-15i, thereby defeating the purpose of the two-level organization of the memory system. To provide a more comprehensive understanding of how packets appearing on a cluster bus relate to the packet traffic on the main or global bus 26 and vice versa, it will be useful to consider the operation of one of the second-level caches, such as the cache 19a, in some additional detail. Whenever the second-level cache 19a receives a RBRqst from a requestor on its cluster bus 15a, the second-level cache 19a may or may not contain a copy of the data block specified by the RBRqst. If it has a copy, the second-level cache returns the data to the requestor via a RBRply, after setting the replyShared bit in the reply packet to the logically ORed Sharedln value of (a) the SharedOut signals that it receives from the first level caches as a result of the RBRqst and (b) the current state of its shared bit for the specified data block (as will be recalled, in a single-level system, the main memory controller 25 evaluates the Sharedln signal level on the Sharedln line 61 a fixed time after it receives the RBRqst from the requestor and copies that evaluated signal level into the replyShared bit of the header for the RBRply packet that it returns to the requestor). If, on the other hand, the second-level cache 19a does not have a copy of the data block that is specified by the RBRqst of its cluster bus requestor, the second-level cache 19a issues a RBRqst packet on the global bus. Upon the return of the RBRply to this request, the second level cache updates itself with the new data block, uses its pendingState for its RBRqst to compute the value of its shared bit for this new data block, and then responds to the requestor by issuing a RBRply on the cluster bus 15a. When a second-level cache, such as the cache 19a, receives a WSRqst from a requestor on its cluster bus, the cache 19a checks to determine if its shared bit for the data block containing the address specified by the WSRqst is set. If its shared bit for that particular data block is not set, the second level cache 19a updates the data in accordance with the WSRqst data, sets its owner bit for the updated data block, and then issues a WSRply (with the replyShared bit at the value of the Sharedln line 61 at the appropriate time) via its cluster bus. On the other hand, if the second level cache 19a has its shared bit for the data block that is subject to the WSRqst set to a true state ( 1 ), it propagates the WSRqst of the cluster-level requestor by issuing a WSRqst on the global bus 26. The main memory controller 25 responds to this global level request some time later by providing a WSRply. When this reply is received, the second-level cache 19a updates its copy of the data block in accordance with the WSRply reflection of the data provided by the WSRqst, sets its owner bit for its copy of the data block, and then issues a WSRply on its cluster bus (with the replyShared bit in the header cycle of this cluster-level WSRply set to the logical OR of the replyShared bit value in the WSRply received via the global bus 26 and the value of the Sharedln line 61 corresponding to the original WSRqst on the cluster bus). Each second-level cache monitors the RBRqst packets on the global bus 26 to identify the RBRqsts for which it has an address match. When such an address match occurs, the second-level cache, such as the cache 19a, checks its owner bit and its existsBelow bit for its copy of the specified data block. If its owner bit for that particular data block is set, the cache 19a responds with the data, but the manner in which the RBRply packet is assembled depends upon whether its existsBelow bit is also set or not. More particularly, if the existsBelow bit is set, the cache 19a first issues a RBRqst on its cluster bus 15a to retrieve the data that is called for by the global-level RBRqst from the first-level cache owner of the specified data block. If, however, the existsBelow bit for cache 19a's copy of the specified data block is not set, cache 19a concludes that its copy is current, so it responds with a global-level RBRply, without propagating the global level requestor's RBRqst. When a second-level cache, such as the cache 19a, matches on the address specified in a WSRqst on the global bus 26, it asserts SharedOut as usual, but it takes no other action. However, when the cache 19a matches on the address specified in a WSRply on the global bus 26, it updates its copy of the data at that address. Additionally, if its existsBelow bit for its copy of the data block containing the address specified by the WSRply happens to be set, the cache 19a also issues a WSRply on its cluster bus 15a. It is noteworthy that this WSRply packet is not preceded by a corresponding WSRqst packet on the cluster bus, so that is another reason why the number of request and reply packets on a bus may be unequal. When a second level cache gets a FBRqst from its cluster bus, it simply updates its copy of the data block to which the request is addressed and sends a FBRply, respectively back to the requestor. The responder for a FlushBlock always is the actual or apparent main memory for the responder, so second level caches ignore all FBRqsts on the global bus. As will be recalled, the WriteBlock transaction is available for use by secondary data producers (data sources that are outside the memory system) to enter data into the physical address space. To that end, this transaction writes a cyclically ordered data block into main memory and into any caches that match on the address specified in the WBRqst. In multilevel systems, the WriteBlock transaction may be restricted for use as a global bus transaction. In that event, WBRqsts are issued only by devices that are interfaced with the global bus 26, and all WBRplys are supplied by main memory 13 (the WBRply for this restricted application of the WriteBlock transaction contains a standard reply header cycle followed by an undefined cycle). Alternatively, the WriteBlock transaction may be redefined to permit lower level caches to invoke it. If so, any WBRqsts that are issued by any of the lower level, local caches are passed on to the second level caches which, in turn, place the WBRqsts on the global bus 26. The write is executed upon receipt of the WBRply. As will be appreciated, this embodiment requires that each of the second-level caches maintain copies of all data blocks that are cached below them. To that end, the second-level caches 19a-19i are each selected to have a data storage capacity that is at least equal to the sum of the storage capacities of the first-level caches on their respective cluster busses. Moreover, the second-level caches 19a-19i are each selected to have a degree of associativity that is at least equal to the sum of the associativities of the first-level caches on their respective cluster busses. For example, if a cluster comprises four first-level direct mapped caches (i. e., caches having one degree of associativity), the second-level cache for that cluster is selected to have at least four degrees of associativity to ensure that it can match on the address of any data block that might appear on its cluster bus. II. An Enhanced EmbodimentA memory system utilizing the present invention is readily extensible and easily enhanced, so some extensions and enhancements will be described to illustrate its potential for modification and improvement. The same topical outline that was used hereinabove to organize the description of the initial embodiment will be followed to identify the subjects to which the distinctive features of this enhanced embodiment pertain. A. System ArchitectureIf desired, multiple busses may be interleaved to operate in parallel (not shown), thereby increasing the usable bus bandwidth at the expense of incurring a proportional increase in the number of bus wires that are required. For example, one implementation permits bits 8 and 9 in the address field of the headers for the request and reply packets (see Figs. 11 and 12, respectively) to be employed for identifying the interleaved bus upon which a given packet is to be transmitted. Thus, in that implementation, one-way, two-way, and four-way interleaves of the bus architecture are permissible. B. Device-Bus InterfaceAs shown in Fig. 13, the standard device-bus interface 101 for the enhanced embodiment incorporates several notable modifications. Some of the differences relate to the terminology that is used to identify the various signals, but others are of substantive importance. The internal logic of the interface 101 is illustrated in Fig. 14. The drivers 104-109 and the receivers 111-117 that are shown in Fig. 14 typically are open drain CMOS devices in keeping with the teachings of the aforementioned EP-A-0 450 871. 1. SignalsThe substantive distinctions that exist between the signal ports of the interface 101 and the interface 41 of Fig. 4 are set forth in some detail under the following headings of this Section. 2. Arbitration InterfaceAs will be recalled, each bus of the memory system of the present invention has an arbiter for ensuring that all contending bus clients are given fair, bounded time access to their host bus and for implementing flow control to avoid packet congestion on the bus. As pointed out above, packet congestion is an issue because the bus or busses are packet switched, which means that a bus client can accumulate transaction requests faster than it is able to service them. In this enhanced embodiment, each client device interacts with the arbiter for its bus via an arbitration port that has three request wires, Req_L[2..0], and three grant type wires, Gnt-Type_L[2..0]. In addition, there is a single Gnt_L wire that is shared by all of the clients that are connected to the arbiter. A bus client communicates its arbitration requests to the arbiter for its bus by using its Req_L wires for either one clock cycle or two consecutive cycles. In the first cycle the client communicates the priority of its request. Additionally, for normal arbitration requests, the client uses a second cycle on one of its Req_L wires for informing the arbiter of the packet length for which it is requesting the bus. Typically, the encodings for the two cycles of these arbitration requests are as follows: First Cycle 7: Stop Arbitration 6: Reply High 5: Pause 4: Reply Low 3: Hold 2: Request High 1: Request low 0: No request Second Cycle L: Packet length (0 = >2 cycles, 1 = >9 cycles) The four priorities Request Low, Request High, Reply Low, and Reply High correspond to normal arbitration requests for the bus. In other words, they are used when the device registering the arbitration request actually intends to send a packet. Reply High is used only for cache replies; Reply Low only for memory replies; and Request High for most requesters such as processor and IO caches Request Low is used only by background devices that can tolerate arbitrarily long delays in getting grants from the arbiter. Again in this embodiment, a client may issue multiple arbitration requests back to back, in which case a separate request is registered for each pair of request cycles. Furthermore, the clients are responsible for ensuring that they do not exceed the implementation limit that is imposed by the arbiter on the number of arbitration requests that the arbiter can register on behalf of a given client. In keeping with the above-described arbitration rules, higher priority arbitration requests are serviced before lower priority requests, and arbitration requests within the same priority level are serviced in approximately round-robin order. The other arbitration priorities that are supported by this embodiment (NoRequest, Hold, pause, and Stop) are available to permit the clients to request special service from the arbiter for their host bus. These special arbitration requests are communicated to the arbiter by one cycle requests that specify the arbitration priority. A bus client uses NoRequest if it does not want to request any service from the arbiter. Hold is used by a client that wants to prevent the arbiter from granting any requests for request packets (priorities below Hold). Thus, Hold is similar in purpose and function to the demand system-wide hold and release demand for system-wide hold encodings of the arbitration requests that were employed in the previously described embodiment. In this embodiment, however, the arbiter stays in the Hold state for only as many cycles as the client asserts the Hold code. Pause is an encoding that is unique to this embodiment. It can be asserted by caches to avoid getting flooded by replies generated by memory. Finally, Stop is used when a device wants to stop all arbitration. It causes the arbiter to stop granting the bus for as many cycles as any client asserts the Stop code. Thus, it will be understood that the Stop code is functionally similar to the SStop signal that was contemplated by the initial embodiment. Gnt_L and GntType_L are used by the arbiter to inform a client that it has been selected by the arbiter to be the next bus master. These signals are asserted for just one cycle to confer bus mastership upon the selected bus client for a sequence of subsequent cycles, with GntType_L indicating the priority of the arbitration request for which the grant is being given. To that end, GntType_L suitably is encoded as follows: 7: Stop Arbitration 6: Grant Reply High 5: Reserved (not used) 4: Grant Reply Low 3: Reserved (not used) 2: Grant Request High 1: Grant Request Low 0: No Grant A given client has a valid grant from the arbiter for its bus only when Gnt_L is asserted and GntType_L for the that client is non-zero. In this embodiment, if Gnt_L and GntType_L are asserted on cycle i at the interface 101 for a given client device, the client can drive its outgoing unidirectional or bidirectional bus segment in cycle i + 2. Fig. 15 shows the timing of the more important arbitration request and grant signals at the device-bus interface 101 of the arbitration requester during the arbitration (a five cycle arbitration latency has been assumed) and the transmission of a packet. Fig. 14 should be kept in mind while reading Fig. 15. As in the above-described embodiment, the arbiter has two different mechanisms for implementing flow control. Arbitration priorities are the first of these flow control mechanisms. As will be understood, client devices that issue both request and reply packets always assign higher priorities to their arbitration requests for the transmission of reply packets than to their arbitration requests for the transmission of request packets. This alone would be sufficient to eliminate the congestion problem if devices were always ready to reply before the onset of congestion, but it may not be possible for all devices to satisfy this requirement. For example, it would impractical to expect slower devices, such as the memory controller 25 (Fig. 1), to respond at the arrival rate to the request packets they may receive. Furthermore, the input queue lengths that such devices would have to be able to accumulate without risk of overflowing would be prohibitively long. Thus, the arbiter implements a second flow control mechanism through its above-described responses to the Hold and pause arbitration request encodings. As will be appreciated, the arbiter's response to a Hold or pause request is not instantaneous, so the client devices have to reserve adequate headroom within their input queues to allow them to accumulate a few incoming packets while their Hold or pause request is taking effect at their bus arbiter. There is, however, a balance to be struck because the bus throughput can be adversely affected needlessly if any of its client devices request a Hold or a Pause too frequently. 3. Data/Control InterfaceThe data port and the optional receive port of the interface 101 (Fig. 13) are similar in purpose and function to the send and receive ports, respectively, of the interface 41 (Fig. 4). However, the HeaderCycleln and HeaderCycleOut signals of the interface 41 have been eliminated in favor of employing an inverse parity syndrome for identifying the header cycles of the packets. This is practical because parity is computed in this enhanced embodiment at the byte-level for each cycle of every packet on each bus. Given that each bus typically provides a 64 bit-wide multiplexed address/data path, this means that there are eight parity bits for each cycle of every packet. As a result, the correct even parity encoding for data cycles is separated from the correct odd parity encoding for header cycles by a Hamming distance of 8, which is believed to be ample separation to prevent this unusual use of parity from compromising the ability to detect parity errors using standard error detection techniques. Another distinguishing feature of the interface 101 is that a BidEN_L signal is applied to its control port to affirmatively indicate whether the interface 101 is connected to a unidirectional bus segment or a bidirectional bus segment. When BidEN_L is asserted or true ( 1 ), the Dataport is operated in a bidirectional mode to support bidirectional packet communications back and forth between a client device and a bidirectional bus segment. One the other hand, when BidEN_L is deasserted or false ( 0 ), the Dataport is operated in a unidirectional output mode, and the ReceiveOption port is operated in a unidirectional input mode. 4. Consistency portThe consistency port of the interface 41 shown in Fig. 4 has no direct counterpart in the interface 101 of Fig. 13, but it will be seen that the consistency signals have been merged into the arbitration port of the interface 101. This presentational change has been made because it has been found that the arbiter for each bus is a convenient place (a) for logically ORing the ReqShared_L signals from the bus clients (identified previously as the SharedOut signals) to provide a GrantShared_L signal (identified previously as the Sharedln signal) for those clients, and (b) for logically ORing the ReqOwner_L signals from the bus clients (identified previously as the OwnerOut signals) to provide a GrantOwner_L signal (identified previously as the Ownerln signal) for them. Indeed, ReqShared_L, GrantShared_L,ReqOwner_L, and SharedOut_L are functionally equivalent to the SharedOut, Sharedln, OwnerOut, and Ownerln signals, respectively, of the interface 41, so the SharedOut, Sharedln, OwnerOut, and Ownerln nomenclature will be used to refer to those signal hereinbelow in the interest of simplifying the description of the extended data consistency protocol. An additional advantage of merging the consistency signals into the arbitration port of the interface 101 is that it facilitates combined parity checking of the arbitration and consistency input and output signals, such as through the use of single bit parity encoding at the interface 101 for the output signals and at the arbiter for the input signals. C. TransactionsThe transactions that have been defined for this embodiment are: Again, the first cycle of every request and reply packet is a header cycle. Returning to Fig 11, it will be seen that the header cycle for the request packets is formatted in this embodiment to have a six bit wide command field (including a request/reply flag bit) to provide sufficient capacity for the encoding of the increased number of transactions that have been defined, together with a forty-two bit wide address field. The two higher order bits of the address field are employed to specify the size (SSize) of an addressed single for the various single transactions that have been implemented (WriteSingleUpdate, I/OReadSingle, etc.), while the forty lower order bits of this field are available for specifying a byte address in either the I/O address space or the memory address space (i. e, the physical address space). One implementation employs only thirty-six of these byte address bits, so the four remaining bits (e.g., the four higher order bits of the byte address) are reserved for future address extensions (see the above description of the provision that is made for reserved or unused address bits). The request packet header cycle of Fig. 11 additionally includes a PLen bit for signaling whether the packet is a long (9 cycle) packet or a short (2 cycle packet). This encoding is redundant with the command that is carried in the command field of the header, but it permits the proper decoding of yet undefined commands that may be associated in some instances with long packets and in others with short packets. Furthermore, there a Ow bit for controlling the state of the owner bit that is maintained on any given data block by a cache requestor which initiates a transaction that may affect the value or the shared status of the given data block. The transactions of this embodiment that fall into that category are WriteSingleUpdate, WriteSinglelnvalidate, SwapSingleUpdate, SwapSinglelnvalidate, and ReadBlock. The state of the Ow bit in the headers of the request packets for those transactions indicates whether the requestor is or is not prepared to accept the ownership of the data block to which the transaction pertains. For all other transactions, the value of the Ow bit is maintained in a false ( 0 ) state. The headers of the request packets of this embodiment also contain an eight bit wide DevicelD field and a four bit wide SublD field, which are similar in purpose and function to the DevicelD's that are carried by the headers of the above-described embodiment (in this instance, the SublD's may be employed for enabling a bus client device to disambiguate replies to multiple outstanding requests, or the SublD field may be employed to encode internal or pendingState for a transaction requestor to avoid having to store that state internally of the requestor (see the discussion of the consistency protocol). The header shown in Fig. 11 additionally includes an error bit (Err) and an unused bit, both of which are maintained in a false ( 0 ) state in request headers (the Err bit is meaningful only in reply headers). A comparison of Fig. 12 with Fig. 11 will confirm that the header cycle for a reply packet is bit-by-bit identical to the header of the corresponding request packet, except that the request/reply bit of the command field is inverted to identify the packet as a reply; the length (i. e., long or short) of the reply packet is encoded by the PLen bit; the Err bit is set to a true ( 1 ) state or maintained in a false ( 0 ) state depending on whether the responder encountered an error or not while assembling the reply; the state of the Ow bit is employed to indicate whether the requestor is or is not permitted to acquire ownership of the data block to which the transaction pertains; and the unused bit of the request header is employed as a shared (Sh) bit to signal whether the data to which the corresponding request was addressed was shared or not at the time the request packet was received (a more rigorous description of such shared data appears hereinabove). 1. Memory Related TransactionsThe memory access transactions that have been provided for this embodiment are ReadBlock, NonCacheableReadBlock, FlushBlock, WriteBlock, WriteSingleUpdate, WriteSinglelnvalidate, SwapSingleUpdate, SwapSinglelnvalidate, and KillBlock. The ReadBlock, WriteBlock, and FlushBlock transactions are equivalent in most respects to the correspondingly named transactions of the first embodiment, except that these and the other block transactions of this embodiment utilize an eight cycle data transport unit (i. e., eight bus cycles, each of which contains eight contiguous bytes). Furthermore, the WriteSingleUpdate transaction is functionally similar to the WriteSingle transaction of the earlier embodiment, but its name has been changed to distinguish it from the newly defined WriteSinglelnvalidate transaction. Likewise, SwapSingleUpdate is a relatively minor modification of the above-described ConditionalWriteSingle transaction (i. e., SwapSingleUpdate is used to perform atomic reads and writes, rather than the atomic read-modify-write that a ConditionalWriteSingle carries out). It is identified as an Update transaction to differentiate it from the newly defined SwapSinglelnvalidate transaction. The Write Singlelnvalidate and SwapSinglelnvalidate transactions have been defined to provide write invalidate-style counterparts to the WriteSingleUpdate and SwapSingleUpdate transactions, respectively. They enable a cache requestor to update its copy of a specified data block, while causing any other cache that contains a copy of the same data block to invalidate its copy, unless the invalidation request is addressed to a data block upon which the receiving cache happens to have a transaction pending. As will be recalled, a cache can invalidate or delete any of its data blocks simply by clearing its Valid bit for the data block to a false ( 0 ) state. In this embodiment, the ownership of a data block that has been modified after being read out of main memory 13 (Fig. 1) does not necessarily belong to the cache for the processor that last wrote into it. Instead, the transfer of data block ownership is controlled by the state of the Ow bit in the header cycles of the request and reply packets for the WriteSingleUpdate, WriteSinglelnvalidate, SwapSingleUpdate, SwapSinglelnvalidate, and ReadBlock transactions. More particularly, all caches, except the requestor, that match on a WSIRply, a WSURply, a SSIRply, or a SSURply unconditionally clear their owner bits for the specified data block to a false ( 0 ) state. The requestor, on the other hand, sets ( 1 ) or clears ( 0 ) its owner bit for that data block upon receiving such a reply depending on the state of the Ow bit in the reply. If the Ow bit in the reply header is set to a true ( 1 ) state, the requestor sets its owner bit for the data block to a true ( 1 ) state. But, if the Ow bit in the reply header is cleared to a false ( 0 ) state, either because the Ow bit in the corresponding request packet was cleared to a false ( 0 ) state by the requestor or because the responder cleared the Ow bit to a false ( 0 ) state for some other reason while preparing the reply, the requestor then clears its owner bit for the data block to which the transaction pertains to a false ( 0 ) state. As will be appreciated, the main memory 13 (Fig. 1) is the default owner of all data blocks in the physical address space. Accordingly, if the header of a WSlRqst, a WSURqst, a SSlRqst, or a SSURqst contains a false ( 0 ) Ow bit, the memory 13 ordinarily is updated in accordance with the new data that is provided by the request. Of course, a cache that issues a SSlRqst or a SSURqst still is responsible for providing the old data to its processor in support of the read phase of these transactions, so the requestor retains that datum value at least until it receives the reply to its request. The Ow bit is also used in ReadBlock transactions. Specifically, it is set to a true ( 1 ) state in a RBRqst that is issued by a cache requestor as a prelude to a write by their associated processors for signaling that the requestor desires to set its owner bit for the specified data block to a true ( 1 ) state when it receives corresponding RBRply. Thus, it will be understood that the Ow bit in the header of a RBRqst permits an accelerated transfer of ownership of the specified data block to the requestor. Another distinguishing feature of the ReadBlock transaction for this embodiment is the provision that has been made for enabling a RBRply to inform the requestor whenever a memory error occurs while fetching the data that should be returned to the requestor in any of the data cycles of the reply. If the responder finds that any such data fetch error has been made, it substitutes a memory fault (MemFault) cycle for each of RBRply data cycles that are affected by the error or errors. A MemFault cycle is uniquely identifiable because (a) the parity for it is inverted to the odd parity of a header cycle, (b) it contains the command code for Noop, and (c) its DeviceID and SubDeviceID helds are empty (all 0's). An error code identifying the type of memory error that occurred is carried by the thirty-two lower order bits of such a MemFault cycle. An important advantage of providing such a memory fault cycle mechanism is that it permits the responder to issue a RBRply while it still is performing the requested memory read operation, which means that the memory latency can be reduced. KillBlock is a new transaction that has been defined to enable second or higher level caches (as well as main memory) to remove unused data blocks from the lower level caches to which they branch For example, returning for a moment to Fig. 1, the cache 19a could initiate a KillBlock to remove all copies of a specified data block from all of caches 16aa-16aj that are on the cluster bus 15a. More particularly, the KillBlock transaction is important because it permits a second or higher level cache to victimize an existing data block so that the storage location that was allocated to that data can be reallocated for storing the new data that the cache acquires by performing a ReadBlock on its upper or higher level bus (i. e., the global bus 26 in the case of the cache 19a). As will be recalled, these higher level caches initiate a ReadBlock on their upper bus whenever they miss on a RBRqst of any of the caches on their lower level bus (e.g., the bus 15a). Thus, the KillBlock transaction has been defined to avoid the potentially cumbersome associator coverage requirement that was imposed on the second or higher level caches of the initial embodiment. More particularly, it will be recalled that associated coverage can be provided for the first level caches by selecting each of the second level caches 19a-19i to have (a) a capacity that at least equal to the sum of the capacities of the first level caches that exist below them, and (b) a degree of associativity that is at least equal to the sum of the associativities of those first level caches. However, the KillBlock transaction provides an alternative and potentially less costly technique for ensuring that the second level caches provide full coverage for the their first level, child caches (i. e., the first level caches to which they branch). To perform a KillBlock, a higher level cache selects a potential victim data block through the use of a suitable victimization algorithm (any of the well known victimization algorithms can be employed), and then checks the state of its owner bit for the selected data block. If its owner bit for the potential victim block is set to a true ( 1 ) state, the KillBlock initiator first issues a RBRqst on its lower level bus (i e., the cluster bus 15a in the case of the second level cache 19a). This RBRqst is addressed to the potential victim, so it allows the KillBlock initiator to update its copy of the potential victim when it receives the corresponding RBRply. After updating itself if necessary (no update is performed if the KillBlock initiator has its owner bit for the potential victim cleared to a false ( 0 ) state), the KillBlock initiator uses its lower level bus to issue a KBRply that is addressed to the potential victim. Each of the lower level caches (e. g., the caches 12aa-12aj) that matches on this KBRply clears its Valid bit for its copy of the specified data block, unless it has a transaction pending thereon. The KillBlock initiator next issues a KBRqst on its lower level bus. This KBRqst is addressed to the potential victim, so the KillBlock initiator checks the state of its GrantShared_L input signal (in other words, its Sharedln signal) when it receives its KBRqst to determine any of the lower level caches asserted ReqShared_L (or SharedOut) in response to its KBRqst. If so, the KillBlock initiator resets itself to postpone the victimization of the selected data block until some future time. However, if none of the lower level caches assert ReqShared_L (SharedOut) upon receiving the KBRqst, the KillBlock iniator has confirmation that there are no copies of the specified data block in any of the caches on its lower level bus, so it theninitiates a FlushBlock on its higher level bus to write its copy of the data block back to main memory 13 (or back to the next higher level cache). Another transaction that has been defined to increase the efficiency of the memory system is the NonCacheableReadBlock transaction. This transaction is equivalent to the above-described ReadBlock transaction, except that it does not affect the shared/not shared status of the data block to which it is addressed. Its application, therefore, is limited to reading data blocks from the consistent memory space (i. e., physical address space) on behalf of non-cache requestors, such as DMA I/O devices. 2 I/O TransactionsThe I/O transactions have been extended to provide additional transactional support for reading and writing data blocks from and to I/O devices (IOReadBlock and IOWriteBlock, respectively) and for performing atomic read-writes to I/O devices (IOSwapSingle). Moreover, the BlOWrite transaction of the first embodiment has been omitted in favor of providing a more specific. Interrupt transaction that is briefly described in the next Section. 3 Miscellaneous TransactionsThe Lock and UnLock transactions are two of the more interesting extensions in this category Lock can be invoked by a cache requestor to prevent any bus client, except for the requestor, from performing any transaction that might affect the value of a specified data block (i. e., WriteBlock, WriteSingleUpdate, WriteSinglelnvalidate, SwapSingleUpdate, SwapSinglelnvalidate, or KillBlock). It, therefore, is useful for imposing a degree of atomic ordering on the transactions that are imposed on a given data block. It also is useful to preventing a cache from having to perform an indefinite number of retries on a RBRqst that returns stale data because of the frequency of the writes to the requested data block. Lock conveniently is invoked by registering the address (LockAddress) of the locked data block with all cache clients and by providing a flag bit (LockAddressValid) bit that is set to a true ( 1 ) state for all caches, other than the requestor. Thus, the current implementation of this feature permits no more than one data block to be locked at any given time. UnLock is the counterpart transaction that the holder of a Lock can invoke to clear its Lock. It accomplishes that by causing each of the caches to clear its LockAddressValid bit for the specified data block. As previously mentioned, an Interrupt transaction also has been defined for signaling interrupts to processors. Processor interrupts are beyond the scope of this invention, but it is noted that this Interrupt transaction may be targeted to a specified processor or broadcast to all processors in the system. Demaplnitiate is similar to the above-described DeMap transaction. In this instance, however, the virtual-to-physical address translation is performed by transaction look aside buffers (not shown) that are provided for the processors 12aa-12ij (Fig. 1), respectively. Thus, a DeMapTerminate transaction has been defined, so that each of the processors 12aa-12ij can cause its first level cache 16aa-16ij to initiate this transaction when the requested DeMap has been completed. The caches 16aa-16ij assert ReqShared_L (SharedOut) while their processors 12aa-12ij are performing a demap operation, so a DeMaplnitiate requestor obtains confirmation that all of the processors 12aa-12ij have completed the requested demap when it matches a DmIRply that has its Sh (in other words, replyShared) bit cleared to a false ( 0 ) state. D. Data ConsistencyThe WriteSinglelnvalidate, SwapSinglelnvalidate and KillBlock transactions that have been defined for this embodiment of the invention reduce the amount of data block sharing that occurs, thereby causing the data consistency protocol to behave as a hybrid update/invalidate protocol, rather than as a pure update protocol as in the first embodiment. This change has been made for the purpose of increasing the efficiency of the consistency protocol. Even though it is still uncertain whether there is a marked improvement in the efficiency of the consistency protocol because of these new transactions, it is clear that the new transactions do not adversely affect either the utility or the efficiency of the consistency protocol. Another change that has been made to the consistency protocol relates to the use of the Ow bit in the header cycles of the request and reply packets. As pointed out above, this bit gives the requestors and responders that partcipate in the reads and writes that are carried out within the consistent memory space some additional control over the transfer of the ownership of the data blocks to which such reads and writes are directed. It does not, however, affect the validity or utility of either the pure update consistency protocol or the hybrid update/invalidate consistency protocol. Rather, it provides support for caches that are implemented using an architecture (not shown) that relies upon replicated, asynchronously maintained, address/status tags for keeping track of whether specified data blocks are shared or not and owned or not. Status changes propagate from tag-to-tag of such a cache, so a race condition can occur whenever a processor issues a write to a locally cached data block that appears to be not shared and not owned from the processor side of the cache. To avoid such race conditions, a cache may be required to initiate a WriteSingle whenever its associated processor issues a write directed toward a data block for which the cache is holding false ( 0 ) shared and owner status bits, but this increases the bus traffic. Therefore, to reduce the frequency of such Write Singles, the Ow bit has been included. Specifically, when issuing a RBRqst to obtain a copy of a data block for which its processor has a pending write, a cache can set the Ow bit in the header cycle of its RBRqst to a true ( 1 ) state, thereby notifying the responder that the requestor is requesting that the Ow bit be set to a true ( 1 ) state in the corresponding RBRply.
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A method for preserving data consistency for all physical addresses used by a shared memory multiprocessor: said multiprocessor having a main memory (13) for storing a complete, non-overlapping data cover for all of said physical addresses; a packet switched bus (26) coupled to said main memory; a plurality of data processing means (12aa-12ij) for manipulating data at respective, potentially overlapping sets of said addresses; and a corresponding plurality of cache memories (16aa-16ij) coupled between said bus and respective ones of said data processing means for giving the respective data processing means read and write access to cached versions of the data stored at a respective sets of said addresses said cache memories being snoopy, write back cache memories for initiating, responding to, and participating in transactions on said bus for reading copies of the data at selected addresses into any given one of said cache memories in reply to a read request made by said given cache memory, and for broadcasting data updates for any selected address from any given one of said cache memories to all of the other of said cache memories in reply to a write request that is made by the given cache memory whenever it is determined that such an update is directed to an address that is shared by a plurality of said cache memories: each of said transactions including a request packet that is issued by the cache memory requesting the transaction and a time dissociated reply packet that is issued by a responder; said request and reply packets uniquely identifying the cache memory requesting the transaction, the requested transaction type, and the address to which the transaction is directed; the reply packet for each read transaction further including a copy of the data at the address to which the read transaction is directed in a data transport unit containing a predetermined number of contiguous addresses that are read into and cached by the cache requesting the transaction as a data block; and the reply packet for each write transaction further including the data update for the address to which the write transaction is directed, such that said update is written into all cached copies of said address in response to the reply packet: said method comprising the steps of maintaining, for each of said cache memories, a shared state and an owner state for each data block cached therein; maintaining, for each of said cache memories, a pending state for each data block cached therein that is subject to a pending transaction of the respective cache memory; monitoring all bus transactions for setting the shared state for any given data block within any given one of said cache memories to a true state whenever it is determined that the given data block is shared by at least one other of said cache memories; setting a reply shared flag in the reply packet for said read or write request to a true state if the request packet is addressed to shared data; checking the shared status within any given cache memory that receives a write from its respective data processing means to determine whether said write is directed to a shared data block and, if so, causing said given cache memory to issue a corresponding write request on said bus for broadcasting said write to all other caches containing said data block; setting the owner state for a given data block to a true state within a given cache memory whenever its respective data processing means is responsible for providing a latest update for said given data block; transferring data block ownership of shared data blocks from cache memory to cache memory upon receiving the reply packets for the write transactions by which said data blocks are updated, whereby the owner state for a given data block is set to a true state in, at most, one of said caches at any given time; checking, on each request, to determine whether any of said cache memories assert ownership of the address to which said read request is directed; reading the data for the reply packet for such a read request from a cache memory owner of the data block containing the address to which the read request is directed or from said main memory, depending on whether ownership is asserted or not, respectively, in response to said read request; updating the pending state for each pending read and write transaction of said cache memories to reflect any changes in the shared status of the address to which said transaction is directed that occur while the transaction is pending; and logically ORing the pending state for each pending read transaction of each cache memory with the reply shared flag in the reply packet for such transaction, so that the shared state for the data block that is loaded into said cache memory in response to said reply packet is set to a true sate if said data block becomes shared at any time prior to the receipt of said reply packet.
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XEROX CORP; XEROX CORPORATION
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DOUADY CESAR B; SINDHU PRADEEP S; DOUADY, CESAR B.; SINDHU, PRADEEP S.
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EP-0489558-B1
| 489,558 |
EP
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B1
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EN
| 19,960,306 | 1,992 | 20,100,220 |
new
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H01R43
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H01R43
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H01R43, H01B13
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H01R 43/20, H01R 43/048
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Electrical harness assembly apparatus
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An apparatus for producing wire harness assemblies, each assembly comprising a plurality of cable wires having opposed ends with terminals (156) mounted to said wires at one end of said cable wires and a housing (154) at one of said ends with a plurality of said terminals mounted therein, said apparatus comprising an insertion station for inserting the terminals into the housing, at least one probe assembly (211) at the insertion station, said probe assembly including a plurality of probes corresponding in number to the number of terminals (156), each said probe being configured to engage a corresponding terminal; means (217) for moving the probes selectively into and out of engagement with the terminals (156); and means (216) for moving the housing (154) relative to the terminals (156) and the probes such that the probes guide the housing during the insertion of the terminals.
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Lighting systems for buildings typically are wired in the field by electricians. The electrician typically will run a shielded multi-conductor cable, such as BX cable, from a central panel through conduits that may be mounted in suspended ceilings or walls of a building. The cables that extend from the central panel typically will lead to distribution boxes, from which the electrician will extend a plurality of separate cables to lighting units, switches or the like. The electrician working in the field will strip insulation from the various cable wires and manually complete the electrical connections at the central panel, the distribution boxes and the junction boxes. Although this standard prior art process is effective, it is extremely labor intensive. Considerable manufacturing efficiencies have been achieved with respect to the stripping of insulation from wires, crimping terminals onto the wires and mounting terminated leads into electrical connector housings. In particular, the prior art includes many variations of apparatuses and processes for making electrical harnesses for signal lines having a plurality of insulated conductors terminated at each respective end, with the terminals thereof mounted in associated housings. The available harness assembling equipment, however, generally is operative to repeatedly perform a plurality of substantially identical operations, with each terminal, each wire and each harness being identical. Some known harness assembling equipment includes means for adjusting the crimp height to enable the harness assembling equipment to be changed over from making harnesses of a first dimension and/or type to making harnesses of a second dimension or type. Examples of this prior art include US-A- 4,587,725 which issued to Ogawa et al. on May 13, 1986; US-A- 4,790,173 which issued to Boutcher, Jr. on December 13, 1988; US -A- 4,707,913 which issued to Moline on November 24, 1987; and US-A- 4,400,873 which issued to Kindig et al. on August 30, 1983. Each of these references shows apparatus for selectively adjusting the stroke of the crimp press. Another prior art terminating press is shown in US-A- 4,576,032 which issued to Maack et al. on March 18, 1986 and which shows a crimp press having deflectable members to account for certain ranges of variations in the dimensions of a crimped terminal. The prior art includes power wire harness assemblies that are intended to eliminate a substantial portion of the on-site wiring that typically is completed by electricians in the field. In particular, extremely effective power wire harness assemblies have been provided by Lithonia-Reloc of Conyers, Georgia. These assemblies include a shielded cable, such as BX cable, having a plurality of insulated conductors therein and having suitable electrical connectors securely mounted at opposed ends. The Reloc power wire harness assemblies can be extended from one junction box to another, from one cable to another or from a cable or junction box to a lighting fixture. Many power wire harnesses sold by Reloc include drop wires which extend from one of the two cable connectors of the power wire harness. The drop wire, with an associated connector mounted thereto, may be adapted to extend into a knockout on a lighting fixture. The typical power wire harness assembly manufactured by Lithonia-Reloc will include drop wires extending from the cable connector only at one end of the cable. The cable connector having drop wires extending therefrom will be mated to a cable connector on another harness assembly that has no drop wires. Thus, a daisy chain of power wire harness assemblies may be created, with drop wires extending from one cable connector in each harness assembly, and from one cable connector in each mated pair of cable connectors. The above described Reloc power wire harness assemblies substantially decrease the amount of on-site labor required by electricians. However, these prior art assemblies have not been well suited for the above referenced prior art automated harness assembling equipment. In particular, the terminations in each power wire harness assembly will vary significantly from one terminal to the next. For example, some terminations will require grounding clips, while others will not. Some terminals will include drop wires, while others will not. The drop wires may be 12 gauge solid or stranded wire, 18 gauge solid wire or 18 gauge stranded wire, with the particular selection of drop wires varying from one harness to the next. In most instances, the terminations at one end of the harness assembly will be significantly different from the terminations at the opposed end. In addition to the differences between the terminations on any single harness assembly, it is necessary to produce many different types of harness assemblies in accordance with the voltage and phasing requirements of the building's electrical system. For example, the gauge and number of conductors in the power cable may vary significantly from one harness assembly to the next. More particularly, the power cables are likely to include anywhere between three and five conductors per cable, with each conductor being either 12 or 18 gauge and being either solid or stranded. The length of the respective cables also will vary significantly from one harness assembly to the next. In view of these variables, the production of power wire harness assemblies has not been automated, and has merely moved the labor intensive assembling work from a largely uncontrolled field location to a more closely controlled factory location. Attempts to improve the efficiency of the above described power wire harness assembling process is also rendered difficult by the high degree of quality control required for power wiring in buildings. Quality control often can be assured by visually inspecting the harnesses at various stages of their manual assembly. Automated harness assembling devices, however, make visual inspection during the manufacturing process more difficult. In many instances, the terminations produced by the prior art apparatus are substantially hidden from view when the completed harness is ejected from the prior art apparatus. In view of the above, it is an object of the subject invention to provide an apparatus for more efficiently producing power wire harness assemblies. It is a further object of the subject invention to provide a power wire harness assembling apparatus that can readily adjust to different termination requirements from one conductor to the next and from one harness assembly to the next. A further object of the subject invention is to provide an apparatus and process for efficiently completing a power wire harness wherein selected terminals of the assembly have drop wires simultaneously terminated with selected cable wires. Still another object of the subject invention is to provide a power wire harness assembling apparatus and process which substantially simultaneously checks the presence of terminals and guides the terminals into a housing. An additional object of the subject invention is to provide a cable fixturing apparatus which places cable wires at a first pitch during trimming, stripping and terminating operations, but which establishes a second pitch for insertion into a housing. SUMMARY OF THE INVENTIONThe subject invention is directed to an apparatus and/or a system of apparatuses operatively connected to one another for assembling power wire harnesses. In particular, the subject invention may comprise conveying means for conveying a multi-conductor cable to a plurality of assembly or work stations at which the various conductors are prepared, terminated and inserted into a housing. A conveying means of the subject invention may cooperate with pallets on which cables of preselected lengths may be coiled and fixtured. The conveying means may comprise means for selectively indexing the pallets to one or more work stations at which various harness assembling steps may be carried out. The system may include means for selectively permitting idling of the pallets while work is being performed at one or more downstream locations. The system may further include means for selectively disengaging pallets from the conveying means and maintaining disengaged pallets at fixed positions in proximity to one or more work stations of the system. Each pallet of the conveying means preferably comprises a pair of fixtures for rigidly fixturing each end of the cable, such that the respective conductors thereof are in controlled spaced relationship to one another, with the respective ends of the conductors being disposed for selected work to be carried out thereon. The fixtures may be operative to change the spacing between the conductors at selected work stations. The system of the subject invention may comprise a work station with means for cutting and stripping drop wires to be terminated with selected conductors of the cable. This station may further comprise means for automatically placing the drop wires into selected wire receiving portions of the fixtures on the pallets. The drop wires may be positioned in the fixtures prior to or after placement of the cable wires therein. The order in which the drop wires are placed in the fixtures may be selected to achieve the most efficient flow of pallets through the work stations of the system. The system may further comprise one or more stations for trimming the cable wires to selected lengths, and/or for stripping selected lengths of insulation from the cable wires. The stripping preferably is carried out by cutting means which cuts through the insulation and subsequently pulls the insulation relative to a fixedly positioned pallet on which the cable wires are fixtured. The positioning of the drop wires relative to the cable wires can be either before or after the trimming and stripping of the cable wires as noted above. However, in embodiments where the drop wires are positioned first, it may be necessary to dispose the stripped end of the drop wire axially rearwardly of the end of the cable wire to prevent interference between the drop wire and the trimming and stripping means for the cable wire. In these latter embodiments, the station for stripping the cable wire may further comprise means for pulling the end of the drop wire axially forwardly and into alignment with the stripped end of the cable wire. The system of the subject invention may further comprise one or more stations for crimping terminals to the ends of the wires. The crimping station may be in proximity to means for feeding grounding clips to selected terminals in the power wire harness. The crimping station preferably is operative to sequentially crimp terminals to the conductors at each end of the power wire harness assembly. However, the sequential crimping may be carried out simultaneously at both ends of the harness assembly. The crimping apparatus may comprise programmable means for selectively varying the crimp height for each sequential crimp as needed. In particular, the crimp height will be adjusted depending upon the gauge of wires to be terminated, the presence or absence of a grounding clip and the presence, absence and/or size of a drop wire. The adjustment of the crimp height may be carried out by at least one cam wedge means which may be linearly slidable relative to the crimping press to effectively alter the position of the head of the crimp press for both the conductor and the insulation at the completion of a crimping cycle. The crimp press also may be programmable to control the number of crimping operations carried out at each end of the harness assembly in accordance with the number of conductors that are present at a particular end of the harness assembly. More than one crimping station may be provided to achieve optimum flow of harness assemblies through the system. The crimping station may further comprise means for assessing the quality of the crimped termination for each terminal. The system of the subject invention may further comprise a station for inserting the terminated wires of the cable into housings. In particular, housings may be sequentially fed into proximity to the fixtured ends of the cables. Means also may be provided for urging the terminated wires into a center-to-center spacing corresponding to the pitch required for the connector. The mounting of the terminals into the housings preferably is carried out with guide means for ensuring that the terminals are urged into the respective housings without potentially damaging contact between the terminals and the housings as part of the insertion process. The guide means may comprise probes that are directed through terminal receiving apertures in the housing and which subsequently engage the terminals. The probes may define either pins for engaging pin receiving terminals on a harness assembly or concave structures for engaging pin terminals, blades or other such male terminal means on the harness. The housing and the terminals may be moved relative to one another after the probes have properly engaged the terminals, to enable the probes to guide the terminals into the housing. The probes may comprise portions of test assemblies which test for the presence of terminals. The test assembly may be programmable to test for the presence of the specified number of terminals for the particular harness assembly. The absence of a specified terminal will be sensed by the probes and may generate a signal to identify an unacceptable harness assembly. The completed harness assembly may advance to other stations for mounting shells over the connector housing. These other stations on the system may be employed to test the completed harness assemblies, mount connectors to the drop wires and/or prepare the completed harnesses for shipment or storage. BRIEF DESCRIPTION OF THE DRAWINGSFIG. 1 is a perspective view of a prior art power wire harness assembly that is manufacturable by the system of the subject invention. FIG. 2 is a schematic view of the system of the subject invention. FIG. 3 is a top plan view of a pallet for use in the system of the subject invention. FIG. 4 is a front elevational view of a pallet in proximity to a crimper of the subject system. FIG. 5 is a side elevational view of the wire continuity and position sensor assembly of the subject system. FIG. 6 is a front elevational view of the crimp station of the subject system. FIG. 7 is a top plan view of a pallet at the crimp station. FIG. 8 is a front elevational view of the crimp adjustment apparatus. FIG. 9 is a front elevational view of an alternate wire gathering assembly at the housing insertion station. FIG. 10 is a front elevational view of a wire lifter assembly for use with the wire gathering assembly. FIG. 11 is a side elevational view of the housing insertion station. FIG. 12 is a side elevational view of an alternative embodiment of the housing insertion station. FIG. 13 is a perspective view partly broken away of the housing push subassembly of the housing insertion station shown in FIG. 12. FIG. 14 is a front elevational view partly broken away of the pitch adjustment subassembly, of the housing insertion station shown in FIG. 12. FIG. 15 is a perspective view of the wire holding subassembly of the housing insertion station shown in FIG. 12. FIG. 16 is a front elevational view of an alternative embodiment of a wire holder mounted on a pallet. FIG. 17 is an exploded perspective view of an alternative wire continuity and position sensor assembly. FIG. 18 is a vertical sectional view, on enlarged scale, taken substantially on line 18-18 of FIG. 8. FIG. 19 is a perspective view of the swing arm assembly of FIG. 15. FIG. 20 is a detail side elevational view of a portion of the terminal positioning subassembly shown in FIG. 12. FIG. 21 is a detail rear elevational view of the portion of the terminal positioning subassembly shown in FIG. 20. FIG. 22 is a detail front elevational view of a portion of the wire separator of FIG. 17. FIG. 23 is a detail side elevational view of a portion of the wire separator of FIG. 22. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTThe system of the subject invention is operative to efficiently produce a prior art power wire harness as indicated generally by the numeral 10 in FIG. 1, which may be one of the harness assemblies of the type manufactured by Lithonia-Reloc. The power wire harness 10 depicted in FIG. 1 is intended for interior applications, such as the fluorescent lighting widely employed in the suspended ceilings of commercial, office or light industrial buildings. It is to be understood, however, that many other applications for the power wire harness 10 exist. The power wire harness 10 comprises a cable 12, which may define a BX type of cable having a flexible outer metal shield. As depicted in FIG. 1, the cable 12 defines a relatively short length. It is to be understood, however, that the length of the cable 12 is subject to great variation depending upon the specifications established for the end use of the power wire harness 10. The cable 12 of the harness 10 includes a plurality of separately insulated conductors or cable wires (not shown) therein. The number and the cross sectional dimension or gauge of the separate cable wires may vary significantly from one power wire harness 10 to another. For example, the cable 12 may comprise a total of four cable wires therein, which are intended to define two hot wires, one neutral wire and one ground on the completed harness 10. Other cables, however, may have only three cable wires, while others may have five. The particular number of cable wires within the cable 12 will depend upon voltage, phasing and other system parameters. The power wire harness assembly 10 further comprises connectors 14 and 16 mounted respectively to the opposed ends of the cable 12. The connectors 14 and 16 include electrically conductive terminals (not shown) mounted therein and corresponding in number to the number of cable wires in the cable 12. The connectors 14 and 16 are defined by outer metallic shells 18 and 20 respectively that are mechanically joined to the cable 12. The connectors 14 and 16 further include non-conductive molded housings 22 and 24 respectively in which the terminals (not shown) are mounted. The connector 16 includes drop wires 25-28 extending therefrom. The drop wires 25-28 are terminated with the cable wires (not shown) to the respective terminals (not shown) within the connector 16. The drop wires 25-28 are terminated to a fixture connector 30 which can be snapped into engagement with a knock-out aperture in a lighting fixture for subsequent pluggable electrical connection to a corresponding connector on a lighting fixture. It will be noted that the connector 14 does not include a corresponding array of drop wires. A plurality of power wire harnesses 10 of selected lengths may be employed in daisy chain fashion by electrically joining the harnesses 10 in end-to-end relationship. Thus, the connector 14 of one power wire harness 10 will be mated with a connector 16 on a second power wire harness 10. The connections between power wire harnesses will be made in proximity to the knock-out apertures in the lighting fixtures, such that the drop wires 25-28 can be directed toward the lighting fixture. The fixture connector 30 then can be snapped into engagement with the knock-out aperture in the lighting fixture. It is to be understood that many of the power wire harnesses manufactured by the system and process of the subject invention will be similar to the harness 10 shown in FIG. 1, but will not include the drop wires 25-28. These harnesses will be used substantially like extension cords, and will minimize inventory problems of the specifically configured harnesses 10 having drop wires 25-28 extending therefrom. It also should be emphasized that the harnesses 10 are subject to many other variations as noted above. In particular, the specifications of the drop wires may vary considerably as to the number of wires, the gauge of the wires, and whether the wires are stranded or solid. The number and gauges of cable wires also can vary. Additionally, certain of the cable wires will be terminated with grounding clips, while others will not. The system for forming the power wire harnesses 10 is illustrated schematically in FIG. 2, and is identified generally by the numeral 32. The system 32 includes a chain track 34 along which pallets 36 are movable. The portion of the chain track 34 illustrated in FIG. 2 is operative to move the pallets 36 linearly in a direction indicated by arrow A . The system 32 further comprises a down elevator 38 and an up elevator 40 which define the extreme ends of the system 32. The system 32 further comprises a lower chain track (not shown) which also connects the down elevator 38 and the up elevator 40 but which is operative to travel in a direction opposite the direction indicated by arrow A . It is to be understood, however, that the system 32 may define a loop disposed at a single elevation and without the elevators 38 and 40. A pallet 36 is illustrated in greater detail in FIGS. 3 and 4. More particularly, the pallet 36 is a generally rectangular planar structure having a top surface 42 and an opposed bottom surface 44. The top surface 42 of the pallet 36 includes a plurality of cable guides 46 rigidly mounted thereto in spaced relationship to one another. The cable guides 46 enable a coil of cable 12 to be securely retained on the pallet 36, as shown in FIG. 3. The pallet 36 further comprises a pair of cable support brackets 48 having generally semi-cylindrical grooves 50 formed therein for receiving portions of the cable 12 adjacent the ends of the metallic shield thereon. The cable support brackets may optionally be provided with clamping means for securely, but releasably, retaining the cables therein. Wire holder assemblies 52 are mounted to the top surface 42 of the pallet 36 adjacent the cable support brackets 48. This particular embodiment of each wire holder assembly 52 comprises a pair of end supports 54 and 56 which are mounted to the top surface 42 of the pallet 36 in spaced relationship to one another. A plurality of wire guides 58-62 are disposed intermediate the supports 54 and 56 respectively. The wire guides 58-62 each include a notch in the top portion thereof dimensioned to engage one of the cable wires and to additionally engage one of the drop wires if required. The wire guide 58 is rigidly mounted to the end support 54. However, spring assemblies 63-66 are sequentially disposed intermediate adjacent wire guides 58-62 as shown in FIG. 3. Thus, the wire guides 59-62 can be collapsed relative to one another and urged respectively toward the wire guide 58. However, the forces exerted by the springs 63-66 will urge the wire guides into a fully extended position relative to one another such that the wire guide 62 is adjacent to the support 56. The wire holder assembly 52 further comprises core pins 68 and 69 which extend slidably through the support 56 and are attached to the wire guide 62. Thus, a force exerted on the core pins 68 and 69 will overcome the forces exerted by springs 63-66 and cause the wire guides 59-62 to be urged toward one another and toward the wire guide 58. In their extended condition, as shown in FIG. 3, the wire guides 58-62 define center to center spacings of approximately 14,93mm (0.588 inch). However, in their collapsed condition the wire guides 58-62 define center to center spacings of only about 8,026mm (0.316 inch) which corresponds to the pitch of the housing as explained below. Other selected center to center spacings in the expanded and collapsed conditions of the wire holder assembly 52 may, of course, be provided depending upon the requirements of the system. The object of the selective expansion and contraction of the wire holder assembly is to provide adequate room for trimming, stripping and crimping operations in the expanded condition, and also to enable efficient insertion of the terminated wires into closely spaced apertures in a housing. Another efficient but substantially less expensive alternative to the above described wire hold assemblies 52 is to replace wire holder assemblies 52 with a rigid wire holder assembly generally designated 200 (FIG. 16) with wire guide receiving slots 201 disposed at a center-to-center spacing of 14,93mm (0.588 inch), or other appropriate spacing for the terminals being employed. Wire holder 200 includes a two piece block assembly 202 and 203 with springs 204 secured therebetween. Block 202 has vertical apertures 205 therethrough to permit block 202 to slide on bolts 206. In the embodiment shown, wire retainer 207 has five wire receiving slots 201 spaced 14,93mm (0.588 inches) apart. Wire retainer 207 is made of polyurethane to permit wires 12c and 12d to be releasably held in each slot 201. As discussed below, an appropriate downstream station may then be provided to remove wires from the wire guides and to collapse the wires to a closer spacing for insertion into a housing as explained and illustrated below. The pallet 36 further includes a plurality of shot pin holes 70 which are engageable by shot pins 72 to lift the pallet 36 from the chain track 34 at selected work stations as shown in FIG. 3, and as explained further below. Returning to FIG. 2, the pallets 36 of the system 32 are movable along the chain track 34 to a plurality of different work stations. The first station is a cable load station 76. A technician may be disposed at location 76 to manually load coils of cable 12 onto the pallet 36 positioned at station 76. The cable 12 typically will be coiled to define a diameter of approximately 381mm (15 inches) with lengths of cable extending between 50,8 mm and 304.8mm (2 inches and 12 inches respectively) beyond the tangent point of the coil. The cable 12 will be pre-cut to a selected length and will have selected lengths of cable wires extending from the respective opposed ends of the shielding. Stations 77 and 78 are located downstream of the cable load station 76 and define stations for fixturing the cable wires within the wire holder assemblies 52. The stations 77 and 78 may be operated by one or more technicians depending upon the cycle times required for the system 32. For example, station 77 may be employed to position and fixture the cable wires at the first end of the cable 12, while station 78 may be employed to position and fixture wires at the opposed second end of the cable 12. The cable wires are mounted in the wire holder assemblies 52 in an unstripped condition. Additionally, in some operations, drop wires may be positioned manually in the fixtures immediately prior to the manual placement of the cable wires. Any drop wires that may be positioned at this station will be stripped and may have terminals attached to the trailing end. The drop wires will be positioned in the fixtures first and the cable wires will then be positioned with their unstripped ends axially forwardly relative to the ends of the precisely positioned drop wires. It should be noted that most drop wires will be automatically positioned at a downstream station as explained herein. Manual placement of drop wires will only be employed to achieve optimum cycle time in some situations. A trim and strip station 80 is disposed downstream from the cable wire fixturing stations 77 and 78. The trim and strip station 80 is initially operative to simultaneously trim the cable wires to specified lengths, such that the trimmed ends of the cable wires are at specified distances forward of the fixtures and the ends of any previously positioned drop wires. The station 80 subsequently is operative to strip a selected amount of insulation from each cable wire. As shown in FIG. 2, the trim and strip station 80 includes first and second trimming and stripping devices 82 and 84 for the respective first and second ends of each cable 12. The trimming and stripping devices 82 and 84 are operative to simultaneously cut all wires on a pallet 36 and then to simultaneously strip all wires on the opposed first and second ends of the cable 12. Such trimming and stripping devices are well known in the art. One manufacturer of such devices is Komax AG, Lucerne, Switzerland. The trimming and stripping devices 82 and 84 are operative to move relative to the pallet 36 for pulling the insulation from the conductor of each cable wire 12. This pulling movement of the trimming and stripping devices 82 and 84 also is operative to grip any drop wire that may be present and pull it forwardly to be aligned with the trimmed end of the cable wire. The drop wire station 86 is operative to programmably pay-out specified lengths of a selected drop wire, which may be 12 gauge solid wire, 18 gauge solid wire or 18 gauge stranded wire. The leading end of the length of drop wire is appropriately stripped and is programmably placed in a selected wire guide 58-62 of the wire holder assembly 52. The opposed end of each drop wire may be stripped, partially stripped or unstripped depending upon the particular connection to be made with the drop wires. As noted above, not all harness assemblies produced by the system 32 will require drop wires. In situations where drop wires are not required, the station 86 will merely define a test station. The drop wire station 86 (FIG. 5) includes testers 88 as shown in FIG. 5. Each tester 88 includes probes 90 which are disposed to be axially in line with any cable wires 12c or drop wires 12d that may be present. The probes 90 are operative to move axially forward to contact the ends of the conductors that may be present, and to test for the presence of each conductor that should be present, to test for proper position of the conductor and to test for continuity between opposed ends of each cable wire 12c. A failure of any test will generate a signal to identify the particular pallet for a special treatment which may vary depending upon the particular sensed condition. In some instances, the cable 12 will have to be scrapped, while in other instances appropriate corrective action may be employed, such as realigning the stripped end of a wire or positioning a drop wire. An alternative testing station indicated generally at 350 is shown in FIG. 17. Testing station 350 has two substations 351 and 352, one for each end of cable 12. The first substation 351 is utilized for testing the end of cable 12 having only cable, wires 12c. The second substation 352 is utilized for testing the end of cable 12 having both cable wires 12c and drop wires 12d. Substation 351 has five spring-loaded test probes 353 reciprocally mounted in lower contact holder 354 and oriented perpendicular to wires 12c. The test probes 353 project out of holder 354 a sufficient distance to permit contact with the conductor of stripped wires 12c. Electrical wires (not shown) are attached in known manner to the system controller. Pneumatic cylinder 355 is fixed to frame 356 and cylinder rod 357 is secured to block 358 which is secured to holder 354. When cylinder 355 is actuated, block 358 is forced upward and slides along guide rods 360 which extend therethrough. Tapered wire guides 359 are provided to guide wires 12c to probes 353. The second substation 352 includes the same structure as that of the first substation 351 and like numbers are used to describe like components. The second substation further comprises a wire separator 361 that is fixed to the top of guide rods 360. Wire separator 361 includes two outer insulating members 362 and 363 with a conductive plate 364 disposed therebetween. A wire (not shown) is attached to conductive plate 364 and extends to the system controller. Upper insulating member 362 is dimensioned so that a portion 365 of the upper surface of conductive plate 364 is exposed so that the stripped portion of drop wires 12d can contact portion 365 (FIG. 23). However, the portion 365 is sufficiently narrow so that a drop test wire probe 366 (described below) will contact the upper non-conductive member 362 rather than conductive plate 364 upon moving probes 366 towards wire separator 361. Drop wire test probes 366 are spring-loaded and mounted for reciprocal vertical movement in upper contact holder 367 in the same manner as probes 353 and also include electrical wiring to the system controller. Pneumatic cylinder 370 is secured to offset bar 371 and the cylinder rod 372 is fixed to block 378. Retracting cylinder 370 pulls block 378 downward and slides it along guide rods 373 which extend therethrough. Upper contact holder 367 is fixed to block 372. Offset bar 371 is fixed to shafts 374A which are driven by powerslide 375 that is fixed to frame 376. Proximity sensors 377 are connected to the system controller in known manner and are associated with proximity flag 380 so that the controller can confirm that the powerslide 375 has completed a stroke. In operation, a pallet 36 arrives at testing station 350 with wires 12c stripped and held in wire holder 200. The pallet is aligned so that wires 12c at each end of the harness 10 are located above probes 353 at the first and second substations 351 and 352. The wires 12c associated with substation 352 are located below wire separator 361 and the wires 12c associated with substation 351 are located beneath plate 379. Drop wires 12d having stripped ends are then inserted into the wire holder at substation 352 so that the stripped ends are located above wires separator 361. Power slide 374 is then actuated to slide offset bar 371 and the test probes 366 mounted thereon horizontally towards the drop wires until the test probes are located above the drop wires 12d and wire separator 361. Pneumatic cylinders 355 are then actuated to force probes 353 into contact with cable wires 12c. Pneumatic cylinder 370 is retracted which forces upper contact holder 367 downward. The drop wire test probes contact any drop wires that are located at substation 352. If no drop wire is present, the probe will contact upper ,insulating member 362. If a drop wire is present and is properly stripped, the probe associated with that drop wire will complete an electrical circuit between the conductive plate 364 and probe 366. The system controller will then test the wires to verify that each wire 12c at both ends of the cable 12 are in the correct position within wire holder 200. That is, the controller will determine whether the wires have been loaded into the wire holder in the incorrect sequence. If the controller does not sense the continuity between the ends of the wires, an error signal is generated. Likewise, if a drop wire is supposed to be present, probe 366 must complete the circuit to conductive plate 364 or else an error signal will be generated. Crimp stations 92 and 94 are disposed downstream from the drop wire station 86. The provision of two crimping stations 92 and 94 is intended to provide the most efficient cycle time and to avoid down time for maintenance. The crimp stations 92 and 94 are otherwise identical, except for the particular cable wires and terminals being crimped, and each is operative to crimp as many as five wires. Thus one crimp station 92 or 94 may be used for all crimps when the other station is down for repair or tool replacement. The crimp station 92 as shown in FIG. 2 and 6-8 includes first and second crimping presses 96 and 98 and a ground clip feed bowl 100 which is operative to feed ground clips (not shown) to the wire guides prior to crimping. The first and second crimp press 96 and 98 each are operative to sequentially crimp terminals fed from reels 102 and 104 to both the conductor and insulator of wires 12c, 12d at the respective first and second ends of the cable 12. The pallet 36 disposed at the crimp station 92 is indexed incrementally between sequential cycles of the crimp presses 96 and 98 by the servo feed shown schematically in FIG. 7 and identified generally by the numeral 106 in FIG. 7. Thus, the crimp presses 96 and 98 will simultaneously crimp a terminal to a first cable wire 12c plus any drop wire 12d or ground clip that may be present in the cable 12. The pallet 36 will then index approximately 14.93 mm (0.588 inch) and the first and second crimp presses 96 and 98 will crimp terminals to second cable wires in the cable 12 plus any drop wire or ground clip that may be present. This cycle will repeat at least a third time after which the pallet 36 may be advanced to a downstream station for either additional terminal crimping operations or for insertion of the terminated wires into the housing as explained below. Thus, crimp press 96 will crimp all of the terminals at one end of cable 12 and crimp press 98 will crimp all of the terminals at the other end. The crimping presses 96 and 98 comprise wire locators 108 and 110 respectively which are slidably mounted on support rods 112 and 114 as shown in FIG. 7. The wire guide locators 108 and 110 are urged downwardly as part of an initial movement of the crimp press 96, 98 to securely retain the wires and ground clips in the wire guides 58-62. The wire guide locators 108 and 110 will slide along the rods 112 and 114 with the indexing of the pallet 36 by servo motor 106 between sequential cycles of the crimp presses 96 and 98. As noted above, the terminations will vary significantly from one terminal to the next, depending upon the gauge and type of cable wire 12c, the gauge and type of any drop wire 12d that may be present, and the presence or absence of grounding clips. The terminals 156, however, are the same regardless of which wires are present. The system of the subject invention includes a programmable controller, indicated schematically by the numeral 116 in FIG. 2, into which control data as to the number and gauges of cable wires 12c, the presence, absence, type and location of drop wires 12d and the location of grounding clips may be entered. In order to achieve the optimum crimp for each terminal 156 as the pallet is indexed at crimp station 92, the travel of the crimp tooling must vary for each crimp depending upon the absence or presence of the various wires. Accordingly, the crimping presses 96 and 98 comprise crimp height controllers 118 as shown most clearly in FIG. 8, which are operatively connected to the programmable controller 116 in which the control data are entered. In this manner, the crimp presses 96 and 98 are operative to perform an optimum crimp on the particular arrangement of wires and grounding clips being presented thereto. More particularly, the crimp height controllers 118 each comprise cam wedges 119 and 120 which are slidably movable in opposed respective linear directions orthogonal to the crimping direction of the crimp presses and under the action of stepper motors 124 and 122, respectively. Conductor crimping punch 121 and insulation crimping punch 123 (FIGS. 8 and 18) are mounted adjacent each other above terminal 156. The punches are slidable vertically and have tapered top surfaces 125 and 127 which contact wedge surfaces 129 and 131 of cam wedges 119 and 120, respectively. Accordingly, by sliding cam wedges 119 and 120 horizontally, the height of punches 121 and 123 above their respective anvils, 133 and 135, and thus the crimp height can be varied. The controlled sliding movement of the cam wedges 118 and 120 determine the maximum crimp stroke enabled by the crimp press for the conductor crimp and insulation crimp respectively. Thus, the crimp height controller is operative to achieve an optimum crimp height and pull out force for each particular crimp, depending upon the programmed characteristics of the wires and/or grounding clips being terminated. After the termination has been completed, the pallet 36 advances downstream to the insertion station 126 as shown in FIG. 2. The movement of the pallet 36 into the insertion station 126 causes the core pins 68, 69 of the wire holder assemblies 52 to be engaged, and thereby collapsing the wire guides 58-62 toward one another. Alternatively, a pallet without collapsible wire holder assemblies may be provided. In this embodiment, as shown in FIG. 9, the insertion station 126 includes a collapsible fixture assembly 128 with separate notched fixtures 130 for engaging the terminated wires. The notched fixtures 130 are connected by pantograph linkage members 132 and are powered by air cylinder 134 to selectively collapse the wires to a 8,026mm (0.316 inch) spacing. The insertion station 126 further includes a wire gripper and lifter assembly 136, as shown in FIG. 10, with selectively rotatable arms 138 and 140 for lifting and gathering the wires 12c into a spacing consistent with the collapsed condition of the fixture assembly 128. The collapsible fixture assembly 128 and the wire gripper and lifter assembly 136 are operative to lift the ends of the cable 12 from the fixture on the pallet and then to effect the collapsing. The insertion station 126 includes a dual track bowl feed and supply hopper 142, as shown generally in FIG. 2, from which molded plastic housings are fed into first and second positions 144 and 146 adjacent the opposed first and second ends of the cable 12. The first and second positions 144 and 146 of the insertion station 126 are in proximity to movable probe assemblies 148 as shown in FIG. 11, which have a plurality of probes 150 corresponding in number to the maximum number of cable wires 12c. Additionally, the spacing between the probes corresponding to the spacing between terminal receiving apertures 152 in the housings 154. The probe assemblies 148 advance toward the housing 154 such that the respective probes 150 pass through the corresponding terminal receiving apertures 152 in the housings 154. Additionally, the movement of the probe assemblies 148 causes the respective probes 150 to contact and engage the terminals 156 crimped to the ends of the respective wires 12c, 12d. The probes 150 are operatively connected to known test circuitry such that the presence of a terminal 156 can be sensed and, if desired, such that the continuity of a cable wire 12c can be sensed. A cable 12 will be identified for rejection if a required terminal is not sensed as being present, or if the probe assemblies 148 fail to accurately sense the necessary continuity along the length of the cable wires 12c. On the other hand, once the probe assemblies 148 have sensed an acceptable product, the insertion station 126 is operative to move the housings 154 relative to the terminals 156 and the probe assemblies 148. The probe assemblies 148 are thus operative to guide the respective terminals 156 into the terminal receiving cavities 152 of the housing 154, while simultaneously ensuring that inadvertent and potentially damaging contact between the leading ends of the terminals 156 and the walls of the housing 154 is avoided. Upon complete movement of the housings 154 over the terminals 156, the probe assemblies 148 are retracted and the pallet 36 is advanced to an unload station at which the completed harness assembly is unloaded. The pallet 36 is then advanced toward the down elevator for recycling in the system. In optional embodiments (not shown), the pallet 36 may advance to locations at which a metallic shell is mechanically engaged around the housing and the jacket of the cable. An alternative insertion station 126 is shown in FIG. 12. Such an insertion station is utilized with a pallet 36 having a constant pitch wire holder 200 (FIG 16). The insertion station 126 includes a housing push subassembly indicated generally at 211 for pushing connector housing 154 onto terminals 156. A pitch adjustment subassembly indicated generally at 212 is provided for securing the wires 12c and 12d and reducing the pitch of the cable wires 12c prior to insertion into housing 154. A wire holding subassembly indicated generally at 213 and a subassembly 214 for depressing the wire holder 200 attached to the pallet are also provided. A terminal positioning subassembly indicated generally at 215 for accurately positioning the terminals 156 prior to insertion into housing 154 is further provided. As previously described, cable 12 has two ends onto which a housing is inserted. Accordingly, as described above, the insertion station 126 includes first and second positions 144 and 146 (FIG. 2) at which the housings 154 are inserted onto the terminals 156. Therefore, it should be understood that only one half of insertion station 126 is described below since each of the mechanisms is required at the first and second positions 144 and 146 of the insertion station. Housing push subassembly (FIG. 13) has two power slides 216, 217 mounted to insertion station frame 218. Power slide 216 is mounted so that center portion 220 is fixed to frame 218 and end portions 221 are reciprocally slidable. A housing push block 222 is fixed to one of end portions 221 so that actuation of power slide 216 reciprocally moves push block 222. Housing push block 222 has apertures 223 through which probes 150 extend towards terminals 156. Limit switches of known type 224 are provided to verify the position of power slide 216 so that the operation occurs in the proper sequence. The distance housing push block 222 can move housing 154 towards pitch adjustment subassembly 212 is adjustable through the use of nut and bolt assembly 219. Power slide 217 is mounted so that end portions 225 are fixed to frame 218 while center portion 226 slides relative to the end portions and the frame. Center portion 226 has bores 227 through which probes 150 extend and are slidable therein. One probe 150 is provided for each terminal 156. The sliding movement of the probes is limited by stops 228 which are fixed to each probe and located between shoulder 229 and shoulder 231. Thus, probes 150 are only capable of limited travel relative to center portion 226. As described in further detail below, the springs 230 are compressed when the probes 150 contact terminals 156 during the end of the stroke of powerslide 217 as it moves to the left in FIG 12. Thus, the probes are mounted on and extend through center portion 226 but the movement of center portion 226 horizontally also moves the probes horizontally through apertures 223 in push block 222 and into contact with terminals 156. Proximity flags 232 are fixed to probes 150. One proximity sensor 233 for each probe 150 is provided at support 234. One additional proximity sensor 235 is provided in support 236 and aligned with the center probe to monitor that the probes are fully retracted when they are supposed to be so that a new housing can be loaded into the insertion station. Wires (not shown) are connected to each proximity sensor and connected to the system controller in known manner. Sensors 233 operates first to determine whether the terminals 156 are properly positioned and then to determine whether they are properly inserted into housing 154. Proximity sensor 235 is used to determine when the probes 150 have been retracted so that a new housing 154 can be loaded into the insertion station 126. Pitch adjustment subassembly 212 (FIG. 14) includes similar lower and upper mechanisms 240 and 241 that are located below and above wires of cable 12, respectively. Each mechanism includes a fixed center arm 242 and inner moveable arms 243 located on opposed sides of center arm 242. Outer moveable arms 244 are located on the sides of inner arms 243 opposite center arm 242. Outer and inner arms 243 and 244 have bores therethrough and are slidably mounted on shafts 245. Pneumatic cylinders 246 are located adjacent the outside edge 247 of each outer arm. Upon actuating pneumatic cylinders 246, the shaft of each cylinder is forced into contact with the outside edge 247 of each outer arm 244 which in turn forces arm 244 towards center arm 242 and into contact with inner arm 243 so that outer arm 244 contacts inner arm 243 and the inner arm contacts center arm 242. Through such an arrangement, the gaps between the arms are eliminated upon actuation of the pneumatic cylinders and the pitch between the wires is changed. Springs 248 are provided between the arms to restore them to their original pitch after pneumatic cylinders 246 are retracted. Each arm of lower subassembly 240 has a vertical wire receiving slot 249 located at the top thereof. Each arm of upper subassembly 241 also has a vertical slot 250 into which a wire contacting pin 251 is slidably located. A compression spring 252 is located in slot 250 to bias pin 251 in a lowered position. The spring actuated pins permit the use of different diameter wires and multiple wire without modification of the tooling. In order to permit the pallets 36 to travel around track 34 of the system, each subassembly of the housing insertion station 126 has a mechanism for vertical movement so that each subassembly has a non-engaged position at which there is sufficient clearance so that the pallet can pass by the insertion station subassemblies. Each subassembly also has an engagement position at which wherein an operation is performed on the pallet or the cable wires. Lower subassembly 240 is moveable vertically on slide bearings 253 through the use of pneumatic cylinder 254 and linkage arms 255 and 256. The lower arm 255 is pinned to frame 218 and the upper arm 256 is pinned to lower subassembly 235. As best shown in FIG. 12, by extending cylinder 254, linkage arms 255 and 256 will move lower subassembly 240 upward so that wires 12c and 12d engage wire receiving slots 249. By actuating pneumatic cylinder 270, shaft 271 forces upper subassembly 241 downward towards pallet 36. Wire holding subassembly 213 (FIGS. 15 and 19) includes upper and lower mechanisms 260 and 261 mounted to plate 262. Upper mechanism 260 includes a power slide 263 fixed to plate 262. Block 264 is fixed to rods 269 of the power slide. A wire clamping block 265 made from a resilient material such as polyurethane is secured to block 264. Lower mechanism 261 includes a rotatable arm 266 secured to cylindrical block 267 (FIG. 19) which is rotatably and slidably mounted on shaft 268. Block 267 has an annular rib 272 at its edge closest to plate 262. A locator block 273 (FIG. 19) having a bore for receiving shot pin 274 is also mounted to arm 266. Shot pin 274 is fixed to the portion of bracket 275 that is parallel to plate 262. A wire clamping block 276 is fixed to the end of arm 266 opposite shaft 268. A first pneumatic cylinder 280 is mounted to plate 262 on the side opposite arm 266. The shaft 281 of cylinder 280 has mounted thereon a cylindrical block 282 having an annular rib 283. Cylinder 280 is located and blocks 267 and 282 are dimensioned so that annular rib 272 of block 266 is adjacent annular rib 283 of block 282. A second pneumatic cylinder 290 (FIG. 15) is provided wherein it is rotatably mounted to plate 262 at one end 291 and swively mounted to arm 266 at its other end 292. Thus, by extending cylinder 290, arm 266 swings through its range of motion from its non-engaged position (shown in phantom) to its engaged wire holding position as shown in FIGS. 12 and 15. Through activation of both upper and lower mechanisms 260 and 261, wires 12c and 12d are engaged between the lower face 293 of wire clamping block 265 and the wire clamping face 294 of arm 266. A third pneumatic cylinder 320 is also mounted to plate 262. The actuation of this cylinder forces push block 321 downward and into contact with cable 12 to ensure it is securely held by its clamping fixture 322. The subassembly 214 (FIG. 12) for depressing wire holder 200 is located between upper pitch adjustment mechanism 241 and wire holding subassembly 213. Subassembly 214 includes a pneumatic cylinder 295 which forces slide bearing 296 and block 297 attached thereto downward into contact with upper surface 298 (FIG. 16) of wire holder block 202. The force from cylinder 295 compresses springs 204 and forces the entire wire holder 200 downward. By actuating holder depressing subassembly 214 after activation of wire holding subassembly 213 and engagement of the wires 12c and 12d by pitch adjustment sub assembly 212, wires 12c and 12d are removed from the wire holder 200 while they are maintained on their pre-removal centerlines. Terminal positioning subassembly 215 (FIGS. 20 and 21) includes a terminal alignment template 300 for centering each terminal along the desired centerline at nesting positions 302. Template 300 has tapered edges 301 that guide the terminals 156 into the terminal nesting positions 302 upon actuation of cylinder 303 which forces shaft 304 and alignment template attached thereto downward towards the terminals. Attached to the template 300 are axial positioning nibs 305 which contact shoulder 306 of terminals 156 when the terminals are properly positioned. A terminal support member 309 is mounted to lower pitch adjustment mechanism 240 in order to support the terminals to ensure that they are not below the proper height before mating with probes 150. Subassembly 215 also includes a terminal rotating mechanism 310 which operates to ensure that none of the terminals 156 are rotated prior to insertion in the housing 154. Fingers 311 are spring loaded on bolts 312 which are secured to block 313 which in turn is fixed to the shaft of cylinder 314. Upon actuation of the cylinder, the fingers are moved downward so that the flat lower surface 315 of each finger contacts the flat portion of the crimp of each terminal. If the terminal is rotated, the force of the finger will rotate the terminal until the terminal is aligned with the crimp section facing upward. Fingers 311 also operate to close the cover (not shown) of housing 154 after terminals 156 have been inserted therein. In operation, pallet 34 arrives at insertion station 126 with wires 12c and 12d loaded into wire holder 200 and terminals 156 crimped on the wires. After the pallet is seated at the station, pneumatic cylinder 254 is actuated which elevates lower pitch adjustment mechanism 240 so that wires 12c and 12d are located within wire receiving slots 249. The height adjustment mechanisms comprised of pneumatic cylinder 254 and lower and upper arms 255 and 256 are adjusted so that wires 12c and 12d and terminals 156 crimped thereon are maintained at the desired centerlines in order to permit mating with probes 150. Upper pitch adjustment mechanism 241 (FIG. 14) is then lowered by actuating cylinder 270. The wire contacting pin 251 associated with each arm of upper subassembly 241 contacts the top surface of the wires and fixes the wires securely within wire receiving slot 249. The springs 252 are provided, in part, so that upper pitch adjustment mechanism 241 can be utilized without modification regardless of whether drop wires 12d are present in each terminal 156. That is, if a drop wire is present in one slot 249, the pin 251 associated with that slot will contact the drop wire before the pins associated with the other slots contact the wire in their respective slots. In such case, the spring 252 of the pin 251 that contacts the drop wire 12d will be compressed a greater amount than if a drop wire were not present. Through such an arrangement, the wires are gripped between the wire holder 200 and terminals 156. It should be noted that a sufficient length of each wire extends axially beyond the pitch adjustment subassembly 212 towards housing 154 so that the housing can be slid onto terminals 156 without the housing contacting the pitch adjustment subassembly 212. The lower and upper mechanisms 260 and 261 (FIG. 15) of wire holding subassembly 213 are then operated to secure the wires 12c and 12d on the side of wire holder 200 opposite pitch adjustment subassembly 212. Pneumatic cylinder 290 is actuated to swing rotatable arm 266 from its non-engaged position to its engaged position whereat wire clamping face 294 of rotatable arm 266 is positioned to support wires 12c and 12d. Pneumatic cylinder 280 is then actuated which forces block 282 into contact with arm 266 adjacent shaft 268 and thus slides arm 266 on shaft 268 away from plate 262. During the sliding motion, shot pin 274 mates with the bore in locator block 273. Arm 266 is secured in this manner to provide a mechanical barrier to prevent rotation rather than relying solely upon the force of pneumatic cylinder 290. As a result, powerslide 263 can exert a greater force on wire clamping face 294 in order to securely retain wires 12c and 12d. After arm 266 is secured in place, powerslide 263 is actuated to force wire clamping block 265 downward towards wires 12c and 12d so that the lower face 293 of that block contacts the wires and secures them between the lower face 293 and wire clamping face 294 of rotatable arm 266. Cylinder 320 is also actuated to force cable 12 downward into its clamping fixture 322. At this point, the wires 12c and 12d are supported on both sides, in an axial direction, of wire holder 200. Pneumatic cylinder 295 (FIG. 12) of the subassembly 214 for depressing the wire holder 200 is then actuated which forces arm 296 and pusher block 297 downward to engage the upper surface 298 of block 202 and force the block 202 and wire retainer 207 downward, thus compressing springs 204. By supporting the wires 12c and 12d on opposite sides of wire holder 200 and then pushing the wire holder downward, the wires are removed from wire holder 200 without changing their centerline. Once the wires 12c and 12d have been removed from wire holder 200, pneumatic cylinders 246 of the pitch adjustment subassembly 212 are actuated to compress the inner and outer arms 242 and 243 of lower and upper pitch adjustment mechanisms 240 and 241 to force the wires and the terminals attached thereto into the desired pitch. Terminal alignment plate 300 (FIGS. 20 and 21) is then lowered by actuating cylinder 303. If the terminals are. located to the side of the correct centerline, they will contact tapered edges 301 of the template and be guided by the taper into terminal nesting position 302 located at the apex of the taper. Vertical alignment occurs through the terminals contacting terminal support member 309 and template 300 at terminal nesting position 302. At this point, terminals 156 are supported between terminal support member 309 and template 300. The various clamps securing the wires 12c and 12d are then released so that the terminals can be located in the axial direction prior to insertion into housing 154. Powerslide 263 is retracted to raise block 265 off of the wires. Cylinder 280 is retracted to pull arm 266 along shaft 268 towards plate 262 so that shot pin 274 disengages from locator block 273. Arm 266 is then rotated back to its non-engaged position by retracting cylinder 290. Cylinder 270 is retracted which raises upper pitch adjustment mechanism 241 and so that pins 251 no longer contact wires 12c and 12d to retain them within slots 249. Accordingly, wires 12c and 12d together with the terminals 156 attached thereto are free to move in the axial direction only. Power slide 217 is actuated so that center portion 226 and probes 150 are moved towards the terminals 156 (to the left in FIG. 12). Near the end of the power slide's travel towards pitch adjustment subassembly 212, probes 150 contact the terminals and force them towards that subassembly until shoulder 306 (FIG. 20) of each terminal contacts axial positioning nib 305. Once the terminals are positioned against nib 305, any additional movement of power slide 217 results in the probes mating with the terminals and compression of spring 230. Cylinder 314 is actuated at this point to lower terminal rotating mechanism 310. The lower flat surface 315 of each finger 311 contacts the flat crimp section of terminal 156 and rotates it if necessary so that the flat crimp section contacts surface 315. Through this operation, all of the terminals will be aligned radially. Each terminal should now be accurately positioned and the system controller then monitors the status of the proximity sensors 233 to determine whether the proximity flags 232 are all in the correct position, thus indicating correct positioning of the terminals 156 and the probes 150. If the terminals and probes are not in the correct position, an error signal is generated by the system controller. Absent such a signal, cylinder 270 is actuated to lower upper pitch adjustment mechanism to reclamp the wires 12c and 12d in slots 249 with pins 251. Cylinders 303 and 314 are then retracted to disengage the terminal positioning subassembly from the terminals 156. The terminals are then supported only by probes 150 and the wires supported only by pitch adjustment mechanism 212. At this time, housing power slide 216 is actuated to move end portion 221 and push block 221 towards terminals 156. Such movement forces a housing 154 over the terminals 156 in a gang-loading operation. Cylinder 314 is then actuated again to force fingers 311 down to close a cover (not shown) located at the top surface of the housing 154. Once the push block 216 has completed its stroke towards terminals 156, the system controller again monitors the proximity sensors 233 to determine that all of the terminals were fully inserted into the housing. If, for example, one terminal were not fully inserted, the probe in contact with that terminal would be further to the left as viewed in FIG. 12 and the system controller would generate an error signal. Both power slides 216 and 217 are then retracted to withdraw the probes 150 from the terminals 156 and disengage the push block 222 from the housing 154. Cylinder 270 is retracted to raise upper pitch adjustment mechanism 241 and thus release wires 12c and 12d from slots 249. Cylinder 254 is retracted to lower the lower pitch adjustment mechanism 240. Cylinder 295 is retracted to release wire holder 200 and permit the pallet 34, having a completed harness, to advance to an unload station or a station for further processing.
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An apparatus for producing wire harness assemblies (10), each assembly comprising a plurality of cable wires (12c, 12d) having opposed ends with terminals (156) mounted to said wires at one end of said cable wires and a housing (154) at one of said ends with a plurality of said terminals mounted therein, said apparatus comprising an insertion station (126) for inserting the terminals into the housing, characterized by : at least one probe assembly (148, 211) at the insertion station, said probe assembly including a plurality of probes (150) corresponding in number to the number of terminals (156), each said probe being configured to engage a corresponding terminal; means (217) for moving the probes (150) selectively into and out of engagement with the terminals (156); and means (216) for moving the housing (154) relative to the terminals (156) and the probes (150) such that the probes guide the housing during the insertion of the terminals. The apparatus as in claim 1 further including means (240, 241) for supporting said terminals (156) prior to engagement of said terminals by said probes (150). The apparatus as in claim 1 or 2 further including means (302) for rotating said terminals (156) about their respective axes and means (150, 217, 305) for moving said terminals axially in order to properly position said terminals prior to insertion of said terminals into said housing. The apparatus as in claim 3 wherein movement of said probes (150) into engagement with said terminals (156) moves said probes axially. The apparatus as in any of the above claims wherein said means (216) for moving said housing (154) relative to said terminals (156) moves said housing towards said terminals along an axis parallel to axes through said terminals. The apparatus as in any of the above claims further including test means (150, 223, 232) for sensing that the terminals are in a predetermined, desired location. The apparatus as in claim 6 wherein said test means utilizes sensing means (223, 232) operatively associated with said probes (150) to determine whether said terminals (156) are properly axially positioned after said terminals are inserted into said housing (154). A method of producing wire harness assemblies (10) including the steps of providing a plurality of wires (12c, 12d), crimping each said wire to a terminal (156), and inserting the terminals into a non-conductive housing (154), characterized by: positioning said terminals (156) crimped to said wires in a spaced, generally planar array; moving a plurality of probes (150) corresponding in number to the number of terminals (156) into engagement with said terminals; and moving the housing (154) relatively towards the terminals (156) and the probes (150) such that the probes guide the housing during the insertion of the terminals. The method of claim 8 further including the steps of rotating said terminals (156) about their respective axes and moving said terminals axially in order to properly position said terminals prior to insertion of said terminals into said housing (154). The method of claim 9 wherein said step of moving said probes (150) into engagement with said terminals (156) moves said terminals axially into their proper position. The method of claims 8-10 further including the step of sensing the position of said probes (150) to determine whether said terminals (156) are in their desired, predetermined position after insertion of said terminals into said housing (154).
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MOLEX INC; MOLEX INCORPORATED
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CAMERON JOHN G; DEROSS ROBERT W; DUDEK RONALD; ERKLIN ROBERT E SNR; INGWERSON PETER; KLEMMER ROBERT; SHAH HASMUKH; SUTHARD ROBERT A; WRIGHT STEVEN F; CAMERON, JOHN G.; DEROSS, ROBERT W.; DUDEK, RONALD; ERKLIN, ROBERT E., SNR.; INGWERSON, PETER; KLEMMER, ROBERT; SHAH, HASMUKH; SUTHARD, ROBERT A.; WRIGHT, STEVEN F.
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EP-0489559-B1
| 489,559 |
EP
|
B1
|
EN
| 19,950,712 | 1,992 | 20,100,220 |
new
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H01L29
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H01L21
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H01L21, H01L29
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H01L 21/336H1L, H01L 29/78
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LDD metal-oxide semiconductor field-effect transistor and method of making the same
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An improved metal oxide semiconductor field-effect transistor (MOSFET) has two diffused regions extending apart in opposite directions from under one and the other edge of the gate (203). At least one of the diffused regions is composed of a first least-doped, short section (204a;204b), a second lightly-doped, short section (207a;207b), and a third heavily-doped, long section (208a;208b). Either diffused region may be used as drain. The series-connection of least-doped and lightly-doped sections of the same longitudinal size or depth improves the current driving capability of the semiconductor device. Also, methods of making such MOSFETs are disclosed.
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The present invention relates to a method of making a metal-oxide semiconductor field-effect transistor structure, and particularly to the drain structure of such a semiconductor device. Also, the present invention relates to a metal-oxide semiconductor field-effect transistor structure made by the method. As is well known, the lightly doped drain structure of a metal-oxide semiconductor field effect transistor (abbreviated MOSFET) comprises a lightly doped section starting from a location under one edge of the gate and extending a relatively short distance apart from said location, and a heavily doped section following said lightly doped section and extending a relatively long distance apart from the gate. The presence of such lightly doped section ahead of the heavily doped section will cause the strength of the electric field appearing in the vicinity of the drain of the device to be reduced so as to suppress appearance of hot carriers. Such hot carriers are liable to invade the gate through the underlying metal oxide and to remain in the gate, and as a result the performance of the device will change with age. Adoption of the lightly doped drain structure in a MOSFET improves substantially the reliability of the device. The lightly doped section, however, functions as a parasitic resistor, and disadvantageously it will lower the current driving capability of the device. In an attempt to solve this problem a profiled lightly doped drain structure (abbreviated PLDD) was proposed (See the paper Profiled Lightly Doped Drain (PLDD) Structure for High Reliable NMOSFETs , Y. Toyoshima et al, Digest of Technical Papers, Symposium on VLSI Technology,pp.118-119, 1985). Fig. 1 shows, in section, a PLDD structure. It comprises a P-type silicon substrate 100, a gate insulating layer 101 formed on the top surface of the substrate 100, a gate 103 built on the gate insulating layer 101, an N-type source diffusion layer 108a, and an N-type drain diffusion layer 108b. The gate 103 has a surrounding wall 106, and the source and drain diffusion layers 108a and 108b have electrodes 109 and 110 respectively. These electrodes 109 and 110 are embedded in an overlying insulating layer 111. It is noted that: the drain diffusion layer is composed of an upper short projection 107 of least concentration of impurity such as arsenic, a surrounding section 104 of less concentration of impurity such as phosphorus, and an elongated section 108b of relatively high concentration of impurity such as arsenic, lying contiguous to the upper projection 107 and surrounding section 104, which end at a location under one edge of the gate 103. The coexistence of less doped core 107 and least doped enclosure 104 prevents effectively the lowering of the current driving capability of the device. In the PLDD structure, however, carriers are liable to come together toward the upper surface of the substrate 100, and as the device size is decreased, hot carriers will be most likely to appear in the vicinity of the upper surface of the substrate 100, invading the gate 103 through the underlying insulating layer 101 to lower the characteristics of the device. Also, further miniaturization of MOSFETs having a PLDD incorporated therein will cause the least doped enclosure 104 to function as a parasitic resistor, thereby lowering the current driving capability of the device. European patent application EP 0187016 describes a device of this type, at figure 4, and also describes at figures 6 to 9 a second type of MOSFET in which three regions of the LDD structure having less, least (intermediate) and highest impurity concentrations are arranged in series. This type of structure is described at figure 2 herein, where the known MOSFET is shown as comprising: a P-type silicon substrate 300; a gate insulating layer 301 of silicon formed on the top surface of the substrate 300; a gate 303 built on the gate insulation 301; an N-type source diffusion layer 304a and an N-type drain diffusion layer 304b extending toward and ending at first locations under one and the other edges of the gate 303 respectively in opposite directions in the substrate 300; and an N-type source diffusion layer 307a and an N-type drain diffusion layer 307b extending toward and ending at second locations under one and the other edges of the gate 303 respectively in opposite directions in the substrate 300. It should be noted that the source diffusion layer is composed of a first relatively short section 304a of least concentration of impurity, a second relatively short section 307a of less concentration of impurity, and a third relatively long section 310a of relatively high concentration of impurity lying contiguous to each other and extending far from the first location in the order named. The drain diffusion layer has also the same structure 304b, 307b, 310b. The first short sections 304a and 304b of least concentration and the second short sections 307a and 307b of less concentration extend to the same depth, thereby causing carriers to travel through an increased transverse area in the semiconductor substrate 300 compared with a PLDD structure, in which carriers come together close to the top surface of the semiconductor substrate 300. Thus, the MOSFET of Figure 2 shows improved freedom from deterioration of the characteristics of the device compared with that of Figure 1. Also, advantageously the parasitic resistance is reduced two to three times, and accordingly the current driving capability is increased. As described in EP 0187016 this structure is made by a sequence of masking and ion implantation steps. The steps involved are illustrated in Figures 4F to 4L herein. First, a semi-fabricated product comprising a P-type substrate 300 with a gate insulating layer 301 of metal oxide formed on its top surface, and a gate 303 built on the gate insulating layer 301 is prepared according to a conventional method. Phosphorus ions (1 x 10¹³cm⁻²; 35 KeV) are injected perpendicular to the top surface of the P-type substrate 300 to form two opposite N-type diffusion layers 304a and 304b of least concentration of phosphorus in the substrate 300. These diffused regions 304a and 304b extend from first and second locations under one and the other edges of the gate 303 respectively in opposite directions. A 1000 angstrom-thick oxide layer 305 is formed on the semi-fabricated product (Fig.4F); and the thick oxide layer 305 is subjected to anisotropic etching until the top surface of the substrate 300 is exposed to leave a side wall 306 surrounding the gate 303 (Fig.4G). Phosphorus ions (1 x 10¹⁴cm⁻²; 35 KeV) are injected perpendicular to the P-type substrate 300 to form two opposite N-type diffusion layers 307a and 307b of less concentration of phosphorus in the substrate 300 (Fig.4H). These diffused regions 307a and 307b extend short of the terminal ends of the diffusion layers 304a and 304b of least concentration of phosphorus. A 2000 angstrom-thick oxide layer 308 is then formed on the sidewalled product (Fig.4I); and the thick oxide layer 308 is subjected to anisotropic etching until the top surface of the substrate 300 is exposed to leave a second side wall 309 surrounding the first side wall 306 of the gate 303 (Fig.4J). Arsenic ions (5 x 10¹⁵cm⁻²; 40 KeV) are injected perpendicular to the P-type substrate 300 to form two opposite diffusion layers 310a and 310b of relatively high concentration of arsenic in the substrate 300 (Fig.4K). These heavily diffused regions 310a and 310b extend from first and second locations under one and the other edges of the second side wall 309 in opposite directions. Finally, a source electrode 311, a drain electrode 312 and a gate electrode (not shown) are formed respectively (Fig.4L). In this process it should be noted that a different mask is required for forming each of the three implanted regions, provided respectively by the gate, the first side wall and the second side wall. US patent No. 4746624 describes a MOSFET structure very similar to that of Figures 2 and 4F to 4L herein and manufactured similarly by using three separate masking steps. Japanese patent publication No. JP-A-60136376, as set out in Patent Abstracts of Japan Vol. 9, No.298, describes a further MOSFET having a LDD structure in which the source and drain each comprise three regions of different impurity concentrations. Two regions are initially implanted, using the gate and a subsequently formed side wall as masks, and the third region formed between the first two by a diffusion process. VLSI Technology, S.M. Sze, editor, McGraw Hill, 1988, pages 362, 363 describes a process for reducing the depth of an ion-implanted region for a given ion type and ion beam energy by tilting the ion beam direction with respect to the implanted surface. This is to enable a relatively shallow ion-implanted region to be formed using a relatively high beam energy. US patent No. 4771012 describes a method of fabricating a FET in which the source and drain are formed by ion implantation using the gate as a mask, the ion beam being tilted to an angle of 7° from a line perpendicular to the substrate surface to avoid channelling in the substrate. The substrate is rotated during implantation to eliminate any effects of shadowing of the substrate by the gate and to reduce any resulting asymmetry of the source and drain structures. At Figure 6, US 4771012 describes the fabrication of a LDD MOSFET having two regions of different impurity concentrations in each of the source and drain. The first region in each is formed using the gate as a mask and the second using a subsequently formed side wall as a mask. Both regions are formed using a 7° tilted ion beam. The invention provides a method of making a metal-oxide semiconductor field-effect transistor (MOSFET) as defined in claim 1, and a MOSFET structure made by the method of claim 1. A preferred feature of the invention is defined in a subclaim. Advantageously, the invention may thus provide an improved method for making a metal-oxide semiconductor field-effect transistor whose structure permits reduction of its size without lowering its current driving capability. Other objects and advantages of the present invention will be understood from the following description of preferred embodiments of the present invention and accompanying drawings. Fig.1 schematically shows, in section, a MOSFET using a first known structure; Fig.2 schematically shows, in section, a MOSFET using a second known structure; Figs.3A to 3D show the manner in which a semi-fabricated MOSFET is prepared according to a conventional method; and Figs.3E to 3J show a manner in which an improved MOSFET according to the present invention is made; and Figs.4F to 4L show a known method of making the MOSFET of Fig.2. Referring to Figs.3A to 3J, a method of making a MOSFET according to the present invention is described. Figs.3A to 3D show how a semi-fabricated product comprising a semiconductor substrate of one conductivity type with a gate insulating layer formed on its top surface, and a gate built on the gate insulating layer can be prepared according to a conventional method. Specifically, a P-type silicon substrate 200 is prepared (Fig.3A); a silicon oxide layer 201 is formed on the top surface of the substrate 200 by heating the substrate 200 in an oxidizing atmosphere (Fig.3B); a polysilicon layer 202 is formed on the silicon oxide layer 201 (Fig.3C); and the polysilicon layer 202 is subjected to anisotropic etching to leave a gate 203 on the silicon oxide layer 201 (Fig.3D). Thus, a semi-fabricated product results. Phosphorus ions (1 x 10¹³cm⁻²; 40 KeV) are then injected perpendicular to the top surface of the P-type substrate to form two opposite N-type diffusion layers 204a and 204b of least concentration of phosphorus in the substrate 200. These diffused regions 204a and 204b extend from first and second locations under one and the other edges of the gate 203 respectively in opposite directions (Fig.3E). A 2000 angstrom-thick oxide layer 205 is formed on the semi-fabricated product (Fig.3F); and the thick oxide layer 205 is subjected to anisotropic etching until the top surface of the substrate 200 is exposed to leave a side wall 206 surrounding the gate 203 (Fig.3G). Phosphorus ions (5 x 10¹³cm⁻²; 50 to 60 KeV) are injected to the P-type substrate 200 at 45 degrees to form two opposite N-type diffusion layers 207a and 207b of less, or an intermediate, concentration of phosphorus in the substrate 200 (Fig.3H). These diffused regions 207a and 207b extend short of the terminal ends of the diffusion layers 204a and 204b of least concentration of phosphorus. Arsenic ions (5 x 10¹⁵cm⁻²; 70 KeV) are injected to the P-type substrate 200 perpendicular to the top surface of the substrate to form two opposite diffusion layers 208a and 208b of relatively high concentration of arsenic in the substrate 200 (Fig.3I). These heavily diffused regions 208a and 208b extend from first and second locations under one and the other edges of the side wall 206 in opposite directions. Finally, a source electrode 209, a drain electrode 210 and a gate electrode (not shown) are formed respectively (Fig.3J). It should be noted that the two diffused regions 208a and 208b are of the same construction. Conveniently this permits either diffused region to be used as drain when the device is actually used. As is seen from Figure 3J, a metal-oxide semiconductor field-effect transistor thus made has two similar diffused regions each extending toward and ending at a location under one or the other edge of the gate 203 in the substrate 200. Each is composed of a first relatively short section 204a, 204b of least concentration of impurity, a second relatively short section 207a, 207b of less concentration of impurity, and a third relatively long section 208a, 208b of relatively high concentration of impurity. As described earlier, this permits either diffused region to be used as drain when actually the device is used.
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A method of making a metal-oxide semiconductor field-effect transistor by preparing a semi-fabricated product comprising a semiconductor substrate (200) of one conductivity type with a gate insulating layer (201) formed on its top surface, and a gate (203) built on said gate insulating layer, forming two diffused regions of the other conductivity type extending apart in opposite directions from under one and the other edges of said gate, and forming drain, source and gate electrodes, at least one of said diffused regions being formed by the following steps; (A) injecting an impurity of the other conductivity type into said semiconductor substrate perpendicular to the top surface of said semiconductor substrate to form a diffusion layer (204a, 204b) of least concentration of impurity in said semiconductor substrate, extending from a location under one edge of said gate; (B) forming a side wall (206) surrounding said gate on said semiconductor substrate; and (C) injecting an impurity of the other conductivity type into said semiconductor substrate perpendicular to the top surface of said semiconductor substrate to form a diffusion layer (208a, 208b) of relatively high concentration of impurity in said semiconductor substrate, extending from a location under a corresponding edge of said side wall; characterised by the step (D) of, after the side wall has been formed, injecting an impurity of the other conductivity type into said semiconductor substrate at a given acute angle with respect to the normal line perpendicular to the top surface of said semiconductor substrate to form a diffusion layer (207a, 207b) of less concentration of impurity in said semiconductor substrate, extending beneath the side wall, short of the end of said diffusion layer (204a, 204b) of least concentration of impurity. A method according to Claim 1, in which both of the two diffused regions are formed according to similar steps, so that in step (A) two opposite diffusion layers (204a, 204b) of least concentration of impurity are formed, extending in opposite directions from first and second locations under the one and the other edges of the gate respectively, in step (C) two opposite diffusion layers (208a, 208b) of relatively high concentration of impurity are formed, extending in opposite directions from first and second locations under the one and the other corresponding edges of the side wall, and in step (D) two opposite diffusion layers (207a, 207b) of less concentration of impurity are formed, extending short of the ends of the diffusion layers (204a, 204b) of least concentration of impurity.
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NIPPON ELECTRIC CO; NEC CORPORATION
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OKABE KAZUHIRO C O NEC CORPORA; SAKAI ISAMI C O NEC CORPORATIO; OKABE, KAZUHIRO, C/O NEC CORPORATION; SAKAI, ISAMI, C/O NEC CORPORATION
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EP-0489560-B1
| 489,560 |
EP
|
B1
|
EN
| 19,970,409 | 1,992 | 20,100,220 |
new
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G03F7
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G03F7
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G03F7, C25D13, H01L21, H05K3, C09D5
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G03F 7/039, G03F 7/16D
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Positive type photosensitive anionic electrodeposition coating resin composition
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A resin composition comprising (A) a copolymer obtained by copolymerising (a) acrylic acid and/or methacrylic acid, (b) at least one compound bearing a group unsatable to acid such as t-amyl acrylate or t-amyl methacrylate and (c) a copolymerizable monomer such as n-butyl acrylate and (B) a photoacid generator is effective for providing electrodeposition baths with good water dispersion stability and may be used to produce electrodeposited films having high sensitivity and high resolution.
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BACKGROUND OF THE INVENTIONThis invention related to a positive type photosensitive anionic electrodeposition coating resin composition, an electrodeposition bath using the same, an electrodeposition process and a process for producing printed circuit boards. As processes for forming resist patterns on surfaces of substrates, there has frequently been used a process comprising forming a photosensitive layer on a substrate surface, irradiating the photosensitive layer with actinic light, followed by development. As to formation of photosensitive layer, there have been known, for example, dip coating, roll coating, curtain coating, etc., using a photosensitive resin composition solution (a coating fluid), and a laminating process wherein a photosensitive film which is obtained by forming a photosensitive layer on a substrate film previously is laminated on a substrate surface using a laminator, etc. Among these processes, the laminating process using the photosensitive film are mainly employed particularly in the field of printed circuit board production due to formation of the photosensitive layer with a uniform thickness easily. With recent progress of higher density and higher precision of printed circuit boards, resist patterns having higher quality are required now. That is, there are required resist patterns having no pin holes and good in adhesion to an underlying substrate surface. In order to meet such a requirement, the laminating process using the photosensitive film and now employed mainly is to be known having a limit. According to the laminating process, conformability to unevenness of substrate surface caused by scars at the time of substrate production, ununiformity of polishing, meshes of glass cloth present in an inner layer of substrate, ununiformity of pits and the like of copper plating on the surface, is poor, resulting in difficulty in obtaining sufficient adhesiveness. Such difficulty can be removed to some extent by carrying out the lamination of photosensitive film under reduced pressure (Japanese Patent Examined Publication No. 59-3740), but a special and expensive apparatus is necessary for such a purpose. Under such circumstances, solution coating processes such as dip coating, roll coating, curtain coatings, etc. have been noticed again recently. But these processes have problems in that control of film thickness is difficult, uniformity of film thickness is insufficient, pin holes are generated, and the like. Recently, there is proposed a new process for forming a photosensitive film by electrodeposition (Japanese Patent Unexamined Publication No. 62-235496). According to this process, there are advantages in that (1) adhesiveness of a resist to a substrate is improved, (2) conformability to unevenness of substrate surface is good, (3) a photosensitive film with a uniform film thickness can be formed in a short time, (4) since the coating fluid is an aqueous solution, pollution of working circumstances can be prevented, and there is no problem in prevention of disasters. Thus, there are made some proposals as to positive type photosensitive electrodeposition which seems to be effective for producing printed circuit boards having through-holes. In most cases, a quinonediazido group as a photosensitive group is used, but there are problems in that photosensitivity is low and water disposition stability of photosensitive materials is poor. On the other hand, as a pattern forming process for producing electronic parts such as semiconductor elements, magnetic bubble memories, integrated circuits, etc., there are proposed processes using many chemical amplified system positive type photosensitive materials comprising a compound which can generate an acid upon irradiation with actinic light, and a compound which is decomposed by the acid generated and shows a property of enhancing solubility in a developing solution. These processes can be expected to show significantly higher sensitivity than the process of using the quinonediazido group. But such materials have not practically been used for electrodeposition. This is because known chemical amplified positive type photosensitive materials are dissolved in organic solvents and used for forming photosensitive films by a coating method, so that these materials cannot be dispersed in water as they are and thus cannot be used as an electrodeposition coating resin composition. In order to use these materials for electrodeposition, it is necessary to fundamentally reconstitute chemical amplified positive type photosensitive materials. SUMMARY OF THE INVENTIONThe present invention seeks to provide a positive type photosensitive electrodeposition coating resin composition with high sensitivity, and high resolution, an electrodeposition bath good in stability (water dispersion stability of photosensitive material), a process for electrodeposition using the said resin composition, and a process for producing a printed circuit board using said resin composition. The present invention provides a positive type photosensitive anionic electrodeposition coating resin composition comprising (A) a copolymer comprising residues of (a) acrylic acid or methacrylic acid or both, (b) at least one polymerizable compound selected from t-butyl methacrylate, t-butyl acrylate, t-amyl methacrylate, t-amyl acrylate, isobornyl methacrylate, isobornyl acrylate and mixtures of two or more thereof, and (c) a polymerizable monomer capable of forming a homopolymer having a glass transition temperature of 0°C or lower, copolymer (A) comprising, per 100 parts by weight of the total amounts of monomer constituting copolymer (A), 2 to 35 parts by weight of component (a), 10 to 80 parts by weight of component (b) and 5 to 75 parts of component (c), and (B) a compound capable of generating an acid when exposed to actinic light. The present invention also provides an electrodeposition bath comprising the above-mentioned resin composition. The present invention further provides the use of a composition or electrodeposition bath according to the invention in electrodeposition using a substrate as an anode. The present invention still further provides a process for producing a printed circuit board which comprises forming an electrodeposited film on a substrate by use of a composition or electrodeposition bath according to the invention and then exposing the film to light and developing the exposed film. The electrodeposited film may be formed by dipping a substrate at least one surface of which has electroconductivity in the composition or bath and applying a direct current while making the substrate an anode. DESCRIPTION OF THE PREFERRED EMBODIMENTSThe copolymer (A) may be obtained by copolymerizing (a) at least one member selected from the group consisting of acrylic acid and methacrylic acid, (b) at least one compound selected from t-butyl methacrylate, t-buthyl acrylate, t-amyl methacrylate, t-amyl acrylate, isobornyl methacrylate and isobornyl acrylate and mixtures thereof, and (c) a polymerizable monomer capable of forming a homopolymer having a glass transition temperature of 0°C or higher. As the monomer component (a), there are used acrylic acid and/or methacrylic acid. It is preferable to use the component (a) so as to make the acid number of the resulting copolymer (A) preferably 20 to 230, more preferably 40 to 150. When the acid number is less than 20, there is a tendency to lower water dispersibility and water dispersion stability of the positive type photosensitive anionic electrodeposition coating resin composition of the present invention after an addition of a base, followed by addition of water as explained later, and to precipitate the composition. On the other hand, when the acid number is more than 230, there is a tendency to lower surface appearance of the photosensitive film after electrodeposition. Acrylic acid and methacrylic acid can be used alone or as a mixture thereof. The amount of the component (a) used is 2 to 35 parts by weight, preferably 5 to 23 parts by weight, per 100 parts by weight of the total amounts of monomers constituting the copolymer (A). When the amount is less than 2 parts by weight, there is a tendency to lessen dispersibility of the coating composition and to lower stability and electrodeposition properties. On the other hand, when the amount is more than 35 parts by weight, there is a tendency to lower uniformity of resulting coated film and resistance to developer. The component (b) compound bears a group which is unstable in the presence of an acid. There is used, as component (b) t-butyl methacrylate, t-butyl acrylate, t-amyl methacrylate, t-amyl acrylate, isobornyl methacrylate, isobornyl acrylate, and mixtures thereof. Preferably, t-butyl methacrylate and t-butyl acrylate can be used alone or as a mixture thereof. It is also possible to use t-amyl methacrylate and t-amyl acrylate alone or as a mixture thereof. It is further possible to use isobornyl methacrylate of the formula: and isobornyl acrylate of the formula: alone or as a mixture thereof. Among these components (b), from the viewpoint of water dispersion stability, the use of tert-amyl (meth)acrylate and isobornyl (meth)acrylate is preferable, the use of tert-amyl (meth)acrylate is more preferable, and the use of tert-amyl methacrylate is particularly preferable. The amount of the component (b) used is 10 to 80 parts by weight, preferably 20 to 60 parts by weight, per 100 parts by weight of the total amounts of monomers consitituting the copolymer (A). When the amount is less than 10 parts by weight, there is a tendency to lower photosensitivity. On the other hand, when the amount is more than 80 parts by weight, there is a tendency to lower electrodeposition properties due to too high glass transition temperature of the copolymer (A). As the component (c), there is used a polymerizable monomer capable of forming a homopolymer having a glass transition temperature of 0°C or lower. The homopolymer obtained from the copolymerizable monomer (c) should have a glass transition temperature of 0°C or lower. The glass transition temperature can be measured by a conventional thermal analysis method, preferably by a differential scanning calorimetric method (DSC). Examples of such copolymerizable monomers are ethyl acrylate, isopropyl acrylate, n-propyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, etc. Among these monomers, n-butyl acrylate and 2-ethylhexyl acrylate are preferable. These monomers can be used alone or as a mixture thereof. The amount of the component (c) used is 5 to 75 parts by weight, preferably 20 to 60 parts by weight, per 100 parts by weight of the total amounts of monomers constituting the copolymer (A). When the amount is less than 5 parts by weight, the glass transition temperature of the homopolymer becomes too high, resulting in showing a tendency to lower electrodeposition properties. On the other hand, when the amount is more than 75 parts by weight, the glass transition temperature of the copolymer (A) becomes too low, resulting in showing a tendency to increase sticking (or tackiness) of coated film after electrodeposition. The preferred amounts of the monomers (a), (b) and (c) constituting the copolymer (A) are 5 to 23 parts by weight of the component (a), 20 to 60 parts by weight of the component (b), and 20 to 60 parts by weight of the component (c), per 100 parts by weight of the total of the components (a), (b) and (c). The copolymer (A) may further contain one or more monomers other than the polymerizable monomers (a), (b) and (c) mentioned above. Examples of such monomers are methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, norbornyl methacrylate, norbornenyl methacrylate, mesityl methacrylate, phenetyl methacrylate, adamantyl methacrylate, tricyclo[5.2.1.02,6]deca-8-(or 9)-yl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl methacrylate, 2,2,2-trifluoroethyl methacrylate, diacetoneacrylamide, acrylonitrile, styrene, vinyltoluene, etc. These monomers can be used alone or as a mixture thereof. These monomers can be used in amounts of preferably 50 parts by weight or less, more preferably 30 parts by weight or less, per 100 parts by weight of the total of copolymerizable monomers (a), (b) and (c). The copolymer (A) can generally be obtained by solution polymerization of the polymerizable monomers in an organic solvent using a polymerization initiator such as azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, or the like. As the organic solvent, the use of hydrophilic organic solvent such as dioxane, methoxyethanol, ethoxyethanol, diethylene glycol, or the like is preferable considering that such an organic solvent is also used for electrodeposition. When a hydrophobic organic solvent such as toluene, xylene, benzene, etc. is mainly used, such a solvent should be removed by distillation after copolymerization and a hydrophilic organic solvent should be substituted therefor. The copolymer (A) has a weight average molecular weight (converted to standard polystyrene) of preferably 5,000 to 150,000, more preferably 20,000 to 90,000. When the molecular weight is less than 5,000, mechanical strength of a resist becomes weak. On the other hand, when the molecular weight is more than 150,000, there is a tendency to lower electrodeposition properties and to lower surface appearance of coated film. The copolymer (A) has a glass transition temperature of preferably 0° to 100°C, more preferably 10° to 70°C, particularly preferably 20° to 50°C. When the glass transition temperature is too low, there is a tendency to increase sticking of coated film. On the other hand, when the glass transition temperature is too high, there is a tendency to lower electrodeposition properties. The copolymer (A) is preferably used in an amount of 60 to 99.999 parts by weight, more preferably 80 to 99.9 parts by weight, per 100 parts by weight of the total weight of the copolymer (A) and the component (B). When the amount is less than 60 parts by weight, stability of electrodeposition bath and coated film against light and heat is lowered. On the other hand, when the amount is more than 99.999 parts by weight, there is a tendency to undesirably make the photosensitivity too low. As the compound capable of generating an acid when exposed to actinic light (hereinafter referred to as photoacid generator ), there can be used phosphonium salts, sulfonium salts, diazonium salts and iodonium salts, individually containing AsF63, ClO43, BF43, SbF63 or PF63 group; oxazole derivatives, e.g., s-triazine derivatives, e.g., disulfone derivatives, e.g., imidosulfonate derivatives, e.g., nitrobenzyl derivatives of the formula: wherein R is an alkyl group preferably having 1 to 6 carbon atoms, for example, Among these compounds, the oxazole derivatives, s-triazine derivatives, disulfone derivatives, imidosulfonate derivatives and nitrobenzyl derivatives, all having no ionic bond in their molecules (having no salt structure), are preferable from the viewpoint of photosensitivity. Particularly, the nitrobenzyl derivatives are more preferable. The photoacid generator (B) is used in an amount of preferably 0.001 to 40 parts by weight more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the total weight of the components (A) and (B). When the amount is less than 0.001 part by weight, the photosensitivity becomes too low, while when the amount is more than 40 parts by weight, there is a tendency to lower the stability of water dispersibility of electrodeposition bath. The positive type photosensitive anionic electrodeposition coating resin composition of the present invention may contain a compound (a sensitizer) which can increase an acid generation efficiency of the photoacid generator. Examples of the sensitizer are anthracene, phenanthrene, pyrene, thioxanthone, benzophenone, anthrone, Michler's ketone, 9-fluorenone, phenothiazine, etc. The sensitizer can be used in molar ratio of sensitizer/photoacid generator in the range of preferably 0.01/l to 20/l, more preferably 0.1/l to 5/l. The positive type photosensitive anionic electrodeposition coating resin composition of the present invention may contain one or more dyes, pigments, plasticizers, adhesion accelerating agents, inorganic fillers, and the like additives. The resin composition of the present invention containing the components (A) and (B) as major components can be made into an electrodeposition coating solution preferably by dissolving the components (A) and (B) and, if necessary, other additives mentioned above, in a hydrophilic organic solvent uniformly. As the hydrophilic organic solvent, there can be used dioxane, methoxyethanol, ethoxyethanol, diethylene glycol, etc., alone or as a mixture thereof. The organic solvent is used preferably in an amount of 300 parts by weight or less per 100 parts by weight of the total solid components. Then, a base is added to the resulting solution to neutralize the carboxyl group containing in the copolymer (A), resulting in making solubilization in water or dispersion in water easy. As the base, there can be used triethylamine, monoethanolamine, diethanolamine, diisopropylamine, dimethylaminoethanol, morpholine, ammonia, sodium hydroxide, etc., alone or as a mixture thereof. The base is used in an amount of preferably 0.3 to 1.0 equivalent weight per equivalent weight of the carboxyl group in the copolymer (A). When the amount is less than 0.3 equivalent weight, there is a tendency to lower water dispersion stability in the electrodeposition bath, while when the amount is more than 1.0 equivalent weight, the thickness of coated film (photosensitive layer) after electrodeposition becomes thin and there is a tendency to undesirably lower storage stability. Then, an electrodeposition bath is prepared by adding water to the resulting composition for dissolving or dispersing the composition in water. The electrodeposition bath preferably has a solid content of 5 to 20% by weight and pH of 6.0 to 9.0, more preferably 7.0 to 9.0. When the pH is too low, the dispersion becomes worse so as to make electrophoresis difficult. On the other hand, when the pH is higher than 9.0, there often brings about redissolution of once electrodeposited film, resulting in failing to form the film. In order to maintain the pH in the above-mentioned preferable range, a base as mentioned above can be added in later stage for adjustment. In order to enhance the water dispersibility or dispersion stability of the positive type photosensitive anionic electrodeposition coating resin composition, it is possible to add a surfactant such as monionic, anionic, cationic, and the like surfactant. Further, in order to increase a coating amount at the time of electrodeposition, it is possible to add a hydrophobic solvent such as toluene, xylene, 2-ethylhexyl alcohol, etc. Using the resulting electrodeposition bath, electrodeposition can be carried out by dipping a substrate in the electrodeposition bath and usually applying a direct current of 50 to 400 V using the substrate as an anode for 10 seconds to 5 minutes. It is preferable to control the temperature of electrodeposition bath at 15 to 30°C. The substrate should have a surface or surfaces covered with a metal such as iron, aluminum, copper, zinc, or the like, or an alloy thereof, or other electroconductive material (e.g. polypyrrole) and show electroconductivity. After electrodeposition, a coated material is taken out of the electrodeposition bath, washed with water, drained and dried with hot air, etc. When the drying temperature is too high, there is a fear of decomposing the unstable group against an acid, e.g. the tert-butyl ester group, tert-amyl ester group, or isobornyl ester group in the positive type photosensitive anionic electrodeposition coating resin composition. Thus, it is preferable to dry at 110°C or lower. The thickness of thus obtained coated film (photosensitive layer) is preferably 2 to 50 µm. When the film thickness is less than 2 µm, the film is poor in resistance to developer and in the case of using the coated film in the production of printed circuit boards, there is a tendency to be poor in resistance to etching solution and in etch factor when subjected to etching treatment after forming a resist pattern. On the other hand, when the film thickness is more than 50 µm, resolution of resist pattern often lowers. The coated film is then irradiated imagewisely with actinic light to generate an acid on the light exposed portions, and if necessary, heated at 80° to 140°C for 1 to 20 minutes, and then developed for removing the light exposed portions to obtain a resist pattern. As a light source of actinic light, there can be preferably used those emitting a light of 300 to 450 nm in wavelength, for example, mercury vapor arc, carbon arc, xenone arc, etc. The development can usually be carried out by spraying an alkaline aqueous solution of, e.g. sodium hydroxide, sodium carbonate, potassium hydroxide, etc., or by dipping in such an alkaline aqueous solution. Thus, a printed circuit board with high density and high precision can be produced by exposing to light and developing an electrodeposited film formed on a substrate. The present invention is illustrated by way of the following Examples. Reference Example 1Copolymers (A-1) to (A-4) were prepared as follows. (A-1)In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introducing pipe, 1130 g of dioxane was placed and heated to 90°C with stirring while introducing a nitrogen gas thereinto. When the temperature became constant at 90°C, a mixed fluid of 100 g of methacrylic acid, 500 g of tert-butyl methacrylate, 400 g of n-butyl acrylate and 10 g of azobisisobutyronitrile was added dropwise to the flask in 3 hours, followed by stirring at 90°C for 3 hours. Then, a solution obtained by dissolving 3 g of azobisdimethylvaleronitrile in 100 g of dioxane was added dropwise to the flask in 10 minutes, followed by stirring at 90°C for 4 hours. The thus obtained copolymer (A-1) had a weight average molecular weight of 45,000 and an acid number of 65. The solid content of the copolymer solution was 45.2% by weight. (A-2)In the same flask as used in (A-1), 1130 g of propylene glycol monomethyl ether was placed and heated to 90°C with stirring, while introducing a nitrogen gas thereinto. When the temperature became constant at 90°C, a mixed fluid of 77 g of methacrylic acid, 350 g of tert-butyl methacrylate, 450 g of 2-ethylhexyl acrylate, 123 g of methyl methacrylate and 7 g of azobisisobutyronitrile was added dropwise to the flask in 3 hours, followed by stirring at 90°C for 3 hours. Then, a solution obtained by dissolving 3 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monomethyl ether was added dropwise to the flask in 10 minutes, followed by stirring at 90°C for 4 hours. The thus obtained copolymer (A-2) had a weight average molecular weight of 53,000 and an acid number of 50.5. The solid content of the copolymer solution was 45.1% by weight. (A-3)In the same flask as used in (A-1), 1130 g of propylene glycol monopropyl ether was placed and heated to 80°C with stirring, while introducing a nitrogen gas thereinto. When the temperature became constant at 80°C, a mixed fluid of 141 g of acrylic acid, 620 g of tert-butyl methacrylate, 239 g of 2-ethylhexyl acrylate, and 10 g of azobisisobutyronitrile was added dropwise to the flask in 3 hours, followed by stirring at 80°C for 4 hours. Then, a solution obtained by dissolving 3 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monopropyl ether was added dropwise to the flask in 10 minutes, followed by stirring at 80°C for 6 hours. The thus obtained copolymer (A-3) had a weight average molecular weight of 63,000 and an acid number of 110.5. The solid content of the copolymer solution was 45.3% by weight. (A-4)In the same flask as used in (A-1), 1130 g of propylene glycol monopropyl ether was placed and heated to 100°C with stirring, while introducing a nitrogen gas thereinto. When the temperature became constant at 100°C, a mixed fluid of 54 g of methacrylic acid, 290 g of tert-butyl methacrylate, 200 g of n-butyl acrylate, 256 g of methyl methacrylate, 200 g of ethyl acrylate and 10 g of azobisisobutyronitrile was added dropwise to the flask in 3 hours, followed by stirring at 100°C for 3 hours. Then, a solution obtained by dissolving 3 g of azobisdimethylvaleronitrile in 100 g of propylene glycol monopropyl ether was added dropwise to the flask in 10 minutes, followed by stirring at 100°C for 4 hours. The thus obtained copolymer (a-4) had a weight average molecular weight of 31,000 and an acid number of 36.1. the solid content of the copolymer solution was 45.1% by weight. Example 1To 221 g of the copolymer (A-1) solution, 1 g of 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine was added, followed by addition of 9.5 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 7.9). Example 2To 222 g of the copolymer (A-2) solution, 2 g of 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine was added, followed by addition of 8.2 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 8.4). Example 3To 221 g of the copolymer (A-3) solution, 2 g of p-nitrobenzyl derivative of the formula (I) wherein R is an ethyl group and 50 g of dioxane were added and dissolved, followed by addition of 12 g of triethylamine for neutralization. Then, 730 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 7.2). Example 4To 222 g of the copolymer (A-4) solution, 4 g of nitrobenzyl derivative of the formula (I) wherein R is a butyl group and 50 g of dioxane were added, followed by addition of 6.5 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 8.9). Comparative Example 1A copolymer was synthesized under the same conditions as (A-1) except for using the same amount of methyl methacrylate in place of n-butyl acrylate (the component (c)) in the monomer composition of (A-1). The resulting copolymer had a weight average molecular weight of 46,000 and an acid number of 65. The solid content of the copolymer solution was 45.3% by weight. Using the resulting copolymer solution, an electrodeposition bath was prepared in the same manner as described in Example 1. In each electrodeposition bath obtained in Examples 1 to 4 and Comparative Example 1 (water dispersion stability of each electrodeposition bath being shown in Table 1), a substrate of copper-clad glass epoxy laminate (MCL-E-62, a trade name, mfd. by Hitachi Chemical Company, Ltd.) as an anode and a stainless steel plate (SUS 304, a size of 200 mm x 75 mm x 1 mm) as a cathode were dipped. A direct current of 150 V was applied for 3 minutes at 25°C to form an electrodeposited film on the surface of copper-clad laminate, which was washed with water, drained and dried at 80°C for 15 minutes (the film thickness after dried and surface appearance of coated film being shown in Table 1). Then, the resulting film was exposed to light via a photomask with a dose of 800 mJ/cm2 from a 3 kW ultrahigh pressure mercury lamp, followed by heating at 130°C for 10 minutes. After cooling the substrate, development was carried out by spraying an aqueous solution of 1% sodium carbonate (spraying pressure: 1.0 kg/cm2). The photosensitivity and the resolution are shown in Table 1. As is clear from Table 1, the water dispersion stability of each electrodeposition bath of the present invention is remarkably good. Further, the photosensitivity of resist is high, so that a good resist pattern with high resolution is formed. On the other hand, the electrodeposition bath of Comparative Example 1 is worse in the water dispersion stability compared with Examples 1 to 4. Further, the film thickness obtained under the same electrodeposition conditions as Examples 1 to 4 is thinner than those of Examples 1 to 4. Electrodeposition properties such as surface appearance of coated film are remarkably poor. As to photosensitive properties, the photosensitivity of Comparative Example 1 has a tendency to lower. In addition, the resolution is low probably due to poor surface state of the film. Reference Example 2copolymers (A-5) to (A-8) were prepared as follows. (A-5)The process of (A-1) in Reference Example 1 was repeated except for using the following mixed fluid: methacrylic acid 100 g tert-amyl methacrylate650 g n-butyl acrylate 250 g azobisisobutyronitrile10 g The thus obtained copolymer (A-5) had a weight average molecular weight of 38,000 and an acid number of 65.2. The solid content of the copolymer solution was 45.1% by weight. (A-6)The process of (A-2) in Reference Example 1 was repeated except for using the following mixed fluid: methacrylic acid77 g tert-amyl methacrylate310 g 2-ethylhexyl acrylate450 g methyl methacrylate163 g azobisisobutyronitrile7 g The thus obtained copolymer (A-6) had a weight average molecular weight of 45,000 and an acid number of 50.2. the solid content of the copolymer solution was 45.3% by weight. (A-7)The process of (A-3) in Reference Example 1 was repeated except for using the following mixed fluid: acrylic acid141 g tert-amyl methacrylate500 g 2-ethylhexyl acrylate359 g azobisisobutyronitrile10 g The thus obtained copolymer (A-7) had a weight average molecular weight of 51,000 and an acid number of 111.1. The solid content of the copolymer solution was 45.1% by weight. (A-8)The process of (A-4) in Reference Example 1 was repeated except for using the following mixed fluid: acrylic acid54 g tert-amyl methacrylate250 g n-butyl acrylate200 g methyl methacrylate296 g ethyl acrylate200 g azobisisobutyronitrile10 g The thus obtained copolymer (A-8) had a weight average molecular weight of 27,000 and an acid number of 37.2. The solid content of the copolymer solution was 45.5% by weight. Example 5To 222 g of the copolymer (A-5) solution, 1 g of 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and 3 g of a p-nitrobenzyl derivative of the formula (I) wherein R is a propyl group were added, followed by addition of 9.5 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 7.9). Example 6To 221 g of the copolymer (A-6) solution, 2 g of 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine and 1 g of a p-nitrobenzyl derivative of the formula (I) wherein R is an ethyl group were added, followed by addition of 8.2 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually with stirring to the resulting fluid to give an electrodeposition bath (pH 8.4). Example 7To 222 g of the copolymer (A-7) solution, 2 g of a p-nitrobenzyl derivative of the formula (I) wherein R is an ethyl group and 50 g of dioxane were added and dissolved, followed by addition of 12 g of triethylamine for neutralization. Then, 730 g of deionized water was added dropwise gradually with stirring to give an electrodeposition bath (pH 7.3). Example 8To 220 g of the copolymer (A-8) solution, 4 g of a p-nitrobenzyl derivative of the formula (I) wherein R is a butyl group and 50 g of dioxane were added, followed by addition of 6.5 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually with stirring to give an electrodeposition bath (pH 8.8). Comparative Example 2A copolymer was synthesized under the same conditions as (A-5) except for using the same amount of methyl methacrylate in place of n-butyl acrylate (the component (c)) in the monomer composition of (A-5). The resulting copolymer had a weight average molecular weight of 37,000 and an acid number of 65. The solid content of the copolymer solution was 45.4% by weight. Using the resulting copolymer solution, an electrodeposition bath was prepared in the same manner as described in Example 5. In each electrodeposition bath obtained in Examples 5 to 8 and Comparative Example 2 (water dispersion stability of each electrodeposition bath being shown in Table 2), a substrate of copper-clad glass epoxy laminate (MCL-E-61, a trade name, mfd. by Hitachi Chemical Company, Ltd.) as an anode and a stainless steel plate (SUS 304, a size of 200 mm x 75 mm x 1 mm) as a cathode were dipped. A direct current of 150 V was applied for 3 minutes at 25°C to form an electrodeposited film on the surface of copper-clad laminate, which was washed with water, drained and dried at 80°C for 15 minutes (the film thickness after dried and surface appearance of the obtained film being shown in Table 2). Then, the resulting film was exposed to light via a photomask with a dose of 800 mJ/cm2 from a 3 kW ultrahigh pressure mercury lamp, followed by heating at 130°C for 10 minutes. After cooling the substrate, development was carried out by spraying an aqueous solution of 1% sodium carbonate (spraying pressure: 1.0 kg/cm2). The photosensitivity and the resolution are shown in Table 2. As is clear from Table 2, the water dispersion stability of each electrodeposition bath of the present invention is remarkably good. Further, the photosensitivity of resist is high, so that a good resist pattern with high resolution is formed. On the other hand, the electrodeposition bath of Comparative Example 2 is worse in the water dispersion stability compared with Examples 5 to 8. Further, the film thickness obtained under the same electrodeposition conditions as Examples 5 to 8 is thinner than those of Examples 5 to 8. Electrodeposition properties such as surface appearance of coated film are remarkably poor. As to photosensitive properties, the photosensitivity of Comparative Example 2 has a tendency to lower. In addition, the resolution is low probably due to poor surface state of the film. Reference Example 3Copolymers (A-9) to (A-12) were prepared as follows. (A-9)The process of (A-1) in Reference Example 1 was repeated except for using the following mixed fluid: methacrylic acid100 g isobornyl acrylate650 g n-butyl acrylate250 g azobisisobutyronitrile10 g The thus obtained copolymer (A-9) had a weight average molecular weight of 36,000 and an acid number of 65.0. The solid content of the copolymer solution was 45.1% by weight. (A-10)The process of (A-2) in Reference Example 1 was repeated except for using the following mixed fluid: methacrylic acid77 g isobornyl methacrylate310 g 2-ethylhexyl acrylate450 g methyl methacrylate163 g azobisisobutyronitrile7 g The thus obtained copolymer (A-10) had a weight average molecular weight of 44,000 and an acid number of 50.6. The solid content of the copolymer solution was 45.0% by weight. (A-11)The process of (A-3) in Reference Example 1 was repeated except for using the following mixed fluid: acrylic acid141 g isobornyl acrylate500 g 2-ethylhexyl acrylate359 g azobisisobutyronitrile10 g The thus obtained copolymer (A-11) had a weight average molecular weight of 50,000 and an acid number of 111.4. The solid content of the copolymer solution was 44.6% by weight. (A-12)The process of (A-4) in Reference Example 1 was repeated except for using the following mixed fluid: methacrylic acid54 g isobornyl methacrylate250 g n-butyl acrylate200 g methyl methacrylate296 g ethyl acrylate200 g azobisisobutyronitrile10 g The thus obtained copolymer (A-12) had a weight average molecular weight of 25,000 and an acid number of 37.7. The solid content of the copolymer solution was 45.2% by weight. Example 9To 223 g of the copolymer (A-9) solution, 1 g of 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and 3 g of a p-nitrobenzyl derivative of the formula (I) wherein R is a propyl group were added, followed by addition of 9.4 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually to the resulting fluid with stirring to give an electrodeposition bath (pH 7.8). Example 10To 222 g of copolymer (A-10) solution, 2 g of 2-(p-methoxstyryl)-4,6-bis(trichloromethyl)-s-triazne and 1 g of a p-nitrobenzyl detrivative of the formula (I) wherein R is an ethyl group were added, followed by addition of 8.3 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually with stirring to the resulting fluid to give an electrodeposition bath (pH 8.3). Example 11To 224 g of copolymer (A-11) solution, 2 g of a p-nitrobenzyl derivative of the formula (I) wherein R is an ethyl group and 50 g of dioxane were added and dissolved, followed by addition of 12 g of triethylamine for neutralization. Then, 730 g of deionized water was added dropwise gradually with stirring to give an electrodeposition bath (pH 7.2). Example 12To 221 g of the copolymer (A-12) solution, 4 g of a p-nitrobenzyl derivative of the formula (I) wherein R is a butyl group and 50 g of dioxane were added, followed by addition of 6.6 g of triethylamine for neutralization. Then, 780 g of deionized water was added dropwise gradually with stirring to give an electrodeposition bath (pH 8.9). Comparative Example 3A copolymer was synthesized under the same conditions as (A-9) except for using the same amount of methyl acrylate in place of n-butyl acrylate (the component (c)) in the monomer composition of (A-9). The resulting copolymer had a weight average molecular weight of 37,000 and an acid number of 65. The solid content of the copolymer solution was 45.4% by weight. Using the resulting copolymer solution, an electrodeposition bath was prepared in the same manner as described in Example 9. Each electrodeposition bath obtained in Examples 9 to 12 and Comparative Example 3 was subjected to evaluation of the water dispersion stability by observing days to generate a precipitate from the initial time of electrodeposition bath while allowing to stand. The results are shown in Table 3. In each electrodeposition bath obtained in Examples 9 to 12 and Comparative Example 3, a substrate of copper-clad glass epoxy laminate (MCL-E-61, a trade name, mfd. by Hitachi Chemical Company, Ltd.) as an anode and a stainless steel plate (SUS 304, a size of 200 mm x 75 mm x 1 mm) as a cathode were dipped. A direct current of 150 V was applied for 3 minutes at 25°C to form an electrodeposited film on the surface of copper-clad laminate, which was washed with water, drained and dried at 80°C for 15 minutes (the film thickness after dried and surface appearance of the obtained film being shown in Table 3). Then, the resulting film was exposed to light via a photomask with a dose of 800 mJ/cm2 from a 3 kV ultrahigh pressure mercury lamp, followed by heating at 140°C for 10 minutes. After cooling the substrate, development was carried out by spraying an aqueous solution of 1% by weight sodium carbonate (spraying pressure: 1.0 kg/cm2). The photosensitivity and the resolution were measured and shown in Table 3. The photosensitivity was evaluated by step tablets using photomasks having an optical density of 0.05 at a first step and an increasing optical density of 0.15 per each step. As is clear from Table 3, the water dispersion stability of each electrodeposition bath of the present invention is remarkably good. Further, the photosensitivity of resist is high, so that a good resist pattern with high resolution is formed. On the other hand, the electrodeposition bath of Comparative Example 3 is worse in the water dispersion stability compared with Examples 9 to 12. Further, the film thickness obtained under the same electrodeposition conditions as Examples 9 to 12 is thinner than those of Examples 9 to 12. Electrodeposition properties such as surface appearance of coated film are remarkably poor. As to photosensitive properties, the photosensitivity of Comparative Example 3 has a tendency to lower. In addition, the resolution is low probably due to poor surface state of the film. Comparative Example 4A copolymer was synthesized under the same conditions as (A-8) except for using the same amount of methyl methacrylate in place of n-butyl acrylate (the component (c)) in the monomer composition of (A-8). The resulting copolymer (P-2) had a weight average molecular weight of 29,000 and an acid number of 40.3. The solid content of the copolymer solution was 45.4% by weight. Using the resulting copolymer solution, an electrodeposition bath was prepared in the same manner as described in Example 8. Comparative Example 5A copolymer was synthesized under the same conditions as (A-1) except for using the same amount of methyl methacrylate in place of tert-butyl methacrylate (the component (b)) in the monomer composition of (A-1). The resulting copolymer (P-3) had a weight average molecular weight of 38,000 and an acid number of 64.9. The solid content of the copolymer solution was 45.5% by weight. Using the resulting copolymer solution, an electrodeposition bath was prepared in the same manner as described in Example 1. Comparative Example 6Using the copolymer solution (P-3) in place of copolymer solution (A-1) and the same amount of 1,2-naphthoquinonediazido-5-sulfonate ester of 2,3,4-trihydroxybenzophenone in place of 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine (the component (B)), an electrodeposition bath was prepared in the same manner as described in Example 1. As mentioned above, the water dispersion stability of each electrodeposition bath of present invention is remarkably good. Furhter, the photosensitivity of resist is high, so that a good resist pattern with high resolution is formed, which shows that the present invention is good for producing higher density printed circuit boards without causing cutting of circuits or short-circuit. On the other hand, the electrodeposition bath of Comparative Examples 1 and 2 using the copolymer synthesized with methyl methacrylate capable of forming a homopolymer having a glass transition temperature of 100°C or higher in place of the component (c) are worse in the water dispersion stability compared with Examples 1 to 12. Further, the film thickness obtained under the same electrodeposition conditions as Examples 1 to 12 is thinner than those of Examples 1 to 12, and surface appearance of coated film is worse, so that electrodeposition properties are remarkably poor. As to photosensitive properties, the photosensitivity of Comparative Examples 4 has a tendency to lower. In addition, the resolution is low probably due to poor surface state of film. In case of Comparative Example 5 using the copolymer synthesized with methyl methacrylate which has no unstable group against an acid in place of the component (b), electrodeposition properties are the same as Examples 1 to 12, but the exposure part cannot be developed, resulting in showing no photosensitivity. In case of Comparative Example 6 using 1,2-naphthoquinonediazido-5-sulfonate ester of 2,3,4-trihydroxybenzophenone in place of the component (B), further, the film thickness obtained under the same electrodeposition conditions as Examples 1 to 12 is smaller than those of Examples 1 to 12, and surface appearance of coated film is worse, so that electrodeposition properties are remarkably poor, and the stability of the electrodeposition bath is worse. As to photosensitive properties, Comparative Example 6 has a tendency to lower the photosensitivity. In addition, the resolution is low probably due to poor surface state of film. As is clear from these results, various improvements of properties shown in Examples 1 to 12 are obtained by using the positive type photosensitive anionic electrodeposition coating resin composition comprising a copolymer (A) obtained from particularly a compound having an unstable group against an acid and a photoacid generator (B). As mentioned above, the water dispersion stability of electrodeposition baths using the positive type photosensitive anionic electrodeposition coating resin compositions of the present invention is remarkably high. Further, electrodeposited films (photosensitive films) obtained by electrodeposition using such electrodeposition baths are remarkably excellent in photosensitivity and high in the resolution to form a resist pattern with desirable good shape. The resulting resist pattern can be used as a relief. Further, by forming a resist pattern using a copper-clad laminate as a substrate and conducting etching or plating, or the like, a printed circuit board with remarkably high in precision and density can be produced.
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A positive type photosensitive anionic electrodeposition coating resin composition comprising (A) a copolymer comprising residues of (a) acrylic acid or methacrylic acid or both, (b) at least one polymerizable compound selected from t-butyl methacrylate, t-butyl acrylate, t-amyl methacrylate, t-amyl acrylate, isobornyl methacrylate, isobornyl acrylate and mixtures of two or more thereof, and (c) a polymerizable monomer capable of forming a homopolymer having a glass transition temperature of 0°C or lower, copolymer (A) comprising, per 100 parts by weight of the total amounts of monomer constituting copolymer (A), 2 to 35 parts by weight of component (a), 10 to 80 parts by weight of component (b) and 5 to 75 parts of component (c), and (B) a compound capable of generating an acid when exposed to actinic light. A composition according to claim 1, wherein the component (b) is t-butyl methacrylate, t-butyl acrylate or a mixture thereof. A composition according to claim 1, wherein the component (b) is t-amyl methacrylate, t-amyl acrylate or a mixture thereof. A composition according to claim 1, wherein the component (b) is isobornyl methacrylate, isobornyl acrylate or a mixture thereof. A composition according to any one of claims 1 to 4 wherein the component (c) is n-butyl acrylate, and 2-ethylhexyl acrylate or a mixture thereof. A composition according to any one of claims 1 to 5 wherein the component (B) is a compound of the formula (I) wherein R is an alkyl group. An electrodeposition bath comprising a composition according to any one of claim 1 to 6. Use of a composition according to any one of claims 1 to 6 or an electrodeposition bath according to claim 7 in electrodeposition using a substate as an anode. A process for producing a printed circuit board comprising forming an electrodeposited film on a substrate by use of a composition according to any one of claims 1 to 6 or an electrodeposition bath according to claim 7 and then exposing the film to light and developing the exposed film.
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HITACHI CHEMICAL CO LTD; HITACHI CHEMICAL CO., LTD.
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AKAHORI TOSHIHIKO; HIRO MASAHIKO; KATO TAKURO; TACHIKI SHIGEO; AKAHORI, TOSHIHIKO; HIRO, MASAHIKO; KATO, TAKURO; TACHIKI, SHIGEO
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EP-0489561-B1
| 489,561 |
EP
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B1
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EN
| 19,960,306 | 1,992 | 20,100,220 |
new
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B44F1
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G09F13
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B32B27, B32B7, B44F1, G09F13
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B44F 1/04, G09F 13/20
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Articles exhibiting durable fluorescence
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Retroreflective article (10) comprising an ultraviolet screening screen layer (18) and a color layer (12) containing a defined daylight fluorescent dye dissolved in a defined polymeric matrix. The article exhibits durable fluorescence and resistance to degradation from exposure to sunlight. If desired, the article can be made retroreflective by forming retroreflective elements (20) in the color layer.
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Field of InventionThe present invention relates to articles which exhibit durable fluorescence, and in one embodiment relates particularly to retroreflective sheetings which exhibit durable fluorescence. BackgroundRetroreflective signs have achieved widespread use for safety and informational signs along roads because of the high nighttime visibility they provide. In order to enhance the daytime visibility of such signs, it has been suggested to make the signs fluorescent as well as retroreflective. U.S. Patent No. 3,830,682 (Rowland) discloses cube-corner type retroreflective sheetings which incorporate fluorescent dyes, e.g., rhodamine and fluorescein dyes. The resultant signs provide fluorescent ambient appearance and bright, colored retroreflection. A problem with fluorescent retroreflective sheetings is that upon, in some cases relatively moderate, exposure to solar radiation, such as is encountered in sunlit outdoor applications, the fluorescent properties of the sheetings degrade. Many fluorescent dyes tend to fade or become colorless. This loss in fluorescent performance causes the ambient color of the subject sheeting to fade as well as changing the retroreflective appearance of the sign, thereby impairing the effectiveness of the sign and reducing the potential safety benefits thereof. In some instances, such degradation can occur over as short a time as six months. U.S. Patent No. 3,830,682 (Rowland) discloses retroreflective articles comprising synthetic plastic resins and fluorescent dyes such as rhodamine and fluoroscein dyes. Japan Kokai No. 2-16042, Application No. 63-165914 (Koshiji et al.) discloses fluorescent articles comprising a screen layer and a layer containing a fluorescent coloring agent wherein the screen layer permits a defined range of transmission of light. According to the reference, the screen layer must have a transmittance of more than 30 percent at 370 nanometers and less than 20 percent at 340 nanometers. The reference further teaches that the coloring agent may be any fluorescent coloring agent and that the binder or matrix of the colored layer is subject to no critical limitation. Summary of InventionThe present invention provides articles that exhibit a surprising enhancement in fluorescent durability, i.e., the fluorescent properties of the articles are retained longer than is expected, even upon prolonged exposure to direct sunlight. Sunlight, i.e., ground level solar radiation, comprises electromagnetic radiation having wavelengths within the range of about 290 nanometers up through visible light range. In brief summary, fluorescent articles of the invention comprise a color layer having first and second sides and a screen layer disposed to the first side of said color layer, wherein: a) the color layer comprises a defined fluorescent dye dissolved in a defined polymeric matrix; and b) the screen layer being substantially transparent to visible light and comprising means for screening substantial portions of ultraviolet radiation which is incident thereto. The color layer and screen layer may be separate layers arranged in the defined manner or may be laminated together, either directly or with an intermediate adhesive layer. In one particularly useful class of embodiments, the article is retroreflective and the color layer is substantially transparent, with the color layer either having retroreflective elements formed on its second, i.e., back side, or having a retroreflective base layer comprising retroreflective elements disposed on its second side. Brief Description of DrawingThe invention will be further explained with reference to the drawing, wherein: Figure 1 is a cross-sectional illustration of a portion of one retroreflective embodiment of the invention; Figure 2 is a cross-sectional illustration of a portion of another retroreflective embodiment of the invention; and Figure 3 is a cross-sectional illustration of another retroreflective embodiment of the invention. These figures, which are idealized, are not to scale and are intended to be merely illustrative and non-limiting. Detailed Description of Illustrative EmbodimentsFigure 1 shows typical fluorescent article 10 of the invention comprising color layer 12 with first, i.e., front, side 14 and second, i.e., back, side 16 and overlay or screen layer 18 disposed on first side 14. In the embodiment illustrated, screen layer 18 is laminated directly to color layer 12. Article 10 is retroreflective, and color layer 16 has retroreflective elements 20, e.g., cube-corner retroreflective elements, formed therein. Figure 2 shows another typical fluorescent article 30 comprising color layer 32 with first side 34 and second side 36 and screen layer 38 disposed on first side 34. In the embodiment illustrated, screen layer 38 is bonded to color layer 32 with intermediate adhesive layer 33. In order to render article 30 retroreflective, retroreflective base sheet 42 has been bonded to second side 36 with intermediate adhesive layer 40. Color layers of articles of the invention comprise a defined daylight fluorescent dye dissolved in a defined polymeric matrix. The polymeric matrix is typically preferably substantially transparent to visible light, particularly to light of the wavelengths emitted by the dye and light of the wavelengths which cause the dye to fluoresce. The polymeric matrix is selected from one or more of the following: polycarbonate, polyacrylic imide, polyester, or polystyrene. In embodiments wherein the color layer has reflective elements formed therein, e.g., cube-corner reflectors, polycarbonate is typically preferred because it tends to exhibit greater dimensional stability than polyester. Preferably, the matrix consists essentially of one of the indicated polymers. Color layers made with a single polymer matrix material will typically tend to exhibit greater transparency than will those made with substantial portions, e.g., 5 weight percent or more each, of two or more polymers. However, blends of two or more substantially transparent polymers that are substantially miscible are typically transparent and may be used herein. The fluorescent dye, which is a daylight fluorescent dye, i.e., one which emits visible light upon exposure to light of a visible wavelength is selected from the following: thioxanthene dye, thioindigoid dye, benzoxazole coumarin dye, or perylene imide dye. If desired, a combination of such dyes may be used. Typically, the color layer contains between about 0.01 and about 1.0, preferably between about 0.05 and about 0.3, weight percent of dye. Color layers that contain lower amounts of dye may not exhibit the degree of bright fluorescence which is desired. As will be understood by those skilled in the art, however, thicker color layers containing a specified loading of dye will typically exhibit brighter fluorescence and deeper color than do thinner color layers containing the same dye loading. Color layers which contain high levels of fluorescent dye may exhibit self-quenching phenomena. It has been observed that between two embodiments of the invention wherein the color layers have substantially equivalent initial fluorescent brightness and appearance, the first color layer being made with relatively greater thickness and a relatively lower dye loading and the second color layer being made with relatively thinner thickness and relatively higher dye loading, the color layer having the lower dye loading exhibited greater fluorescent durability than the other color layer. Both embodiments, however, exhibited greater fluorescent durability than expected. In some instances, the dye in the color layer will consist essentially of thioxanthene, thioindigoid, benzoxazole coumarin, and/or perylene imide dyes. In other instances, however, the color layer may also contain coloring agents such as pigments or other dyes in addition to those described above to adjust the color and appearance of the article. For instance, polycarbonate typically has a slight yellowish cast or appearance and minor amounts, e.g., about 0.01 weight percent or less, of colorants sometimes referred to as bluing agents may be incorporated therein to yield a substantially colorless or water white appearance. Typically, the color layer will contain at most limited quantities of dyes other than those described above as other dyes typically do not exhibit desired durable fluorescence and color layers which contain high proportions thereof will be subject to detrimental effects upon prolonged exposure to sunlight. If desired, non-fluorescent dyes or pigments may also be used, however, such dyes should be selected so as to not undesirably interfere with the fluorescent performance of the daylight fluorescent dyes discussed above or with the overall appearance of the article. In the case of retroreflective articles, any non-fluorescent dyes or pigments used should not undesirably impair the transparency of the color layer. In some embodiments, e.g., wherein the article is a retroreflective sheeting, the color layer is typically between about 2 and about 25 mils (50 and 625 micrometers) thick as such thicknesses offer a useful balance of cost and performance, particularly for retroreflective embodiments. If desired, however, color layers having thicknesses outside this range may be made in accordance with the invention. The screen layer is disposed to the first or front side of the color layer so as to shield same from ultraviolet radiation which is incident to the article. This is the side of the article which is displayed and is desirably fluorescent. In the case of retroreflective embodiments, this side exhibits retroreflective properties, i.e., light such as from vehicle headlights that is incident thereto is retroreflected. As shown in Figure 1, screen layer 18 may be in direct contact with color layer 12, or, as shown in Figure 2, screen layer 38 may be bonded to color layer 32 with intermediate layer 33, or, as shown in Figure 3, screen layer 58 may be arranged in front of color layer 52 substantially without contacting it. Preferably, the screen layer and color layer are substantially coextensive such that the screen layer protects substantially all of the color layer. The screen layer and, if used, the adhesive intermediate to the screen layer and color layer, are preferably substantially transparent to visible light of the wavelength emitted by the fluorescent dye in the color layer as well as being substantially transparent to light of the wavelength which excites the dye. At ground level solar radiation comprises electromagnetic radiation having wavelengths greater than about 290 nanometers, with the range of about 400 to about 700 nanometers typically being considered the visible light range. Radiation having lower wavelengths is believed to be the most damaging to fluorescent durability of dyes in the color layer, thus the screen layer preferably blocks a substantial portion, i.e., at least about 10 percent, more preferably at least about 50 percent, and most preferably substantially all, of the incident radiation having a wavelength below about 340 nanometers, more preferably below about 370 nanometers, and most preferably below about 400 nanometers. Radiation of these ranges is a major cause of the loss of fluorescent brightness of fluorescent dyes in polymeric matrices. In some embodiments, the screen layer may even screen electromagnetic radiation having wavelengths above about 400 up to, but below, the wavelengths which excite the dye. Although such screen layers would provide more effective protection to the color layer, they would tend to have a colored appearance which must be taken into account when formulating the color of the color layer such that the resultant article is of desired color. If desired, tinting screen layers, color layers, and/or intermediate adhesive layers (if any) to screen selected visible wavelengths could be used to tune the fluorescent response of the article. The screen layer comprises means for screening ultraviolet radiation; it may be made of a material that inherently screens radiation as desired, or it may comprise a matrix which contains a selected screening agent to impart desired characteristics thereto. If an intermediate adhesive is used, it may contain ultraviolet screening agent so as to function as a screen layer. It has been observed that incorporating ultraviolet radiation screening agents in the color layer may tend to provide minor improvements in fluorescent durability of the fluorescent dye contained therein, but the effect is relatively minor in relation to the advantages provided by use of separate screen and color layers as provided herein. Although we do not wish to be bound by this theory, it is believed that, by screening radiation as discussed above, the screen layer prevents an as yet undefined degradation and/or reaction between the dyes and polymeric matrix materials which would otherwise occur. Insofar as we know, the advantages of the present invention are attained through the use of the combinations of fluorescent dyes and polymeric matrix materials discussed herein. As discussed above, in some embodiments, articles of the invention are retroreflective. Such capability may be achieved as shown in Figure 1 by forming retroreflective elements 20 on second side 16 of color layer 12, or alternatively as shown in Figure 2 by attaching retroreflective base sheet 42 to second 36 of color layer 32, either with transparent intermediate adhesive layer 40 as shown or by laminating the base sheet and color layer in direct contact with one another (not shown). As shown in Figure 2, retroreflective base sheet 42 comprises a member with cube-corner retroreflective elements formed on back side 46 thereof. In other embodiments, the retroreflective base sheet may comprise a microsphere-based retroreflective structure, e.g., comprising a monolayer of transparent microspheres and reflective means disposed on the opposite side of the monolayer as the color layer. For instance, a screen layer/color layer combination of the invention may be laminated to the front surface of the cover film of an encapsulated-lens retroreflective sheeting such as is disclosed in U.S. Patent No. 3,190,178 (McKenzie) or it may even be used as the cover film of an encapsulated-lens sheeting. In retroreflective embodiments, the color layer or at least that portion of it which is disposed in front of the retroreflective elements, i.e., between the retroreflective elements and the screen layer, should be substantially transparent to visible light. Figure 3 illustrates another retroreflective embodiment of the invention wherein the article of the invention is a button-type retroreflector. Article 50 comprises color layer 52 with first side 54 and second side 56, screen layer 58 disposed to first side 54, and base member 60, with screen layer 58 and base member 60 enclosing color layer 52. Second side 56 has retroreflective elements 62 formed therein. Screen layer 58 and color layer 52 can be disposed spaced apart from one another as shown, or alternatively may be placed in contact with one another. Article 50 can be mounted on a backing (not shown), e.g., a sign panel, such that first side 54 is presented for viewing and retroreflective effect, with screen layer 58 protecting the fluorescent durability of color layer 52 as described herein. If desired, articles of the invention may be made in substantially rigid or flexible form. For example, in some embodiments the article may be sufficiently flexible to be wound about a mandrel having a diameter of about 1 centimeter. ExamplesThe invention will be further explained by the following illustrative examples which are intended to be nonlimiting. Unless otherwise indicated, all amounts are expressed in parts by weight. The following abbreviations are used in the examples: Abbreviation Meaning AUAcrylic urethane; PAIPolyacrylic imide; PCPolycarbonate; POPolyolefin copolymer; PECPolyester carbonate; PETPolyethylene terephthalate; PMMAPolymethylmethacrylate; PSPolystyrene; PVCPolyvinyl chloride (plasticized); SCASolution cast acrylic; RED GGHOSTASOL RED GG - Solvent Orange 63 thioxanthene dye from Hoechst Celanese; RED 5BHOSTASOL RED 5B - Vat Red 41 thioindigoid dye from Hoechst Celanese; LUMOGENLUMOGEN F240 Orange - perylene imide dye from BASF; MACROLEXMACROLEX 10GN - Solvent Yellow 160:1 benzoxazole coumarin dye from Mobay Corp.; 3GHOSTASOL YELLOW 3G - Solvent Yellow 98 thioxanthene dye from Hoechst Celanese; and GREEN GOLDFLUOROL GREEN GOLD 084 - Solvent Green 5 perylene dye from BASF. To simulate outdoor exposure to sunlight on an accelerated basis, in Examples 1-4 samples were exposed in accordance to ASTM G 26 - Type B, Method A, with a water-cooled xenon arc device with borosilicate inner and outer filters for periods of 102 minutes of exposure at a Black Panel temperature of about 63?C following by 18 minutes of exposure while subjecting the sample to deionized water spray. One thousand hours exposure on this device is believed to be equivalent to several months exposure to direct sunlight in an outdoor setting. Unless otherwise indicated, the following test methods were used. ColorColor was determined by one of two techniques as indicated. In the first technique, referred to herein as ISC , a Spectrosensor Integrating Sphere Colorimeter from Applied Color Systems was used at the following settings and conditions: D65 Illuminate, d/0 Geometry, Large Area View - Specular Included, 2 Degree Observer, 200 Percent Reflectance Setting, with measurements being taken every 10 nanometers over a range of 400 to 700 nanometers. In the second technique, referred to herein as CSC , a Compuscan Colorimeter from Applied Color Systems was used at the following settings and conditions: D65 Illuminate, 0/45 Geometry, 30 millimeter port size, 2 Degree Observer, with measurements being taken every 20 nanometers over a range of 400 to 700 nanometers. ISC and CSC are believed to provide equivalent color definition results. Peak Retention, was calculated as the ratio in percent of percentage reflectance of the sample after exposure for the indicated time to the percentage reflectance of the sample before exposure at the wavelength of the initial peak percentage reflectance. The CIELAB color difference, Delta E, between the sample after exposure for the indicated period of time and the unexposed sample was determined. Delta E is a function of several color vector components. Accordingly, it should be understood that the Delta E results provided herein should be compared only within pairs of Samples wherein the color layers are equivalent as presented in the tables, but not between Samples of separate pairs. For instance, the Delta E obtained by Sample 5-1 can be meaningfully compared with Sample 5-A, but does not provide any meaningful significance with respect to the Delta E obtained with Sample 5-B or 5-2. Retained FluorescenceFluorescence was determined using a SPEX Brand Fluorolog Spectrophotometer consisting of a xenon lamp powered by a ELXE 500 watt power supply, Model 1680 0.22 meter double spectrometer detector, Model 1681 0.22 meter spectrometer source, and a Products-for-Research Photomultiplier Model R298/115/381 operated by SPEX DM 300 software at a resolution of 2 nanometers. Retained Fluorescence was calculated as the ratio in percent of fluorescent intensity of the sample after exposure for the indicated time to the fluorescent intensity of the unexposed sample, at the wavelength of peak emission of the unexposed sample. Example 1Example 1 illustrates the relationship between composition of polymer matrix of the color layer and utility of screen layer in accordance with the invention. In each of the samples, the color layer contained 0.2 weight percent of HOSTASOL Red GG, a thioxanthene dye. In Sample 1-1 and Comparative Sample 1-A, the color layers consisted essentially of 12 mil (300 micrometer) thick extruded films of water white ultraviolet-stabilized polycarbonate, LEXAN 123R-112 from General Electric Company, believed to contain a small amount of blueing agent and mold release agent. In Sample 1-1, the screen layer was a 3 mil (75 micrometer) thick film consisting essentially of polymethyl methacrylate, LUCITE 47K from Du Pont, and 1.2 weight percent TINUVIN 327, a benzotriazole ultraviolet absorber from Ciba-Geigy. In Comparative Sample 1-A, a similar film without the ultraviolet absorber was used as the screen layer. In Sample 1-2 and Comparative Sample 1-B, the color layers consisted essentially of 6 mil (150 micrometer) thick extruded films of KAMAX T-260, a polyacrylic imide from Rohm and Haas, to which 0.2 weight percent CYASORB UV 5411, a benzotriazole ultraviolet absorber from American Cyanamid, was added. In Sample 1-2, the screen layer was a 2 mil (50 micrometer) thick solvent cast film consisting essentially of an aliphatic acrylic polyurethane and 3 weight percent solids UVINUL 400, a benzophenone ultraviolet absorber from BASF, with a 1 mil (25 micrometer) thick layer of pressure-sensitive adhesive, isooctylacrylate/acrylic acid crosslinked with aziridine, on one side thereof. U.S. Patent No. 4,808,471 (Grunzinger) discloses such films and U.S. Patent No. Re. 24,906 (Ulrich) discloses such adhesives. In Comparative Sample 1-B, a similar film without the ultraviolet absorber was used as the screen layer. In Sample 1-3 and Comparative Sample 1-C, the color layers consisted essentially of 6 mil (150 micrometer) thick extruded films of polyethylene terephthalate (intrinsic viscosity of 0.59 and molecular weight of about 20,000 to 25,000). In Sample 1-3 and Comparative Sample 1-C, the screen layers were like those used in Sample 1-2 and Comparative Sample 1-B, respectively. In Sample 1-4 and Comparative Sample 1-D, the color layers consisted essentially of 6 mil (150 micrometer) thick extruded films of impact modified polystyrene, STYRON 615APR from Dow Chemical Company, to which 0.2 weight percent CYASORB UV 5411 was added. In Sample 1-4 and Comparative Sample 1-D, the screen layers were like those used in Sample 1-2 and Comparative Sample 1-B, respectively. The respective screen layers were bonded to the first sides of the color layers with an intermediate adhesive as in Sample 1-2 and Comparative Sample 1-B. In Comparative Samples 1-E and 1-F, the color layers consisted essentially of 12 mil (300 micrometer) thick extruded films of LUCITE 47K, polymethyl methacrylate from Du Pont containing 0.2 weight percent CYASORB UV 5411. In Comparative Sample 1-E, the screen layer was like that used in Comparative Sample 1-B. In Comparative Sample 1-F, no screen layer was used. In Comparative Samples 1-G and 1-H, the color layers consisted essentially of 6 mil (150 micrometer) thick extruded films of APEC DP9-9308NT, polyester carbonate from Mobay Corp. containing 0.2 weight percent of CYASORB UV 5411. In Sample 1-G, the screen layer was like that used in Sample 1-2. In Comparative Sample 1-H, a similar film without the ultraviolet absorber was used as the screen layer. In Comparative Samples 1-I and 1-J, the color layers consisted essentially of 2 mil (50 micrometer) thick solution cast films of acrylic urethane. In Sample 1-I, the screen layer was like that used in Sample 1-2. In Comparative Sample 1-J, a similar film without the ultraviolet absorber was used as the screen layer. In Comparative Samples 1-K and 1-L, the color layers consisted essentially of 3 mil (75 micrometer) thick solution cast films of plasticized polyvinyl chloride. In Sample 1-K, the screen layer was like that used in Sample 1-2. In Comparative Sample 1-L, a similar film without the ultraviolet absorber was used as the screen layer. In Sample 1-1 and Comparative Samples 1-A, 1-E, and 1-F, the respective screen layer and color layer combinations were placed, with the screen layer in contact with the first side of the color layer, in a stamper shaped to form cube-corner retroreflective elements and stamped at about 204°C to form cube-corner retroreflective elements on the second surface of the color layer. In Samples 1-2, 1-3, and 1-4 and Comparative Samples 1-B, 1-C, 1-D, 1-G, 1-H, 1-I, 1-J, 1-K, and 1-L, the screen layers were bonded to the first sides of the color layers with intermediate adhesive as described above. A retroreflective base sheet, SCOTCHLITE Brand Retroreflective Sheeting Diamond Grade No. 3970 from 3M, was then bonded to the second sides of the color layers with the same adhesive. The results are tabulated in Table I. Sample MatrixScreenTimePeak RetenDelta ERetain Fluor1-1PCYes1000711885 1-APCNo1000553067 1-2PAIYes1000841490 1-BPAINo1000733172 1-3PETYes1000936103 1-CPETNo100084979 1-4PSYes5007721NM⁷ 1-DPSNo5006829NM1-EPMMAYes1000572752 1-FPMMANone1000572760 1-GPECYes1000692076 1-HPECNo1000692070 1-IAUYes5004884NM1-JAUNo5004788NM1-KPVCYes50041100NM1-LPVCNo50040100NMThese results illustrate that the effectiveness of the invention is dependent upon the polymeric matrix material of the color layer. Example 2Example 2 illustrates changing the polymeric matrix of the screen layer. In Samples 2-1, 2-2, and 2-3 and Comparative Samples 2-A, 2-B, and 2-C, the color layers consisted essentially of 12 mil (300 micrometer) thick extruded films of polycarbonate, LEXAN 123R-112 containing 0.12 weight percent of HOSTASOL RED GG. In Sample 2-4 and Comparative Sample 2-D, the color layers were similar except they contained 0.2 weight percent of the fluorescent dye. In Sample 2-1 and Comparative Sample 2-A, retroreflective elements were embossed in the second sides of the color layers and then screen layers were bonded to the first sides of the color layers with an intermediate layer of adhesive as used in some samples of Example 1. The screen layers were 2 mil (50 micrometer) thick films of acrylic polyurethane. In Sample 2-1 the screen layer contained 3 weight percent UVINUL 400. In Sample 2-2 and Comparative Sample 2-B, retroreflective elements were embossed in the second sides of the color layers and then the screen layers were hot laminated directly to the first sides of the color layers. The screen layers were 2 mil (50 micrometer) thick films of ethylene/acrylic acid copolymer. In Sample 2-2 the screen layer contained an ultraviolet absorber. In Sample 2-3 and Comparative Sample 2-C, retroreflective elements were embossed in the second sides of the color layers and then screen layers were solvent cast on the first sides of the color layers and dried. The screen layers were 0.8 to 1.0 mil (20 to 25 micrometer) thick films of solution cast acrylic, ACRYLOID B66 from Rohm and Haas. In Sample 2-3 the screen layer contained 1.2 weight percent TINUVIN 327. In Sample 2-4 and Comparative Sample 2-D, retroreflective elements were embossed in the second sides of the color layers and polymethyl metharylate screen layers were laminated to the first sides of the color layers as in Samples 1-1 and 1-A, respectively. The screen layers were 3 mil (75 micrometer) thick films of LUCITE 47K. In Sample 2-4 the screen layer contained 1.2 weight percent TINUVIN 327. The percentage transmittance of the screen layers at the indicated wavelengths (in nanometers) was as follows: Screen Wavelength 400 370 340 300 2-1844300 2-A78756959 2-280200 2-B84777067 2-3871011 2-489888886 2-456000 2-D87817167 The fluorescent durability results obtained with the resultant fluorescent articles are tabulated in Table IIb. Sample MatrixScreenTimePeak RetenDelta ERetain Fluor2-1AUYes100085791 2-AAUNo1000761285 2-2POYes100089 7103 2-BPO No 1000 79 1386 2-3SCAYes1000828NM2-CSCANo10007513NM2-4PMMAYes1000771585 2-DPMMANo1000642367 These results illustrate that the effectiveness of the screen layer is dependent upon its screening properties and not its composition. Example 3Example 3 illustrates color layers containing different amounts of Red GG fluorescent dye in two different polymeric matrix materials. In each sample, the color layer consisted essentially of a 12 mil (300 micrometer) thick extruded film of the indicated matrix polymer containing the indicated amount of dye. The samples were all exposed for 1000 hours. The results are tabulated in Table III. Sample MatrixDyeScreenPeak RetenDelta E3-1PC0.01Yes918 3-APC0.01No8215 3-2PC0.1Yes888 3-BPC0.1No7217 3-3PC0.3Yes6323 3-CPC0.3No4143 3-DPMMA0.01Yes6344 3-EPMMA0.01No7131 3-FPMMA0.1Yes7431 3-GPMMA0.1No7630 3-HPMMA0.3Yes5227 3-IPMMA0.3No5127 These results illustrate that the invention is effective over a range of dye concentrations with polycarbonate color layers, but not with polymethyl methacrylate color layers. Example 4Example 4 illustrates different dyes and color layer polymeric matrix materials. The results are tabulated in Table IV. Sample MatrixDyeScreenTimePeak RetenDelta E4-1PCRED 5BYes500947(ISC) 4-APCRED 5BNo5008111(ISC) 4-BPMMARED 5BYes5005771(CSC) 4-CPMMARED 5BNo5005469(CSC) 4-2PCMACROLEXYes1000879(ISC) 4-DPCMACROLEXNo10008312(ISC) 4-EPMMAMACROLEXYes5005857(CSC) 4-FPMMAMACROLEXNo5006143(CSC) 4-3PCLUMOGENYes2000829(ISC) 4-GPCLUMOGENNo20006521(ISC) 4-HPMMALUMOGENYes20008515(CSC) 4-IPMMALUMOGENNo20008215(CSC) 4-JPCGREEN GOLDYes5006523(ISC) 4-KPCGREEN GOLDNo5007317(ISC) In Samples 4-1, 4-A, 4-2, 4-D, 4-3, and 4-G, when used in a color layer comprising polycarbonate the dyes exhibited substantially improved fluorescent durability with use of a screen layer as provided herein. However, in corresponding Samples 4-B, 4-C, 4-E, 4-F, 4-H, and 4-I the same dyes when used in a color layer comprising polymethyl methacrylate did not exhibit a substantial change in fluorescent durability with use of such a screen layer. In Samples 4-J and 4-K, GREEN GOLD dye was shown to not exhibit improved fluorescent durability in a color layer comprising polycarbonate used with a screen layer as provided herein. Example 5Example 5 illustrates the improved fluorescent durability attained in laminates of the invention in outdoor exposure. Each sample, about 7 X 18 centimeters in size, was adhered to an aluminum coupon which was mounted on a black painted panel facing upward at 45° from vertical and facing south and exposed for 10 months in Arizona. In each sample, the screen layer consisted essentially of a 3 mil (75 micrometer) film of LUCITE 47K to which, in the indicated samples, 1.2 weight percent of TINUVIN 327 was added. The color layers consisted essentially of the indicated polymeric matrix material and 0.2 weight percent of the indicated fluorescent dye. The results are tabulated in Table V. Sample MatrixDyeScreenPeak RetenDelta ERetain Fluor5-1PCRED GGYes642176 5-APCRED GGNo533065 5-BPMMARED GGYes622283 5-CPMMARED GGNo692285 5-2PCRED 5BYes683046 5-DPCRED 5BNo453532 5-3PCLUMOGENYes90494 5-EPCLUMOGENNo731683 5-4PCMACROLEXYes762188 5-FPCMACROLEXNo702380 5-5PC3GYes92589 5-GPC3GNo632671 5-HPCGREEN GOLDYes485118 5-IPCGREEN GOLDNo474247
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A fluorescent article characterized in that it comprises a color layer having first and second sides and a screen layer disposed to said first side of said color layer, wherein: a) said color layer comprises daylight fluorescent dye dissolved in a polymeric matrix, said fluorescent dye comprising one or more of the following: thioxanthene dye, thioindigoid dye, benzoxazole coumarin dye, or perylene imide dye and said matrix being one or more of the following: polycarbonate, polyacrylic imide, polyester, or polystyrene; and b) said screen layer being substantially transparent to visible light and comprising means for screening substantial portions of ultraviolet radiation incident thereto. The article of claim 1 further characterized in at least one of the following: a) said color layer contains between about 0.01 and about 1.0 weight percent of said dye; or b) said color layer contains between about 0.05 and about 0.3 weight percent of said dye; or c) said color layer is between about 50 and about 625 micrometers thick. d) said color layer further comprises an additional coloring agent. The article of claim 1 further characterized in at least one of the following: a) said screen layer substantially blocks electromagnetic radiation having a wavelength below about 340 nanometers; or b) said screen layer substantially blocks electromagnetic radiation having a wavelength below about 370 nanometers; or c) said screen layer substantially blocks electromagnetic radiation having a wavelength below about 400 nanometers; or d) said screen layer screens at least 50 percent of the ultraviolet radiation incident thereto. The article of claim 1 further characterized in one of the following: a) said screen layer is in direct contact with said color layer; or b) said screen layer is bonded to said first side of said color layer with an intermediate layer of adhesive. The article of claim 1 further characterized in that it further comprises a retroreflective base sheet disposed on said second side of said color layer. The article of claim 5 further characterized in that said retroreflective base sheet comprises a monolayer of transparent microspheres and reflective means disposed on the side of said microspheres opposite said color layer. The article of claim 1 further characterized in that said color layer has retroreflective elements formed on said second side. The article of claim 7 further characterized in that said color layer is laminated directly to said screen layer and said retroreflective elements are cube-corner retroreflective elements. The article of claim 1 further characterized in that said article is sufficiently flexible to be wound about a mandrel having a diameter of about 1 centimeter. A fluorescent retroreflective article characterized in that it comprises a color layer having first and second sides and a screen layer disposed to said first side of said color layer, wherein: a) said color layer consists essentially of daylight fluorescent dye dissolved in a polymeric matrix, said fluorescent dye consisting essentially of one or more of the following: thioxanthene dye, thioindigoid dye, benzoxazole coumarin dye, or perylene imide dye and said matrix consisting essentially of one or more of the following: polycarbonate, polyacrylic imide, polyester, or polystyrene; and b) said screen layer being substantially transparent to visible light and comprising means for screening substantial portions of ultraviolet radiation incident thereto; said article comprising retroreflective elements on said second side of said color layer or a retroreflective base sheet disposed on said second side of said color layer.
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MINNESOTA MINING & MFG; MINNESOTA MINING AND MANUFACTURING COMPANY
|
BURNS DAVID R; JOHNSTON RAYMOND P; PAVELKA LEE A; SHINBACH EDWARD S; BURNS, DAVID R.; JOHNSTON, RAYMOND P.; PAVELKA, LEE A.; SHINBACH, EDWARD S.; Burns, David R., c/o Minnesota Mining and; Johnston, Raymond P. Minnesota Mining &; Pavelka, Lee A., c/o Minnesota Mining and; Shinbach, Edward S. Minnesota Mining &
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EP-0489562-B1
| 489,562 |
EP
|
B1
|
EN
| 19,940,608 | 1,992 | 20,100,220 |
new
|
B60C23
| null |
B60C23
|
B60C 23/06A
|
Method of detecting a deflated tyre on a vehicle
|
A method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocit, speed signals from wheel speed sensors one at each wheel characterised by, before the comparison of the signals is carried out, calculating corrected wheel speed signals for each of the second, third and fourth wheels giving corrections for a set of factors comprising vehicle speed, lateral acceleration and longitudinal (fore/aft) acceleration, the said corrections each comprising a constant for the factor concerned times the respective factor, the set of constants for each wheel being derived by taking the vehicle through a range of speeds, lateral and fore/aft accelerations and using multiple regression techniques and the respective factors being calculated from the set of uncorrected wheel speed signals so that comparison of the wheel speeds can be made without false signals from tyre deflections caused by speed, lateral or fore/aft acceleration induced tyre deflections.
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This invention relates to a method of detecting a deflated tyre on a vehicle suitable for cars, trucks or the like, and particularly to the system disclosed in for example French Patent Publication FR-A-2 568 519 and European Patent Publication EP-A-0 291 217. These patent applications propose using wheel speed signals from the vehicle wheels, such as for example the signals from anti-lock braking systems which are multi-pulse signals or single-pulse signals for each rotation of each wheel. They compare the speed derived signals of the wheels in various ways to try to avoid false signals due to factors such as vehicle cornering, braking, accelerating, uneven and changing load etc. The method disclosed in French Patent Publication FR-A-2 568 519 monitors the sums of the speeds of the diagonally opposed pairs of wheels for a long time or distance period so that it averaged out some of these errors. The result however was that the device operated very slowly taking many kilometres to sense pressure loss. The method disclosed in European Patent Publication EP-A-0 291 217 substantially improved this situation by calculating the lateral and longitudinal accelerations of the vehicle using the same four-wheel speed signals and setting fixed limits above which the detection system was inhibited to avoid false signals due to cornering and acceleration. This system also suggested a correction for high vehicle speeds and for the first time introduced the ability to calibrate the system to suit the particular vehicle, and indeed the actual tyres fitted which themselves could have different properties from one another in respect of rolling radius. The calibration was carried out in straight line running, however, so whilst some vehicle conditions were allowed for the problems of detection during high speed running, cornering and braking under modern road conditions and particularly in higher performance vehicles could not be allowed for. The resultant system still needed to be inhibited for detection in a fair percentage of the vehicle running time. All attempts to improve this position resulted in loss of sensitivity of the system and/or loss of ability to sense which wheel or wheels was deflated if false signals were not to occur and made application of the system less effective. An object of the present invention is to provide, in a system of the above type, the ability to sense deflations during higher levels of vehicle acceleration both laterally and longitudinally without false signals. According to one the present invention there is disclosed a method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocity speed signals from wheel speed sensors one at each wheel. The method is characterised by, before the comparison of the signals is carried out, calculating corrected wheel speed signals for each of the second, third and fourth wheels giving corrections for a set of factors comprising vehicle speed, lateral acceleration and longitudinal (fore/aft) acceleration, the said corrections each comprising a constant for the factor concerned x the respective factor, the set of constants for each wheel being derived by taking the vehicle through a range of speeds, lateral and fore/aft accelerations and using multiple regression techniques and the respective factors being calculated from the set of uncorrected wheel speed signals so that comparison of the wheel speeds can be made without false signals from tyre deflections caused by speed, lateral or fore/aft acceleration induced tyre deflections. Preferably in addition the corrections comprise a further constant x the square of the lateral acceleration; and/or a further constant x fore/aft acceleration x lateral acceleration; and/or a further constant x speed x lateral acceleration; and/or a further constant x speed x fore/aft acceleration; and/or a further constant x speed x lateral acceleration x fore and aft acceleration; and/or a further constant x speed squared and/or a further fixed constant. Having carried out the corrections to the speed signals various comparisons between the speeds of the respective wheels can then be made depending upon the particular choice of ratios made. The speed signals themselves may be multi-pulse signals such as are typical from ABS-type wheel speed generators or may comprise single-pulses from a wheel speed signal generator which gives a pulse for each revolution of the wheel. The speed signals may therefore be digital pulse signals or time periods timing the time for one rotation of each wheel and in that case a correction may be made to give the four wheel speeds at the same instant in time such as is described in our copending UK Patent Application No 9002925.7 dated 9 February 1990, published as EP-A-0 441 600 and US-A-5 192 929. The comparison of the wheel speed signals preferably comprises subtracting the sum of the signals from one pair of diagonally opposite wheels from the sum of the signals of the other pair of diagonally opposite wheels, sensing when the magnitude of the result is between 0.05% and 0.6% of the mean of the sums and when that magnitude is in said range operating a warning device to indicate a tyre is partially or completely deflated. In addition the comparison may comprise comparing the non-corrected signals from each of the four wheels in turn with the non-corrected signals for each of the other wheels, sensing when one of said signals is different from the average of all four signals by more than 0.1% and in the event of both this signal and the diagonals comparison being in the specified ranges then indicating that the tyre is partially or completely deflated. These signals may be corrected by a simple set of controls to allow for variations between the tyre by means of calibration carried out at a constant speed in a straight line. These later comparisons provide means of detecting which particular wheel of the set is deflated and therefore the provision of an indication to the driver as to which wheel is concerned. Further aspects of the present invention will become apparent from the following description by way of example only in conjunction with the attached diagrammatic drawings, in which: Figure 1 is a schematic diagrammatic drawing showing a deflation warning device for a car with four wheels. The apparatus shown in Figure 1 provides a deflation warning device for four wheels, 1, 2, 3, and 4, the wheels 1 and 2 being the front wheels and the wheels 3 and 4 the rear wheels of a car. Each wheel 1, 2, 3 and 4 has a wheel speed generating device associated with it. This may be of the toothed wheel type as used to provide a digital signal for electronic ABS equipment or merely the single-pulse type which generates a pulse one per wheel revolution. In this case the generator may be a single magnet attached to each wheel for rotation therewith and a stationary pickup mounted on the suspension. The signals from each wheel are carried through cables 5 to provide input 6, 7, 8 and 9 to a central processing unit 10. Four outputs from the central processing unit are connected to four warning indicators 12, 13, 14 and 15, one for each of the wheels respectively. The central processing unit 10 is basically a computer and in the case where the vehicle already has an ABS-system fitted may be the same computer as the ABS-system. Alternatively a separate central processing unit may be provided. The central processing unit 10 monitors the various signals and compares them to determine whether or not it should give an outward signal to indicate that any tyre on the vehicle is deflated. The central processing unit 10 can calculate substantially what the vehicle is doing using the four wheel speed signals. Firstly it can calculate the vehicle speed at any instant using either a single wheel as a reference or all four and calculating the mean. Secondly it can calculate the apparent longitudinal acceleration of the vehicle by comparing the angular velocity signals from the front and rear pairs of wheels with the forward speed calculated from the mean of the angular velocities of all four wheels. It can also calculate the apparent lateral acceleration of the vehicle comparing the angular velocity signals for the wheels on each side of the vehicle and then comparing them with the forward speed calculated from the mean of the angular velocities of all four wheels. Thus the central processing unit 10 can calculate substantially accurately what the vehicle is physically doing which allows it to then use a particular formula which will be described below to correct the wheel speed signals for three of the wheels allowing for what the vehicle is doing. Having obtained the four corrected wheel speed signals C1, C2, C3 and C4 the system can then calculate an error signal dT by comparing the angular velocities of the wheels according to the formula dT = 2 x (C1-4 - C2-3)(C2-3 + C1-4) x 100 where C1-4 = C1 + C4 and C2-3 = C2 + C3. This error or dT signal is monitored and the processing unit senses and indicates a deflation if the signal is greater than 0.05% and less than 0.6%. The next step is to find which tyre is punctured. The unit carries out this determination by looking at the difference between each wheel's non-corrected angular velocity in turn and the average speed of the four wheels using non-corrected speeds C1, C2, C3 and C4. If the difference between any one wheel and the average is more than 0.1% a second signal is generated to indicate which wheel is partially or substantially deflated. This check may be performed using speed signals corrected to allow for tyre differences in the set of tyres by means of simply correcting. This is done by running the vehicle in a straight line at a constant speed and deriving correction factors. As mentioned above this system detects whether or not a puncture exists using the corrected wheel speed C2, C3 and C4 corrected on the basis of C1 being itself correct. The correction in speeds is achieved by using a formula which comprises: C = A1 x speed² + A2 x speed + A3 x (lateral acceleration)² + A4 (lateral acceleration) + A5 (fore/aft acceleration) + A6 x speed x lateral acceleration + A7 x speed x fore and aft acceleration + A8 x lateral acceleration x fore and aft acceleration + A9 x speed x lateral acceleration x lateral fore and aft acceleration + A10 where A1 to A10 are constants for the particular wheel concerned. The constants A1 to A10 are determined by a prior calibration for the vehicle and provide corrections for the wheel speed concerned to allow for changes in rolling radius caused by changes in weight on the particular wheel concerned by the effects of acceleration, braking, etc on the vehicle. The constants also correct for the particular vehicle concerned for differences due to tyre growth due to wheel speed. The constants are found by a practical method by means of using a calibration routine which comprises driving the vehicle through a full range of accelerations both longitudinally and laterally in both directions of left and right turns and covering all other possible vehicle use conditions. This can readily be achieved by driving the vehicle on a mixed road test and the central processing unit constantly monitors the effects on wheel speeds and records them. The entire top range results are then ignored to avoid later errors, i.e. the top 5 or 10% of acceleration figures. The central processing unit is then set into a multiple regression analysis procedure using any of the standard techniques to calculate the ten constants A1 to A10 which gives it the necessary correction system to make sure that wheel speeds are made independent of extraneous factors such as weight transfer in the vehicle and cornering and acceleration. It should be noted that it is not necessary to calibrate each vehicle in a particular type by this method and the central processing unit may be reprogrammed for that model of vehicle because it allows for the basic vehicle characteristics which are set by its body shape, centre of gravity position and suspension characteristics. In some circumstances similar calibration can be used for more than one type of vehicle without recalibrating but the basic principal of the invention is that it provides the ability to correct wheel speeds for all vehicle characteristics in use. This correction system may be used with other wheel speed comparisons to provide deflation warning and can if necessary be used for correction of wheel speeds for calculation of other vehicle factors, such as for example torque control.
|
A method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocity speed signals from wheel speed sensors one at each wheel characterised by, before the comparison of the signals is carried out, calculating corrected wheel speed signals for each of the second, third and fourth wheels giving corrections for a set of factors comprising vehicle speed, lateral acceleration and longitudinal (fore/aft) acceleration, the said corrections each comprising a constant for the factor concerned times the respective factor, the set of constants for each wheel being derived by taking the vehicle through a range of speeds, lateral and fore/aft accelerations and using multiple regression techniques and the respective factors being calculated from the set of uncorrected wheel speed signals so that comparison of the wheel speeds can be made without false signals from tyre deflections caused by speed, lateral or fore/aft acceleration induced tyre deflections. A method according to Claim 1 characterised in that the corrections comprise a further constant times the square of the lateral acceleration. A method according to Claim 1 or 2 characterised by a further constant times fore/aft acceleration times lateral acceleration. A method according to any one of Claims 1, 2 or 3 characterised by a further constant times speed times lateral acceleration. A method according to any one of Claims 1, 2, 3 or 4 characterised by a further constant times speed times fore/aft acceleration. A method according to any one of Claims 1, 2, 3, 4 or 5 characterised by a further constant times speed times lateral acceleration times fore and aft acceleration. A method according to any one of Claims 1 to 6 characterised by a further constant times speed squared. A method according to any one of Claims 1 to 7 characterised by a further fixed constant. A method according to any one of Claims 1 to 8 characterised by a comparison of the corrected wheel speed signals comprising subtracting the sums of the signals from one pair of diagonally opposite wheels from the sum of the signals from the other pair of diagonally opposite wheels, sensing when the magnitude of the result is between 0.05% and 0.6% for the mean of the sums and when the magnitude is in said range operating a warning device to indicate the tyre is partially or completely deflated. A method according to Claim 9 characterised by additionally comparing the non-corrected signals from each of the four wheels in turn with the non-corrected signals for each of the other wheels, sensing when one of said signals is different from the average of all four signals by more than 0.1% and in the event of both said signals being present indicating that the tyre is partially of completely deflated. A method according to Claim 9 characterised in that the signals are corrected relative to one another based on constants derived from straight line running of the vehicle at a single speed.
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SUMITOMO RUBBER IND; SUMITOMO RUBBER INDUSTRIES LIMITED
|
REHAL LAVINDER SINGH; WALKER JOHN CHARLES; REHAL, LAVINDER SINGH; WALKER, JOHN CHARLES
|
EP-0489563-B1
| 489,563 |
EP
|
B1
|
EN
| 19,940,608 | 1,992 | 20,100,220 |
new
|
B60C23
| null |
B60C23
|
B60C 23/06A
|
Method of detecting a deflated tyre on a vehicle
|
A method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocity signals from wheel speed sensors at each wheel characterised by calculating the factors C1 + C2C3 + C4 C1 + C3C2 + C4 C1 + C4C2 + C3 where C1, C2, C3 and C4 are the signals for the speeds of the front left-hand, front right-hand, rear left-hand and rear right-hand wheels of the vehicle, monitoring these factors and if the value of one or more factor becomes greater than 1.0005 or less than 0.9995 producing a warning signal to indicate that a tyre has become partially or completely deflated.
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This invention relates to a method of detecting a deflated tyre on a vehicle suitable for cars, trucks and the like, and particularly to the system disclosed in for example French Patent Publication FR-A-2 568 519 and European Patent Publication EP-A-0 291 217. These patent applications propose using the wheel speed signals from the vehicle wheels such as for example a multi-pulse signal as used for ABS equipment or a single-pulse signal for each rotation of each wheel. They compare the speed derived signals of the wheels on a diagonal sum basis by differencing the sums of the speeds of the diagonally opposed pairs of wheels and this is monitored looking for a difference above a critical level. In the case of the French Patent application FR-A-2 568 519 error problems due to cornering and acceleration etc were allowed for by making the period of checking a very long distance or time so that the effect of cornering and braking was averaged out. In the case of the European Patent Publication EP-A-0 291 217 the system first calculats the lateral and longitudinal accelerations of the vehicle and by setting strict limits in which the system was inhibited thereby avoiding false signals. This system goes on to look at the speed of each wheel compared with the mean of the set of wheels to detect which of the four wheels was in fact punctured. However the system is not able to reliably detect two simultaneous punctures because these may give the same effect as cornering or braking or accelerating depending which two are deflated and therefore resulted in inhibition of the system. It is an object of the present invention to add to the prior art systems using diagonal sum comparisons further features allowing correct identification of punctures including two simultaneous punctures. According to the present invention a method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocity signals from wheel speed sensors at each wheel is characterised by calculating the factorsC1 + C2C3 + C4 C1 + C3C2 + C4 C1 + C4C2 + C3where C1, C2, C3 and C4 are the signals for the speeds of the front left-hand, front right-hand, rear left-hand and rear right-hand wheels of the vehicle, monitoring these factors and if the value of one or more factor becomes greater than 1.0005 or less than 0.9995 producing a warning signal to indicate that a tyre has become partially or completely deflated. More preferably a warning signal is indicated when the value of one of the factors becomes greater than 1.001 or less than 0.999. In each case the other factors remain substantially one, the small variations being due to noise in the signals. Preferably a warning signal is only given after two or more, or more preferably five successive time periods during which monitoring shows that one or more of the factors is greater than the specified limit, this being to avoid potential false signals. The system may also determine which wheel or pair of wheels is deflated by means of comparing all the factors with a Truth Table as follows: In this Table +ve means the factor is greater than 1.0005, -ve means the factor is less than 0.9995 and zero means that the factor is substantially one. To ensure that false signals are not given it is preferable to correct the wheel speed signals to allow for different tyre sizes and other variations by calculating constants for correcting the speed signals by running the vehicle in a straight line at a constant speed. Preferably the signals comprise multi-pulse electrical signals from each wheel of the type used for an anti-lock braking system. Alternatively the signals may comprise a single electrical pulse for each rotation of each wheel and the time period between successive pulses is used for the angular velocity value. Further aspects of the present invention will become apparent from the following description by way of example only of one embodiment. The device comprises a central computer or processor which takes the speed signals from each of the four wheels of the car. These signals can be the usual multi-pulse (i.e. 48 or 96 pulses per wheel), such as the electrical signals which are used for anti-lock braking systems of the electronic type or may instead be a single pulse per wheel generated by a magnet attached to the wheel or brake disc and a stationary pick-up attached to the suspension. The first type of signal is a digital signal and the second is a single pulse signal but both have the ability to generate signal proportional to the wheel speed. In the latter case this signal is most conveniently generated by means of the time for a single rotation. In the case of the single pulse system it is necessary to set up a computer derived speed signal generating system for each of the wheels so that the true speeds at any single instant of all four wheels can be determined. Such a process is described in our co-pending UK Patent Application No 9002925.7, published as EP-A-0 441 600 and US-A-5 192 929. The four signals are taken to the computer or central processing unit and converted to four separate signals directly proportional to the speed of each of the four wheels. A compensation to allow for variations between the different tyres of a vehicle because in fact they are tolerances on tyres and other simple car factors such as front and rear weight variation which may cause slight differences in the rolling radius of the tyres on the vehicle can be achieved by means of a precalibration to determine constants used to correct the speeds. This is carried out at a constant speed in straight running but is not a particularly important part of the present invention and further detail will not be here given. The four wheel speed signals C1, C2, C3 and C4 are those calculated by the first stages of the computer. The computer then calculates the factorsC1 + C2C3 + C4 C1 + C3C2 + C4 C1 + C4C2 + C3These factors are stored. As long as the four tyres of the vehicle are substantially at the same pressure these factors all remain substantially at one although there is some small variation usually less than 0.0004 due to noise from the electrical signals. If one or more of these factors exceeds 1.0005 or less than 0.9995 in value then one of the tyres has a relative pressure deflation of 0.3 bar or more difference to the others. The device then produces a warning signal which indicates on the dashboard by illuminating a light that a tyre has been partially or completely deflated. To avoid false errors this signal does not in fact produce a warning signal until five successive time periods of five seconds have given a constant signal greater than 1.0005 or less than 0.9995. The signal level for a warning may also be set at greater than 1.001 or less than 0.999 which is equivalent to 0.6 bar pressure loss in a single tyre. The computer also compares the factors calculated with the following Truth Table which allows it to determine whether tyre 1, tyre 2, tyre 3, tyre 4 or indeed combinations of two or three of these tyres are deflated. In this Table +ve means the factor is greater than 1.0005, -ve means the factor is less than 0.9995 and 0 means that the factor is substantially one. Accordingly an indication can be given after the initial deflation warning as to which particular tyre(s) is concerned. In the case where two tyres are deflated then a 0.6 bar pressure loss in each of the two tyres causes a value of 1.0017 or 0.9983 to be generated. Accordingly the system is able to detect a puncture or relative deflation in a tyre and more importantly detect and indicate which wheel or wheels are affected.
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A method of detecting a deflated tyre on a vehicle by comparing the rolling radii of the tyres by means of comparing angular velocity signals from wheel speed sensors at each wheel characterised by calculating the factors C1 + C2C3 + C4C1 + C3C2 + C4C1 + C4C2 + C3 where C1, C2, C3 and C4 are the signals for the speeds of the front left-hand, front right-hand, rear left-hand and rear right-hand wheels of the vehicle, monitoring these factors and if the value of one or more factor becomes greater than 1.0005 or less than 0.9995 producing a warning signal to indicate that a tyre has become partially or completely deflated. A method according to Claim 1 characterised in that a warning signal is indicated when the value of the factors becomes greater than 1.001 or less than 0.999. A method according to Claim 1 or 2 characterised in that the warning signal is only given after the value of a factor is in the claimed range for two successive time periods. A method according to Claim 1 or 2 characterised in that a warning signal is only given after the value of a factor is in the claimed range for five successive time periods. A method according to any of Claims 1 to 4 characterised in that the comparison of the factors is by means of the Truth Table where +ve or -ve means that a factor is greater or less than the set values respectively and the tyre or tyres deflated are thus determined. A method according to any of Claims 1 to 5 characterised in that the signals for the speeds are corrected relative to one another based on constants derived from straight line running of the vehicle at a single speed. A method according to any of Claims 1 to 6 characterised in that the signals comprise multipulse electrical signals from each wheel of the type used for an anti-lock braking system. A method according to any of Claims 1 to 6 characterised in that the signals comprise a single electrical pulse for each rotation of each wheel and the time period between successive pulses is used for the angular velocity value.
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SUMITOMO RUBBER IND; SUMITOMO RUBBER INDUSTRIES LIMITED
|
REHAL LAVINDER SINGH; WALKER JOHN CHARLES; REHAL, LAVINDER SINGH; WALKER, JOHN CHARLES
|
EP-0489565-B1
| 489,565 |
EP
|
B1
|
EN
| 19,950,614 | 1,992 | 20,100,220 |
new
|
A47L9
| null |
A47L9
|
A47L 9/16D, A47L 9/16C2B
|
Shroud and cyclonic cleaning apparatus incorporating same
|
A disc-shaped shroud having a cylindrical section (50c, 132) adjacent to an inner surface 15b, 111b) of a cyclonic container (15, 111) including a preferred combined shroud disc unit (50) for use in a dual inner and outer cyclonic vacuum cleaner (10) is described. The combined shroud and disc unit fits on the outside surface (20c) of the inner cyclone (20) and aids in removal of first and fibrous matter from the airflow in the outer cyclone (15). Improved airflow between the outer cyclone (15) and inner cyclone (20) is achieved because of the shroud and disc unit (50).
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The present invention relates to an improved shroud for a dual cyclonic cleaning apparatus. In particular, the present invention relates to a shroud which has a perforated section that is parallel with and spaced from the inside surface of the outer cyclone or container and which allows air to pass into a frusto-conically shaped inner cyclone without plugging the inlet openings to the inner cyclone within the apparatus. Cyclonic vacuum cleaning apparatus are shown in our US Patents Nos. 4, 573, 236; 4, 593, 429; 4, 571, 772; 4, 643, 748; 4,826, 515; 4,853,011 and 4,853,008. Our US Patent No. 4,853,008 describes dual cyclonic cleaning apparatus wherein a combined disc and shroud unit is mounted on the outside of the inner cyclone in order to retain dirt in the outer cyclone. The shroud has a perforated lower section adjacent and above the disc which is parallel to the conical outside surface of the cyclone. The perforated section acts as an air inlet to the inner cyclone while the disc retains large dirt particles and fibrous matter in the outer cyclone. The combined disc and shroud work well; however, there was a need for an improved design which would prevent the shroud perforations from being filled with dirt before the outer cyclone was full of separated dirt. It is therefore an object of the present invention to provide improved cleaning apparatus wherein the shroud is designed to substantially reduce the tendency for dirt particles and fibrous matter to obstruct the shroud openings leading to the inner cyclone air inlet. Further, it is an object of the present invention to provide a combined disc and shroud which is easily mounted on the outside of the inner cyclone. Still further, it is an object of the present invention to provide an improved shroud which is simple and inexpensive to construct and easy to clean and which at the same time prevents escape of fibrous matter from the outer cyclone. These and other objects will become increasingly apparent to those skilled in the art and by reference to the drawings. The invention provides shroud means for use in cleaning apparatus as set out in claim 1. The invention further provides cleaning apparatus as set out in claim 14. Further advantageous features of the invention are set out in the dependent claims. It is unexpected that the perforated section could be arranged directly facing the parallel inside wall of the container and have a relatively close spacing of 0.6 inches to 1.4 inches (1.5 cm to 3.6 cm) with respect to the inside wall and still be so effective in dirt separation. For upright vacuum cleaners as shown in Figures 1 and 2, the preferred diameter of the cylindrical section of the wall of the shroud and the diameter of the inside surface of the container is about 4.3 inches and 6.4 inches (10.9 and 16.3 cm), respectively. For tank type vacuum cleaners as shown in Figure 7, the diameter of the cylindrical section of the wall of the shroud and the diameter of the inside surface of the container is about 8.2 inches and 10.6 inches (20.8 cm and 26.9 cm), respectively. It was found that as low a pressure drop as possible through the shroud is preferred. This means that a large number of openings, preferably round, should be provided in the perforated section of the shroud. Embodiments of the invention will now be described with reference to the accompanying drawings, wherein: Figure 1 is a left side perspective view of a preferred upright type vacuum cleaning appliance according to the present invention, particularly showing an outer cyclone surrounding the combined shroud and disc unit mounted on the outside of an inner cyclone; Figure 2 is a partial front cross-sectional view along line 2-2 of Figure 1 showing the shroud and disc unit positioned between the inner cyclone and the outer cyclone; Figure 2A is a partial front cross-sectional view along a plane perpendicular to line 2-2 of Figure 1 showing the spring catch for removing the outer cyclone and receiver from the inner cyclone; Figure 2B shows a first alternative version of the shroud and disc unit; Figure 2C shows a second alternative version of the shroud; Figure 3 is a plan cross-sectional view along line 3-3 of Figure 2 showing the dirty air inlet passage, the clean air exhaust passage and the intermediate handle mounted on the outside of the outer cyclone; Figure 4 is a plan cross-sectional view along line 4-4 of Figure 2 showing the tangential air inlet into the inner cyclone; Figure 5 is a plan cross-sectional view along line 5-5 of Figure 2 showing the perforated opening through the shroud member; Figure 6 is an exploded perspective view showing the positioning of the inner cyclone inside the shroud and disc unit; Figure 7 is a front cross-sectional view of preferred tank-type cleaning apparatus of the present invention and particularly showing an outer cyclone, an inner cyclone, a dirt collection receiver, and an inlet scroll and associated shroud for the inner cyclone; Figure 8 is a plan cross-sectional view along line 7-7 of Figure 7 showing the inlet passage to the outer cyclone with a spiral member for inlet into the inner cyclone; Figure 8A is an alternative plan cross-sectional view similar to that shown in Figure 8 showing the inlet scroll having two spiral members rather than one; Figure 9 is an isometric, exploded view of the inner cyclone, inlet scroll, and the ring with openings; and Figure 10 is a graph showing area of opening versus pressure drop across a cylindrical section of the shroud and disc unit. Figs 1 and 2 show an upright-type vacuum cleaning apparatus or appliance 10 which is adapted for use in both the upright mode and the cylinder mode, the vertical mode being illustrated. The functioning of the appliance 10 will now be described with reference to this upright mode. The cleaning appliance 10 includes a cleaning head 11 connected to a casing 12 which supports a motor fan unit (not shown) which is mounted behind conventional floor engaging brushes (not shown) and inside wheels (not shown). Exterior wheels 13 are mounted behind the casing 12. An outer cyclone or container 15 is mounted on the casing 12. The outer cyclone 15 is preferably made of clear plastic so that a person can see the outer cyclone 15 fill with dirt. The outer cyclone 15 has a circular cross-section along a longitudinal axis a-a and is preferably cylindrical, or else it can be outwardly tapering if space and dimensions permit. A skirt 16 is mounted on the outer cyclone 15 and extends to the casing 12. The outer cyclone 15 has a bottom wall formed by the frusto-conical section 40d of a receiver 40 that tapers downwardly and outwardly from the axis a-a, and a cylindrical inner surface 15a (Figure 3) which extends from the bottom wall 40d of the receiver 40. Supported on the outer cyclone 15 is a circular cross-sectioned airflow directing head 18 which is sealed to the upper edge of the outer cyclone 15 by means of a flexible inverted L-shaped seal 19 and an annular lip member 15c of the outer cyclone 15 (Figure 2). Positioned radially inwardly of the outer cyclone 15 and head 18 is an inner cyclone 20. The outer cyclone 15 and the inner cyclone 20 are preferably relatively long and slender along the longitudinal axis a-a. The casing 12 is provided with a vertical extension 12a (Figure 3) which forms a rigid socket for slideably receiving the lower end of a tubular pipe or wand 21. The pipe 21 includes a grip 22. When the pipe 21 is fitted in the extension 12a, the hand grip 22 enables the appliance 10 to be used as an upright-type machine. In contrast, when the pipe 21 is slideably removed from the extension 12a, the pipe 21 is then used as a cleaner head at the end of a flexible hose (not shown) thus converting the appliance 10 into a cylinder type machine. The conversion of the appliance 10 from one mode of operation to the other and vice versa is described more fully in our US Patent No. 4,377,882. Positioned adjacent the outside wall 15b of the outer cyclone 15 and mounting the outside wall 18a of the head 18 on opposed sides of pipe 21 are spaced apart dirty air inlet and clean air exhaust passages 27 and 28, respectively. The lower half of dirty air inlet passage 27 is formed by a rigid tube 29 adjacent the outside wall 15b of the outer cyclone 15, as shown in Figure 1. Tube 29 extends from a dirty air inlet passage (not shown) in casing 12 to a tube 30 mounted on the outside wall 18a of the head 18 which forms the upper half of dirty air inlet passage 27, (Figure 3). Tube 30 communicates through the upper part of the outside wall 18a of the head 18 through an inlet passage 31 so as to effect tangential entry and set up a swirling, cyclonic flow of air in a passage 32 of the head 18 leading to the outer cyclone 15. As shown in Figure 2, depending from the circular upper plate 18b of head 18 is a conduit 18c which forms a clean air exhaust passage 33 from the inner cyclone 20. Exhaust passage 33 is in communication through head 18 with the upper half of the clean air exhaust passage 28 (Figure 3) which is formed by a tube 34 mounted on the outside wall 18a of the head 18. The lower part of tube 34 leads to a rigid lower exhaust tube (not shown) which is mounted on the outside wall 15b of the outer cyclone 15. The lower exhaust tube (not shown) forms the lower half of the clean air exhaust outlet (not shown) in the casing 12 which cools the motor fan unit and exhausts at casing vents 12b below the skirt 16 as shown in Figure 1. The inner cyclone 20 is a frusto-conical body, extending downwardly and tapering inwardly towards the axis a-a, and is connected to an inlet scroll 36. The inner cyclone 20 comprises an inner wall 20a leading to a cone opening 20b and an outer surface 20c of the inner wall 20a. The inlet scroll 36 comprises a horizontal web 37 (Figure 6) which extends from the upper edge 20d of the inner cyclone 20 to the inner surface 18d of the head 18. A sleeve 38 extends through the majority of the length of the inlet scroll 36 from the junction of the upper end surface 20d of the inner cyclone 20 and web 37 to the bottom side of plate 18b. A second horizontal web 39 extends from the upper end 38a of sleeve 38 to the junction where the inside wall 18d of head 18 meets plate 18b. A portion 38b (Figure 4) of sleeve 38 extends, in the form of a spiral, from the junction of the upper end surface 20d of the inner cyclone 20 and the web 37 to the inside wall 18d of the head 18 thereby competing the inlet scroll 36 and providing a tangential entry to the inner cyclone 20 in order to be capable of setting up a swirling cyclonic flow of air. The cone opening 20b of the inner cyclone 20 is connected to the dirt collecting receiver 40 for collecting dirt from the inner cyclone 20. The lower end of the outer surface 20c of the inner cyclone 20 engages a circular plate 40a which meets a frusto-conical member 40b that tapers downwardly and outwardly from the axis a-a. The lower edge of frusto-conical member 40b meets the upper edge of a short cylindrical member 40c of the receiver 40. Interposed between the inner cyclone 20 and the plate 40a of receiver 40 is a flexible annular sealing member 41. Depending from the bottom edge of the cylindrical member 40c is the frusto-conical section 40d which forms the bottom wall of the outer cyclone 15 and which extends downwardly and outwardly from the axis a-a to the inner surface 15a of outer cyclone 15 about 1.1 inches (2.7 cm) above the bottom wall 40e of receiver 40. The maximum diameter of the frusto conical section 40d is preferably at least three times the diameter of cone opening 20b, as described in US Patent No. 4,826,515. Figure 2a shows an alternative preferred version of the connection between the cone opening 20b of the inner cyclone 20 and a receiver 140 which is similar to receiver 40. The receiver 140 has a frusto-conical section 140a secured directly to the cone opening 20b through inverted U-shaped annular seal 141a. The frusto-conical section 140a tapers downwardly and outwardly from the axis b-b to an inner annular ring member 140b. A bottom plate 140c, circular in plan view, extends to and meets a first frusto-conical member 140d which tapers upwardly and outwardly from axis b-b. The upper edge of the first frusto-conical 140d meets a first cylindrical member 140e which extends to and meets a second frusto-conical member 140f. The second frusto-conical member 140f tapers upwardly and outwardly from the axis b-b to a second cylindrical member 140g. The second cylindrical member 140g seals against the inner surface 16a of skirt 16 through annular ring seal 141b. The receiver 140 is completed by annular ring seal 141c which is disposed between the inner annular ring member 140b and the second cylindrical member 140g thereby sealing the outer cyclone 15 from the receiver 140. A combined shroud and disc unit 50 is mounted on the inner cyclone 20 intermediate the passage 32 leading to inlet scroll 36 and the cone opening 20b as particularly shown in Figure 2. The upper part of the unit 50 is tapered with wall 50a preferably parallel to the outer surface 20c of the inner cyclone 20 and forming passage 52. The wall 50a ends in a flange 50b which limits and encloses the inlet passage 32 to the inner cyclone 20. Cylindrical section 50c depends from the lower end of wall 50a to an annular web 50d. A plurality of openings 50e (partially shown in Figure 5), located that are in and around the circumference of the cylindrical section 50c, serve as an outlet from the outer cyclone 15 to passage 51 leading to passage 52. Web 50d extends between the cylindrical section 50c and the outer surface 20c of the inner cyclone 20 where it meets conical member 50f leading to a cylindrical section 50g. Depending from the cylindrical section 50g is a disc 50h which can be conically shaped with a large downwardly tapered portion 50i facing the bottom wall 40d of the outer cyclone 15. The disc 50h can have a downward inclination forming an angle of between about 97-1/2° to 110° with the axis a-a or 7-1/2° to 20° with a line perpendicular to the axis a-a (not shown). Figure 2B shows another version of the combined shroud and disc unit 150 that fits over the outer surface 20c of the inner cyclone 20, inside the head 18 and the outer cyclone 15, similar to the shroud and disc unit 50 shown in Figure 2. The upper part of the unit 150 is formed by a frusto-conical section 150a that tapers upwardly and outwardly from the axis e-e to a flange 150b. A cylindrical section 150c depends from the lower end of the frusto-conical section 150a to an annular web 150d. A plurality of openings 150e, located in and around the circumference of the cylindrical section 150c, serve as an outlet from the outer cyclone 15. Web 150d extends between the cylindrical member 150c toward the axis e-e and contacts the outer surface 20c of the inner cyclone 20. Web 150d meets a conical member 150f that together with web 150d forms a seal between the inner cyclone 20 and the lower end of the combined shroud and disc unit 150. Extending from the junction of the cylindrical member 150c and the web 150d is a disc 150h which can be conically shaped with a large downward inclination forming an angle of between about 97-1/2° to 110° with the axis e-e or 7-1/2° to 20° with a line perpendicular to the axis e-e. The disc 150h can also be perpendicular to the axis e-e (not shown). Figure 2C shows still another version of the shroud unit 250 that fits over the outer surface 20c of the inner cyclone 20, inside of head 18 and the outer cyclone 15, similar to the shroud and disc unit 50 shown in Figure 2. The upper part of the unit 250 is formed by a frusto-conical section 250a that tapers upwardly and outwardly from the axis f-f to a flange 250b. A cylindrical section 250c depends from the lower end of the frusto-conical section 250a to an annular web 250d. A plurality of openings 250e located in and around the circumference of the section 250c, serve as an outlet from the outer cyclone 15. Web 250d extends between the cylindrical section 250c toward the axis f-f where it contacts the outer surface 20c of the inner cyclone 20 similar to web 150d of the shroud and disc unit shown in Figure 2B. Web 250d meets a conical member 250f that, together with web 250d, forms a seal between the inner cyclone 20 and the lower end of the shroud unit 250. The shroud unit 250 does not have a disc to help to keep large dirt particles and fibrous matter in the outer cyclone 15 as is characteristic of the shroud and disc unit 50 in Figure 2 and the shroud and disc unit 150 in Figure 2B. In operation of the preferred version of the upright-type vacuum cleaning apparatus 10 as shown in Figure 2, the fan unit in casing 12 pulls air into dirty air inlet passage 27 through tubes 29 and 30 and into inlet passage 31 leading to the outer cyclone 15. The air cyclones down and around the inner surface 15a and bottom wall 40d of outer cyclone 15, over the outside of walls 40c, 40b and 40a of the receiver 40 and up the outer surface 20c of the inner cyclone 20, then over the disc 50h, through openings 50e and up passages 51 and 52 defined by the shroud 50 and the outer surface 20c of the inner cyclone 20. The air then moves into passage 32 before entering the inlet scroll 36 leading to the inner cyclone 20 wherein the air cyclones down the inner wall 20a to the cone opening 20b before moving upward to the exhaust passage 33 formed by conduit 18c. The air finally moves to the clean air exhaust passage 28 defined by tube 34 and a lower exhaust tube (not shown) adjacent the outside wall 15b of the outer cyclone 15 before being exhausted to the atmosphere or to the motor fan unit in the casing 12 to assist with cooling. The dirt collects on the bottom wall 40d of the outer cyclone 15 and on the bottom wall 40e of the receiver 40 as shown in Figure 2. Finer dirt collects primarily in the receiver 40. It was surprising that the openings 50e in the cylindrical section 50c (Figure 2) could be positioned closely adjacent the inner surface 15a of the outer cyclone 15. During testing, it had been thought that the cylindrical section 50c should be as distant as possible from the dirt swirling around the inner surface 15a of the outer cyclone 15. It had been felt that a large distance between the cylindrical section 50c and the inner surface 15a of the outer cyclone 15 would make it less likely that dirt, fluff or fibrous material would become caught up in the airflow exiting the outer cyclone 15 through the openings 50e in cylindrical section 50c. However, with the cylindrical section 50c set as far away as possible from the inner surface 15a of the outer cyclone 15, fluff and fibrous material became trapped on the outer surface 50k of the cylindrical section 50c. Surprisingly, it was found that, by positioning the cylindrical section 50c closely adjacent the inner surface 15a of the outer cyclone, the outer surface 50k of the cylindrical section 50c did not attract fibrous material and that dirt did not pass directly from the airflow circulating around the inner surface 15a of the outer cyclone 15 to the openings 50e in cylindrical member 50c. In fact, the outer surface 50k of the cylindrical member 50c was apparently being wiped clean by the airflow circulating around the inner surface 15a of the outer cyclone 15. With this construction, the dirt can accumulate to a relatively high level in the outer cyclone 15 (about level L) with good separation of the dirt. As shown in Figure 2A, the outer cyclone 15 and receiver 40 (not shown) or receiver 140 are removable from the head 18 for emptying by releasing a spring catch 55 housed within the skirt 16. The catch 55 comprises a central spring arm member 55a that attaches at its proximal end 55b to the bottom surface 140h of the bottom plate 140c of the receiver 140 through mounting bracket 140i. The distal end 55c of the spring arm 55a is formed into a first inverted U-shaped member 55d. The spring arm 55a and a proximal leg 55e of the first inverted U-shaped member 55d form a U-shaped junction 55f that secures in a mating locking member 12c mounted on the casing 12. A distal leg 55g of the first inverted U-shaped member 55d acts as a finger grip that protrudes out from underneath the skirt 16 adjacent the casing 12. A second inverted U-shaped guide member 140j is mounted on the bottom surface 140h of the bottom plate 140c of the receiver 140 spaced apart from mounting bracket 140i and adjacent the apex of the first inverted U-shaped member 55d. The second inverted U-shaped guide member 140j serves as a guide for an arrow tab 55h extending from the first inverted U-shaped member 55d of the catch 55 which helps to secure the receiver 140 and outer cyclone 15 to the head 18 and the inner cyclone 20 when the vacuum cleaning apparatus 10 is being used. When the outer cyclone 15 and the receiver 140 become full of accumulated dirt, the operator raises the distal leg 55g of the first inverted U-shaped member 55d which releases the junction 55f of catch 55 from the locking member 12c and the arrow tab 55h from the second inverted U-shaped member 140j. The operator then pulls the outer cyclone 15, receiver 140 and skirt 16 away from the handle 21 (Figure 1) which causes the annular lip member 15c of the outer cyclone 15 to release from the head 18 at the flexible inverted L-shaped seal 19 and the receiver 140 to release from the inner cyclone 20 at the annular seal 141a, thereby exposing the rigid tube, the rigid lower exhaust tube (not shown) and the bottom part of the intermediate pipe 21. The outer cyclone 15 and the receiver 140 can then be emptied and replaced into the vacuum cleaning apparatus 10 by fitting annular lip member 15c of the outer cyclone inside the flexible inverted L-shaped seal 19 and by fitting annular seal 141a around the cone opening 20b of the inner cyclone 20. The operator then pushes the outer cyclone 15 and receiver 140 towards the pipe 21 until the junction 55f of catch 55 locks into locking member 12c of casing 12 and arrow tab 55h secures into U-shaped member 140j. Figure 7 shows a tank type vacuum cleaning apparatus 110, which comprises an outer cyclone 111 around an inner cyclone 112, a dirt collection receiver 113 and a motor driven fan unit 114. The inner and outer cyclones 111 and 112 have circular cross-sections with respect to a longitudinal axis c-c. The outer cyclone 111 has a base 111a and a cylindrical inner surface 111b which extends from the outer periphery of the base 111a. A circular cross-sectioned flange 111c extends radially outwardly from the upper end part of the outside wall 111d of the outer cyclone 111 and serves as one-half of a seal for the outer cyclone 111. A removable cover 115 with hemispherical outer surface 115a fits over the top of the outer cyclone 111. The lower edge of the outer surface 115a of cover 115 has an annular rim 115b with a depending lip 115c which serves as a hand grip for removing the cover 115 from the outer cyclone 111. Extending inwardly from rim 115b toward the axis a-a is a horizontal support web 115d which meets the upper edge of a right-angled cross-sectioned protrusion 115e. An annular gasket 116 is mounted intermediate the protrusion 115e and the rim 115b on web 115d so as to be in contact with the circular cross-sectioned flange 111c. The gasket 116 serves to seal the cover 115 to the outer cyclone 111 while the apparatus 110 is in operation. The lower edge of the protrusion 115e meets the top edge of a frusto-conical section 115f which tapers radially inwardly and downwardly toward the axis c-c. An annular ring member 115g depends from the distal end of the conical section 115f and has openings 115h for bolts 117. Openings 115i are provided on the hemispherical outer surface 115a which serve as an exhaust port for the motor fan unit 114. A cylindrical dirty air inlet passage 118 communicates through the upper part of the outside wall 111d of the outer cyclone 111. The end part 118a of the dirty air inlet passage 118, remote from the outer cyclone 111, is joined by a flexible tube (not shown) to a cleaner head (not shown) for contacting a dirty surface. Flanged section 118b of inlet passage 118, adjacent the outside wall 111d of the outer cyclone 111, has openings 119 for bolts 120 to secure the inlet passage 118 to the outside wall 111d of the outer cyclone 111. Inlet passage 118 leads to a dirty air inlet passage 121. As long as inlet passage 121 communicates through the upper part of the outside wall 111d of the outer cyclone 111 so as to make a tangential entry and to set up a swirling, cyclonic flow of air in the outer cyclone 111, the exact position of the inlet passage 121 around the circumference of the outer cyclone 111 is not critical. A plate 124, circular in plan view, with dependent tube 125 centered around the axis c-c is positioned above the inner cyclone 112. The dependent tube 125 extends downwardly along axis c-c from the plate 124 substantially coaxially with the inner cyclone 112. The motor driven fan unit 114 is located on the plate 124 and is arranged so as to draw air from the inner cyclone 112 through dependent tube 125. Extending from the top side 124a of the plate 124 is annular ring member 124b which is outside and adjacent the depending ring member 115g. Annular ring 124b has openings 126, centered on the axis d-d coinciding with the openings 115h in the depending ring member 115g, which enable bolts 117 to secure the cover 115 to the plate 124. The inner cyclone 112 has a frusto-conical body extending radially downwardly and inwardly towards the axis c-c and a dependent inlet scroll 127. The inner cyclone 112 comprises a frusto-conical inner surface 112a leading to a cone opening 112b and an outside wall 112c. The inlet scroll 127 comprises the sleeve 123 which depends from the plate 124 to a horizontal annular web 128 (Figures 7 and 8). The web 128 extends between the upper end 112d of the frusto-conical body and the lower end part of sleeve 123. A second dependent sleeve 129 extends between the cover 124 and the junction of the upper end 112d of the frusto-conical body and the web 128. The second sleeve 129 is located radially inwardly of the tubular sleeve 123 and through the majority of its length sleeve 129 extends from the upper end 112d of the frusto-conical body where the upper end 112d joins the inner periphery of the web 128. As shown in Figure 8, a portion 130 of the second sleeve 129 extends, in the form of a spiral, from the junction of the upper end 112d of the frusto-conical body and the web 128 to the tubular sleeve 123 thereby completing the inlet scroll 127 and providing a tangential entry to the inner cyclone 112 in order to be capable of setting up a swirling cyclonic flow of air. Figure 8A shows another version of the inlet scroll 127 wherein two diametrically opposed sections 130a and 130b extend from the junction of the upper end 112d of the frusto-conical body and the web 128 to the tubular sleeve 123. In this manner, the inner cyclone 112 is provided with two opposed tangential entry points which are capable of setting up a swirling, cyclonic flow of air. It should be noted that the inlet scroll 127 can be completed by any number of sections 130 spiralling radially outwardly from the sleeve 129 to the tubular sleeve 123 as long as the sections 130 create at least one tangential entry point to the inner cyclone 112. Depending from the scroll 127 and spaced from the outside wall 112c of the inner cyclone 112 is a shroud 131 which comprises a tubular ring 132 that depends from the junction of the tubular sleeve 123 and the web 128. The ring 132 of shroud 131 is totally perforated with a plurality of openings 133 (partially shown in Figure 9) that serve as an air outlet from the outer cyclone 11 to scroll 127 leading into the inner cyclone 112. The tubular ring 132 lies parallel to and spaced from the inner surface 111b of the outer cyclone 111. The shroud 131 is completed by a web 134 that extends between the lower end portion of ring 132 and the outside wall 112c of the inner cyclone 112, in particular a cylindrical support member 135 that depends from the outside wall 112c of the inner cyclone 112 and which, together with the upper surface 134a of the web 134, forms a right-angled closure from the outer cyclone 111 at an intermediate seal 136. The dirt collection receiver 113 for the inner cyclone 112 comprises a cylindrical portion 113a which meets the upper edge of a frusto-conical section 113b extending downwardly and outwardly from the axis c-c to the base 111a of outer cyclone 111. Adjacent and radially inwardly of frusto-conical section 113b is an annular ring member 111e of the outer cyclone 111 which extends beyond the upper edge of frusto-conical section 113b adjacent the inside wall 113c of the receiver 113, thus forming a seal between the receiver 113 and the outer cyclone 111. The cylindrical portion 113a lies intermediate the inner surface 111b of the outer cyclone 111 and the outside wall 112c of the inner cyclone 112 and is below the web 134 of the shroud 131. The receiver 113 is completed by a rubber seal 137 that extends from the top of the cylindrical portion 113a to the outside wall 112c of the inner cyclone 112 adjacent the web 134. In another embodiment (not shown), cylindrical portion 113a can meet and seal against the web 134 of the shroud 131. The following are parameters for the preferred vacuum cleaner. 1. Number of Holes in ShroudIn the preferred version of the upright-type vacuum cleaning apparatus 10 as shown in Figure 2, and the preferred version of the tank-type vacuum cleaning apparatus 110 as shown in Figure 7, there should be approximately the number and size of openings or holes 50e in the cylindrical section 50c of the shroud and disc unit 50 and openings 133 in the tubular ring 132 of shroud 131 to position the pressure differential through the cylindrical section 50c and the pressure differential through the ring 132 of shroud 131 as far along from the pressure increase rise of the graph (Figure 10) as possible. It was found that, if there was a high differential pressure through the cylindrical section 50c and through the ring 132 of shroud 131, large dirt particles that collect in the outer cyclones 15 and 111 when the dirt level in the outer cyclones 15 and 111 is below level L are pulled through the openings 50e in cylindrical section 50c and the openings 133 in the tubular ring 132 of shroud 131 where they will then enter the inner cyclones 20 and 112. The high differential pressure probably causes large particles and fluff to attach to and block the openings of 50e in the cylindrical section 50c of the shroud and disc unit 50 and the openings 133 in the tubular ring 132 of shroud 131. This result is undesirable because the large dirt particles will not separate out in the inner cyclones 20 and 112. Instead, the large dirt particles will be drawn through the exhaust passage 33 of the inner cyclone 20 and through the dependent tube 125 exhausting from the inner cyclone 112, where the large dirt particles will then be drawn into the motor fan units 14 and 114. This will damage the motor fan units 14 and 114 and can also result in dirt being expelled into the atmosphere. The above discussion is also applicable for the pressure between the inside surface 150j and the outside surface 150k of the cylindrical section 150c (Figure 2B) and for the pressure between the inside surface 250j and the outside surface 250k of the cylindrical section 250c (Figure 2C). The circumference of the cylindrical section 50c of shroud and disc unit 50 in Figure 2 was 13.6 inches (34.5 cm), the diameter was 4.3 inches (10.9 cm), and the height was 2.6 inches (6.6 cm). Where there were approximately 58 holes per row, a combination lying in the range of 32 to 38 rows of holes of 2.2 mm diameter was found to be best for the cylindrical section 50c of the shroud and disc unit 50 of the cleaning apparatus 10 shown in Figures 1 and 2. Also, the circumference of the ring 132 of the shroud 131 of the tank type vacuum cleaning apparatus 110 shown in Figure 7 was 15.5 inches (64.8 cm), the diameter was 8.2 inches (20.8 cm), and the height was 2.5 inches (6.4 cm). Where there were approximately 208 holes per row, a combination lying in the range of 34 to 38 rows of holes of 2.2 mm diameter was found to be best for the ring 132 of the shroud 131. A 2.2 mm diameter hole is sufficiently small to block the passage of particles of a greater size than would be successfully separated by the inner cyclone 20 of Figure 2 and the inner cyclone 112 of Figure 7. It was believed that the greater the total area of holes 50e and 133 the less pressure there would be at each hole. This is beneficial because the cylindrical section 50c and the ring 132 of the shroud 131 would be better at not attracting fluff. Also, a lower pressure at each opening 50e of the upright type vacuum cleaning apparatus 10 and at each opening 133 of the ring 132 of the shroud 131 of the tank type vacuum cleaning apparatus 110 would make it easier for fine dirt to gather at and maybe block rather than be drawn through the openings 50e and 133, thereby signalling to the operator that it is time to empty the respective vacuum cleaners 10 and 110. 2. Thickness of Material for the ShroudIt was found that better results were obtained when material at least 2 mm thick was used for the shrouds 50 and 131. Material 1 mm thick did not work as well. It was assumed that the thicker material causes a sharper change in direction for the clean air and therefore contributes to a better separation than is achieved by the thinner material. 3. Distance Between the Shroud and the Inner Surface of the Outer CycloneFor the upright type vacuum cleaner 10 in Figures 1 and 2, the distance range between the cylindrical section 50c of the shroud and disc unit 50 and the inner surface 15a of the outer cyclone 15 is preferably from 0.59 inches to 1.18 inches (1.5 cm to 3.0 cm). For the tank type vacuum cleaning apparatus 110 in Figure 7, the distance range between the ring 132 of the shroud 131 and the inner surface 111b of the outer cyclone 111 is preferably from 0.75 inches to 1.26 inches (1.9 cm to 3.2 cm). However, if the distance between the cylindrical section 50c of the shroud and disc unit 50 is too close, fluff will bridge between the disc 50b and the inner surface 15a of the outer cyclone 15. Alternatively, if the distance is too great, fluff attaches to the cylindrical section 50c and blocks the openings 50e. The exact distance is dependent on the diameter of the outer cyclone and the inner cyclone of the respective vacuum cleaning apparatus 10 and 110. It is intended that the foregoing description be only illustrative of the present invention and that the present invention be limited only to the hereinafter appended claims.
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Shroud means (50,150,250) for use in cleaning apparatus (10), the cleaning apparatus (10) including: a container (15) having a circular cross-section and comprising a bottom (40d) and a sidewall extending to and meeting the bottom (40d), the sidewall having an interior surface (15a), a dirty air inlet (27) which is oriented for supplying dirt laden air into the container (15) tangentially to the interior surface (15a) of the sidewall, and an air outlet from the container (15); a circular cross-sectioned cyclone (20) having a longitudinal axis and mounted inside the container (15), the cyclone (20) comprising a cyclone air inlet (36) at an upper end of the cyclone (20) in air communication with the air outlet of the container, an interior dirt rotational surface (20a) of frusto-conical shape for receiving an air flow from the air inlet (36) and for maintaining its velocity to a cone opening (20b) smaller in diameter than the diameter of the upper end of the cyclone (20), the air inlet (36) being oriented for supplying air tangentially to the interior dirt rotational surface (20a), an outer surface (20c) of frusto-conical shape, and a cyclone air outlet (33) communicating with the interior of the cyclone (20) adjacent the upper end of the cyclone (20); a dirt collecting receiver (40) extending from the cone opening (20b); and means for generating an airflow which passes sequentially through the dirty air inlet (27), the container (15), the cyclone air inlet (36), the cyclone (20), the dirt receiver (40) and the cyclone air outlet (33), the airflow rotating around the frusto-conical interior surface (20a) of the cyclone (20) and depositing dirt in the receiver (40); the shroud means (50, 150, 250) being mountable on and around the outer surface (20c) of the cyclone (20) and, when in use, having opposed ends spaced in the direction of the longitudinal axis of the cyclone (20) and providing an air passageway from the container (15) to the air inlet (36) of the cyclone (20), one of the ends of the shroud means (50, 150, 250) being sealed against the outer surface (20c) of the cyclone (20), characterised in that a portion of the shroud (50, 150, 250) has a perforated section (50c, 150c, 250c) having a large number of perforations (50e, 150e, 250e), the perforated section (50c, 150c, 250c) being spaced from the interior wall (15a) of the sidewall of container (15) such that a low differential pressure is created between an outside surface (50k, 150k, 250k) and an inside surface (50j, 150j, 250j) of the perforated section (50c, 150c, 250c) so as to prevent dirt from being drawn through the perforated section (50c, 150c, 250c) by the flow of air from the container (15) to the cyclone air inlet (36). Shroud means as claimed in claim 1, wherein the perforated section (50c, 150c, 250c) is cylindrical. Shroud means as claimed in claim 1 or 2, wherein the end of the shroud means (50, 150, 250) which is sealed against the outer surface (20c) of the cyclone (20) comprises a web section (50d, 150d, 250d) which abuts directly against the outer surface (20c). Shroud means as claimed in any one of the preceding claims, wherein the perforations (50e, 150e, 250e) through the perforated section (50c, 150c, 250c) are circular and are provided around a circumferential extent of the perforated section (50c, 150c, 250c) of the shroud means (50, 150, 250). Shroud means as claimed in any one of the preceding claims, wherein, in use, the perforated section (50c, 150c, 250c) of the shroud means (50, 150, 250) is located between 0.59 inches and 1.38 inches (1.5 cm and 3.5 cm) from the inside wall (15a) of the container. Shroud means as claimed in any one of the preceding claims, wherein the shroud means (50, 150, 250) has a flanged section (50b, 150b, 250b) above the cylindrical section (50c, 150c, 250c), the flanged section (50b, 150b, 250b) being locatable around the longitudinal axis at an end of the cyclone (20) adjacent the air inlet (36) and in closely spaced relationship to the outside (20c) of the cyclone (20) so as to provide, in use, a chamber (32) leading to the air inlet (36). Shroud means as claimed in any one of the preceding claims, wherein disc means (50h, 150h, 250h) are provided at a lower longitudinal extent of the shroud means (50, 150, 250), the disc means (50h, 150h, 250h) being locatable around the axis of the cyclone (20) with a space between the interior surface (15a) of the sidewall of the container (15) and the disc means (50h, 150h, 250h) for passage of air therebetween, such that, in use, the disc means (50h, 150h, 250h) aid in dirt removal in the container (15) by preventing some of the dirt from flowing to the air inlet (36) of the cyclone (20). Shroud means as claimed in claim 7, wherein the shroud means (50, 150, 250) and the disc means (50h, 150h, 250h) form an integral unit slidable over the outer surface (20c) of the cyclone (20) such that the cone opening (20b) protrudes below and out of the unit. Shroud means as claimed in claim 7 or 8 when depedent on claim 3, wherein a lower section (50f, 150f, 250f) of the shroud means (50, 150, 250) depending from a radius of the web section (50d, 150d, 250d) of the shroud means (50, 150, 250) supports the disc means (50h, 150h, 250h) and is locatable in sealed relationship with the outside wall (20c) of the cyclone (20) so that, in use, the airflow in the container (15) must travel over the disc means (50h, 150h, 250h) and past an outside surface of a lower section of the shroud means (50, 150, 250) before passing through the openings (50e, 150e, 250e) in the cylindrical section (50c, 150c, 250c) leading to the air inlet (36) of the cyclone (20). Shroud means as claimed in any one of claims 7 to 9, wherein the disc means (50h, 150h, 250h) are circular in cross-section. Shroud means as claimed in any one of claims 7 to 10, wherein the disc means (50h, 150h, 250h) have a conical shape around the shroud means (50, 150, 250) such that, in use, a larger portion of the conical shape faces towards the bottom (40d) of the container (15). Shroud means as claimed in claim 11, wherein the conical shape, when viewed as a cross-section of the shroud means (50, 150, 250) and disc means (50h, 150h, 250h) through the longitudinal axis, is downwardly inclined at an angle of between 7-1/2° and 20° with respect to a line perpendicular to the longitudinal axis of the cyclone (20). Shroud means as claimed in any one of claims 7 to 12, wherein, in use, the disc means (50h, 150h, 250h) are positioned at about one third of the distance between the cone opening (20b) and the air inlet (36) of the cyclone (20). Cleaning apparatus (10) including a container (15) having a circular cross-section and comprising a bottom (40d) and a sidewall extending to and meeting the bottom (40d), the sidewall having an interior surface (15a), a dirty air inlet (27) which is oriented for supplying dirt laden air into the container (15) tangentially to the interior surface (15a) of the sidewall and an air outlet from the container (15); a circular cross-sectioned cyclone (20) having a longitudinal axis and mounted inside the container (15), the cyclone comprising a cyclone air inlet at an upper end of the cyclone in air communication with the air outlet of the container, an interior dirt rotational surface (20a) of frusto-conical shape for receiving an airflow from the air inlet (36) and for maintaining its velocity to a cone opening (20b) smaller in diameter than the diameter of the upper end of the cyclone (20), the air inlet (36) being oriented for supplying air tangentially to the interior dirt rotational surface (20a), an outer surface (20c) of frusto-conical shape, and a cyclone air outlet (33) communicating with the interior of the cyclone (20) adjacent the upper end of the cyclone (20); a dirt collecting receiver (40) extending from the cone opening (20b); and means for generating an airflow which passes sequentially through the dirty air inlet (27), the container (15), the cyclone air inlet (36), the cyclone (20), the dirt receiver (40) and the cyclone air outlet (33), the airflow-rotating around the frusto-conical interior surface (20a) of the cyclone (20) and depositing the dirt in the receiver (40); characterised in that the cleaning apparatus (10) further includes shroud means (50, 150, 250,) according to any one of the preceding claims. Cleaning apparatus as claimed in claim 14, wherein the dirt collecting receiver (40) is mounted on the outer surface (20c) of the cyclone (20) and has a conical portion (40d) adjacent the bottom of the container (15) which tapers outwardly towards the sidewall and the bottom of the container (15). Cleaning apparatus as claimed in claim 15, wherein the dirt collecting receiver (40) has a cyclindrical portion (40c) which extends from an outer edge of a circular plate portion (40a), an inner edge of which contacts the outer surface (20c) of the cyclone (20) adjacent the cone opening (20b), and wherein the cylindrical portion (40c) extends to the conical portion (40d). Cleaning apparatus as claimed in claim 16, wherein the cylindrical portion (40c) has a diameter smaller than a diameter of the disc means (50h,150h,250h). Cleaning apparatus as claimed in any one of claims 14 to 17, wherein the cleaning apparatus (10) is an upright-type vacuum cleaner with a handle (21,22), wherein the airflow generating means is mounted in a casing (12) that supports the container (15), the cyclone (20) and the dirt collecting receiver (40), and wherein, in use, the floor engaging cleaner head (11) contacts a surface to be cleaned and an airflow control cover is mounted on an open end of the container (15) for directing airflow of dirt-laden air into the container (15) and for directing airflow out of the outlet (33) from the cyclone (20). Cleaning apparatus as claimed in claim 18, wherein separate tubes (30,34) are mounted on the outside of the container (15) parallel to the longitudinal axis of the container (15), the separate tubes (30,34) being on opposed sides of and in closely spaced relationship to the handle (21,22) and being in air flow communication with the casing (12) so that, in use, one tube (30) serves as a dirty air inlet to the container (15) and clean air from the cyclone (20) is removed through the other tube (34) and is used to cool the air flow generating means.
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NOTETRY LTD; NOTETRY LIMITED
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DYSON JAMES; DYSON, JAMES
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EP-0489566-B1
| 489,566 |
EP
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B1
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EN
| 19,960,904 | 1,992 | 20,100,220 |
new
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H03K19
| null |
H03K19
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H03K 19/0175B2, H03K 19/0175B2D
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Apparatus and method for translating voltages
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An apparatus and method for translating voltages between logic levels is provided having an input section (11), a level shifter section (89) and an output section (137). Input section (11) provides two control voltages to the level shifter section (89) in response to an input signal provided at input terminal (12). Level shifter section (89) comprises two inverters coupled to the control voltages. One inverter comprises p channel field-effect transistor (90) and n channel field-effect transistor (98). Another inverter comprises p channel field-effect transistor (106) and n channel field-effect transistor (114). For each inverter, the channel of the p channel field-effect transistor is over twice as wide as the channel of the n channel field-effect transistors. Each transistor (90, 98, 106 and 114) conducts current in response to a control voltage being anywhere within the voltage range, such that outputs of the inverters transition quickly in response to a transition of the control voltages. Output section (137) generates an output signal in response to the inverter outputs.
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TECHNICAL FIELD OF THE INVENTIONThis invention relates in general to the field of electronic circuitry, and more particularly to voltage level translators. BACKGROUND OF THE INVENTIONIn contemporary digital circuit applications, it is common to combine various logic structures using, for example, ECL, CMOS and TTL design. While CMOS and TTL are generally compatible, ECL uses substantially different voltages to represent a logical high and a logical low. In conventional ECL, -1.7 volts is used to represent a logical low and -0.95 volts is used to represent a logical high. Pseudo-ECL logic may also be used in order to take advantage of existing voltage supply rails. For example, with 0 volt and 5 volt supply rails, a pseudo-ECL circuit would use a signal of 3.3 volts for a logical low and a signal of 4.05 volts for logical high. Because different voltages are often used in a single circuit, it is necessary to provide circuitry for translating ECL signals to suitable CMOS or TTL counterparts. Various circuits have been designed to translate the ECL signals to CMOS-compatible or TTL-compatible signals. An ECL signal, however, must propagate through the translator to the inputs of the CMOS or TTL circuits. Consequently, the propagation delay time through the translator becomes very important. Translation propagation times of 1-2 nanoseconds are considered short for modern technology. Nonetheless, a propagation delay of this magnitude may be unacceptable for many applications. Therefore, a need has arisen for a circuit and method for providing ECL-to-CMOS/TTL translations such that the propagation delay associated with both low-to-high transitions and high-to-low transitions is minimized. Toute l'électronique (1989), No. 544, pages 22-26 (see Fig. 11), on which the preambles of claims 1 and 8 are based, NEC Research & Development (1989), No. 95, pages 31-36 (see Fig. 3a) and US-A 4 697 109 (see Fig. 9) all disclose circuits for converting ECL logic signals to CMOS logic signals, the first two of these documents anticipating all features set out in the preamble portions of the independent Claims. The invention provides an apparatus for translating voltages comprising: an input section for generating first and second control voltages within a voltage range in response to an input signal; a level shifter section comprising first and second inverters respectively coupled to said control voltages, each of said inverters comprising a plurality of transistors, wherein each transistor maintains current in response to one of said control voltages being anywhere within said voltage range, such that outputs of said first and second inverters are operable to transition quickly in response to a transition of said first and second control voltages respectively; and an output section for generating an output signal in response to said output of said first and second inverters, the invention lying in that said level shifter section comprises a bias voltage device coupled to one of said inverters and operable to maintain the output of said one inverter above a desired bias voltage, such that said one inverter is operable to quickly adjust said output of said one inverter away from said bias voltage in response to a transition of a respective one of said control voltages. The invention also provides a method for translating voltages comprising the steps of: generating first and second control voltages within a voltage range in response to an input signal; maintaining current through each of a plurality of transistors in response to one of said control voltages being anywhere within said voltage range, said transistors forming first and second inverters respectively coupled to said control voltages, such that outputs of said first and second inverters transition quickly in response to a transition of said first and second control voltages, respectively; and generating an output signal in response to said outputs of said first and second inverters; the invention lying in the step of maintaining the output of one of said inverters above a desired bias voltage, such that said one inverter quickly adjusts said output of said one inverter away from said bias voltage in response to a transition of a respective one of said control voltages. The present invention provides the technical advantage of a significantly lower propagation delay associated with both low-to-high and high-to-low input transitions. The present invention is compatible with ECL-to-CMOS and ECL-to-TTL conversions. BRIEF DESCRIPTION OF THE DRAWING For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following description taken in conjunction with the accompanying drawing, in which: FIGURE 1 is a schematic illustrating an ECL-to-CMOS/TTL voltage level translator with high current drive capability. DETAILED DESCRIPTION OF THE INVENTIONThe preferred embodiment of the present invention and its advantages are best understood by referring to FIGURE 1. FIGURE 1 is a schematic illustrating an ECL-to-CMOS/TTL voltage level translator 10 with high current drive capability. Input section 11 of voltage level translator 10 begins at input terminal 12, which is coupled to base 14 of npn transistor 16. Npn transistor 16 has a collector 18 coupled to first voltage line 20 (shown as Vcc), and an emitter 22 coupled through resistor 24 to second voltage line 26 (shown as ground). Emitter 22 of npn transistor 16 is also coupled to base 28 of npn transistor 30 at node A. Npn transistor 30 has a collector 32 coupled to first voltage line 20 through resistor 14, and an emitter 36 coupled to emitter 38 of npn transistor 40 and further coupled to collector 42 of npn transistor 44. Npn transistor 40 has a collector 46 coupled to first voltage line 20 through resistor 48, and a base 50 coupled to reference voltage Vbb1. Emitter 52 of npn transistor 44 is coupled through resistor 54 to second voltage line 26. Base 56 of npn transistor 44 is coupled to voltage Vcs. Npn transistor 58 has a collector 60 coupled to first voltage line 20, and a base 62 coupled to collector 46 of npn transistor 40 at node B. Emitter 64 of npn transistor 58 is coupled to drain 66 of n channel field effect transistor (FET) 68. N channel FET 68 has a source 70 coupled to second voltage line 26, and a gate 72 coupled to emitter 74 of npn transistor 76. Npn transistor 76 has a collector 78 coupled to first voltage line 20, and a base 80 coupled to collector 32 of npn transistor 30 at node C. Emitter 74 of npn transistor 76 is further coupled to drain 82 of n channel FET 84. N channel FET 84 has a source 86 coupled to second voltage line 26, and a gate 88 coupled to emitter 64 of npn transistor 58. Level shifter section 89 receives signals at nodes D and E. P channel FET 90 has a source 92 coupled to first voltage line 20, and a gate 94 coupled to gate 96 of n channel FET 98 and further coupled to emitter 64 of npn transistor 58 at node D. N channel FET 98 has a drain 100 coupled to drain 102 of p channel FET 90. Source 104 of n channel FET 98 is coupled to second voltage line 26. P channel FET 106 has a source 108 coupled to first voltage line 20, and a gate 110 coupled to gate 112 of n channel FET 114 and further coupled to emitter 74 of npn transistor 76 at node E. N channel FET 114 has a drain 116 coupled to drain 118 of p channel FET 106. Source 120 of n channel FET 114 is coupled to collector 122 of npn transistor 124. Npn transistor 124 has an emitter 126 coupled to second voltage line 26, and a base 128 coupled to collector 122 of npn transistor 124 and to emitter 110 of npn transistor 132. Npn transistor 132 has a collector 134 coupled to first voltage line 20 and a base 136 coupled to voltage Vcs. Output section 137 receives signals at nodes F and G. P channel FET 138 has a source 140 coupled to drain 118 of p channel FET 106 and further coupled to drain 116 of n channel FET 114 at node F. Gate 142 of p channel FET 138 is coupled to second voltage line 26. Drain 144 of p channel FET 138 is coupled to drain 146 of n channel FET 148. N channel FET 148 has a gate 150 coupled to drain 102 of p channel FET 90 and further coupled to drain 100 of n channel FET 98 at node G. Source 152 of n channel FET 148 is coupled to drain 154 of n channel FET 156. N channel FET 156 has a gate 158 coupled to first voltage line 20, and a source 160 coupled to second voltage line 26. Npn transistor 162 has a collector 164 coupled to first voltage line 20, and a base 166 coupled to node F. Emitter 168 of npn transistor 162 is coupled to output terminal 170. Output terminal 170 is further coupled to drain 144 of p channel FET 138 and to drain 146 of n channel FET 148. Collector 172 of npn transistor 174 is also coupled to output terminal 170. Npn transistor 174 has an emitter 176 coupled to second voltage line 26, and a base 178 coupled to source 152 of n channel FET 148 and further coupled to drain 154 of n channel FET 156. For purposes of explaining operation of translator 10, the voltage level provided at input terminal 12 is assumed to be a pseudo-ECL signal ranging between 3.29 volts and 4.02 volts. Although voltage level translator 10 will be described in connection with the pseudo-ECL voltage levels defined above, other voltage levels could also be provided at input terminal 12. For example, first voltage line 20 can be set to 0 volts, second voltage line 26 can be set to -5 volts, Vbb1 can be set to -2.14 volts, and Vcs can be set to -3.705 volts, resulting in CMOS inverted voltage levels at output terminal 170 ranging between -0.14 volts and -4.93 volts corresponding to standard ECL voltage levels at input terminal 12 ranging between -0.95 volts and -1.7 volts. In the illustrated embodiment, first voltage line is set to 5 volts, second voltage line is set to 0 volts, Vbb1 is set to 2.86 volts, and Vcs is set to 1.295 volts, resulting in CMOS voltage levels at output terminal 170 ranging between 4.86 volts and 0.07 volts corresponding to pseudo-ECL voltage levels at input terminal 12 ranging between 4.02 volts and 3.29 volts. Furthermore, the voltages provided at output terminal 170 ranging between 4.86 volts and 0.07 volts are compatible with TTL circuits. In operation, transistor 16 of input section 11 operates to reduce the voltage provided at input terminal 12 by one Vbe (approximately 0.85 volts), thereby conserving power. Transistors 10 and 40 operate together as a differencial amplifier which compares the voltage at node A with Vbb1. Vbb1 is a reference voltage set to determine whether the voltage at node A is a logic high or a logic low signal. Transistor 44 acts as a current source to the differential amplifier. In the preferred embodiment, Vcs is set to approximately 1.295 volts which draws a higher current than conventional ECL input circuits. This higher current combines with increased values in resistors 34 and 48 to increase the voltage drop across resistors 34 and 48, thereby increasing the signal swings at nodes C and B, respectively. Either transistor 30 or transistor 40 supplies the required current to transistor 44, depending on whether the voltage at node A is greater than or less than Vbb1. If node A is at a voltage greater than Vbb1 (i.e., the input is a logical high), then the voltage at node B equals the voltage of first voltage line 20 (i.e., 5 volts) and the voltage at node C equals approximately 3.62 volts (which may be adjusted by varying the values of Vcs and resistor 34). Conversely, if the input is a logic low, node C has a voltage of approximately 5 volts and node B has a voltage of 3.62 volts (which may be adjusted by varying the values of Vcs and resistor 48). In the preferred embodiment, each of resistors 34 and 48 has a resistance of 1,958 ohms, resistor 54 has a resistance of 585 ohms, and resistor 24 has a resistance of 9,375 ohms. Transistors 58 and 76 are configured as emitter-followers, which reduce the voltages at each of nodes B and C by one Vbe. N channel transistors 68 and 84 function as active loads to emitter-follower transistors 58 and 76, respectively. The loads provided by transistors 68 and 84 adjust as needed according to voltages at nodes D and E, thereby conserving power. Transistors 90 and 98 form a CMOS inverter which inputs the signal at node D. Similarly, transistors 106 and 114 form a CMOS inverter which inputs the signal at node E. As described in greater detail hereinbelow, in order to increase the speed of the circuit, the two CMOS inverters have trip voltages which are skewed higher than the normal CMOS inverter trip voltage of 2.5 volts. Transistors 132 and 124 maintain node F (the output of the inverter formed by transistors 106 and 114) above a bias voltage of 0.8 volts, which is the voltage potential between base 128 and emitter 126 of transistor 124. Transistors 162 and 174 accelerate the output transition time for output terminal 170. If node F is at a logic high, then transistor 162 quickly pulls output terminal 170 to one Vbe under the voltage of first voltage line 20. P channel transistor 138 further pulls output terminal 170 to the voltage at node F (approximately 4.86 volts). Conversely, if the voltage at node G (the output of the inverter formed by transistors 90 and 98) is near a logical high, transistor 174 pulls output terminal 170 to one Vbe over the voltage of second voltage line 26. Transistor 156, together with transistor 148, further pulls output terminal 170 toward the voltage of second voltage line 126. The operation of the circuit will be described for both logical high and logical low signals provided at input terminal 12. If input terminal 12 is provided a logical low signal (i.e., 3.29 volts), then transistor 16 conducts, and node A has a voltage of 2.44 volts. With node A at 2.44 volts, thus falling below the 2.86 volts at Vbb1, transistor 30 does not conduct, and transistor 40 does conduct and therefore supplies required current to transistor 44. Since transistor 30 does not conduct, the voltage level at node C is 5 volts. While transistor 40 conducts, the voltage level at node B is 3.62 volts, because of a 1.18 volt drop across resistor 48. Even larger voltage level differences between node B and node C can be achieved by further increasing the value of resistor 48 and the current flow through transistor 44. The voltage potential between base 62 and emitter 64 of transistor 58 is 0.85 volts. Similarly, the voltage potential between base 80 and emitter 74 of transistor 76 is also 0.85 volts. Therefore, since the voltage at node B is 3.62 volts, the voltage at node D is 2.77 volts. Since the voltage at node C is 5 volts, the voltage at node E is 4.15 volts. Transistors 68 and 84 function as low power active pull-downs for transistors 58 and 76, respectively. For a typical CMOS inverter, the ratio of channel width for a p channel transistor compared to an n channel transistor is set to 2:1. In the preferred embodiment, the ratio of channel width for p channel transistor 90 compared to n channel transistor 98 is set at 7.72:1, which correspondingly decreases the ratio of voltage level drop across transistor 90 compared to transistor 98. The inverter formed by transistors 90 and 98 is thus set to a trip voltage (the voltage at which the inverter switches its logical output levels) skewed higher than the normal CMOS inverter trip voltage of 2.5 volts. The 2.77 volts applied to gates 94 and 96 causes both transistors 90 and 98 to conduct current, but transistor 90 conducts with less resistance than transistor 98 and therefore less voltage drop. Since transistor 90 conducts current with less voltage drop than transistor 98, node G is pulled toward the voltage of first voltage line 20. While the voltage at node D is 2.77 volts, node G is approximately 4.2 volts, because of a 0.8 volt drop across transistor 90. In the preferred embodiment, the ratio of channel width for p channel transistor 106 compared to n channel transistor 114 is set to 9.6:1, which correspondingly decreases the ratio of voltage level drop across transistor 106 compared to transistor 114. The inverter formed by transistors 106 and 114 is thus set to a trip voltage skewed higher than the normal CMOS inverter trip voltage of 2.5 volts. The 4.15 volts applied to gates 110 and 112 causes transistor 114 to almost fully conduct current, while transistor 106 conducts slightly. While transistor 106 slightly conducts and transistor 114 almost fully conducts, node F is pulled toward the voltage of second voltage line 26, subject to the voltage potential between base 128 and emitter 126 of transistor 124. Thus, in this situation, node F has a voltage of approximately 0.8 volts. Since the voltage at node F is 0.8 volts, transistor 162 does not conduct. In this case, the corresponding 4.2 volt level at node G causes transistor 148 to conduct. Therefore, the voltage of output terminal 170 is coupled to base 178 of transistor 174, thereby causing transistor 174 to conduct (assuming output terminal 170 was previously in a logical high state). Bipolar transistor 174 quickly pulls output terminal 170 toward the voltage of second voltage line 26, subject to the voltage potential between base 178 and emitter 176, which approximates 0.7 volts. While transistors 148 and 156 are also conducting, output terminal 170 is eventually pulled further toward the voltage of second voltage line 26 to approximately 70 millivolts. Transistor 174 therefore provides this voltage level translator 10 with high current drive capability, while transistors 148 and 156 pull output terminal 170 to a desired low voltage. If input terminal 12 is provided a logical high signal (i.e., 4.02 volts), then transistor 16 conducts, and node A has a voltage of 3.17 volts. With node A at 1.17 volts, thus rising above the 2.86 volts at Vbb1, transistor 30 conducts and therefore supplies required current to transistor 44, and transistor 40 does not conduct. Since transistor 40 does not conduct, the voltage level at node B is 5 volts. While transistor 30 conducts, the voltage level at node C is 3.62 volts, because of a 1.38 volt drop across resistor 34. Even larger voltage level differences between node B and node C can be achieved by further increasing the value of resistor 34 and the current flow through transistor 44. Since the voltage at node B is 5 volts, the voltage at node D is 4.15 volts. Transistor 90 slightly conducts, and transistor 98 almost fully conducts. Therefore, node G is pulled toward the voltage of second voltage line 26. Thus, in this situation, node G has a voltage of approximately 43 millivolts, because of a 43 millivolt drop across transistor 98. Since the voltage at node C is 3.62 volts, the voltage at node E is 2.77 volts. Transistor 106 conducts current with less voltage drop than transistor 114. Therefore, node F is pulled toward the voltage of first voltage line 20. While the voltage at node E is 2.77 volts, node F is approximately 4.86 volts, because of a 0.14 volt drop across transistor 106. Since the voltage at node G is 43 millivolts, transistor 148 does not conduct, nor do transistors 156 and 174. In this case, the corresponding 4.86 volt level at node F causes transistor 162 to conduct, along with transistor 138. Bipolar transistor 162 quickly pulls output terminal 170 toward the voltage of first voltage line 20, subject to the voltage potential between base 166 and emitter 168, which approximates 0.7 volts. While transistor 138 also conducts, output terminal 170 is eventually pulled further toward the voltage at node F to approximately 4.86 volts. Transistor 162 therefore provides this voltage level translator 10 with high current drive capability, while transistor 138 pulls output terminal 170 to a desired high voltage. Transistor 174 does not conduct because the voltage on node G is less than the 0.7 volt Vbe between base 178 and emitter 176 of transistor 174. The voltage level translator 10 has a nominal propagation delay of under 500 picoseconds with a nominal power dissipation of 12.5 milliwatts. This 500 picosecond delay is partially achieved by increasing the ratio of channel width for p channel transistor 90 compared to n channel transistor 98. This increased ratio of channel widths enables both transistors 90 and 98 to conduct current even when the voltage at node D is only as low as 2.77 volts, which produces a voltage at node G of 4.2 volts sufficient to drive output section 137. Conversely, when the voltage at node D is 4.15 volts, transistor 98 almost fully conducts while transistor 90 conducts slightly, which produces a voltage at node G of approximately 43 millivolts sufficient to operate output section 137. Therefore, the increased ratio of channel width for p channel transistor 90 compared to n channel transistor 98 effectively narrows the voltage range necessary for node D to sufficiently operate output section 137, and this increased ratio also allows both transistors 90 and 98 to conduct current for all voltages within the narrowed voltage range of node D, thus shortening the required transition time for transistors 90 and 98 to fully adjust to a new voltage at node D. Similarly, the 500 picosecond delay is further achieved by increasing the ratio of channel width for p channel transistor 106 compared to n channel transistor 114. This increased ratio effectively narrows the voltage range necessary for node E to sufficiently operate output section 137, and it also allows both transistors 106 and 114 to conduct current for all voltages within the narrowed voltage range of node E, thus shortening the required transition time for transistors 106 and 114 to fully adjust to a new voltage at node E. Furthermore, the 500 picosecond delay is achieved by inserting transistor 124 to provide a voltage potential between base 128 and emitter 126 of transistor 124. This voltage potential maintains node F above a minimum voltage of 0.8 volts, which narrows the range of voltages for node F and therefore shortens the necessary transition time for node F to fully adjust to a new voltage at node E, particularly when node F adjusts from a logic low level to a logic high level. Also, by using transistor 124 to raise the minimum voltage at source 120 of transistor 114, the trip voltage of the inverter formed by transistors 106 and 114 is further skewed higher than the normal CMOS inverter trip voltage of 2.5 volts, because gate 112 of transistor 114 must therefore, apply a higher voltage for transistor 114 to conduct current. Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims.
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An apparatus for translating voltages comprising: an input section (11) for generating first and second control voltages (D,E) within a voltage range in response to an input signal; a level shifter section (89) comprising first and second inverters (90,98;106,114) respectively coupled to said control voltages, each of said inverters comprising a plurality of transistors, wherein each transistor (90,98,106,114) maintains current in response to one of said control voltages (D,E) being anywhere within said voltage range, such that outputs (G,F) of said first and second inverters are operable to transition quickly in response to a transition of said first and second control voltages (D,E) respectively; and an output section (137) for generating an output signal in response to said output of said first and second inverters; characterised in that said level shifter section comprises a bias voltage device (124) coupled to one of said inverters (106,114) and operable to maintain the output of said one inverter above a desired bias voltage, such that said one inverter (106,114) is operable to quickly adjust said output of said one inverter away from said bias voltage in response to a transition of a respective one of said control voltages (E). The apparatus of claim 1 wherein each of said first and second inverters comprises a p channel field effect transistor (90,106) and an n channel field effect transistor (98,114). The apparatus of claim 2 wherein the channel of said p channel field effect transistor (90,106) is over twice as wide as the channel of said n channel field effect transistor (98,114). The apparatus of any one of claims 1 to 3, wherein said bias voltage device comprises: a first npn bipolar transistor (124) having an emitter coupled to a first reference voltage (26), a collector (122) and a base (128), said collector coupled to said base and to said one inverter (106,114); and a second npn bipolar transistor (132) having an emitter (130) coupled to said base of said first npn transistor (124), a collector (134) coupled to a second reference voltage (20), and a base (136) coupled to a third reference voltage (Vcs). The apparatus of any preceding claim wherein said output section (137) comprises an npn bipolar transistor (162) for providing high current drive capability for said output signal, having a base (166) coupled to one of said inverter outputs (F), an emitter (168) coupled to said output signal, and a collector (164) coupled to a reference voltage (20). The apparatus of any preceding claim wherein said output section comprises: an n channel field effect transistor (148) having a gate (150) coupled to one of said inverter outputs (G), a drain (146) coupled to said output signal, and a source (152); and an npn bipolar transistor (174) for providing high current drive capability for said output signal, having a base (178) coupled to the source (152) of said n channel transistor (148), a collector (172) coupled to said output signal, and an emitter (176) coupled to a reference voltage (26). The apparatus of any preceding claim wherein said input section comprises a differential amplifier (30-56) coupled to said input signal and to a reference voltage (VBB1) operable to generate said first and second control voltages. A method for translating voltages comprising the steps of: generating first and second control voltages (D,E) within a voltage range in response to an input signal; maintaining current through each of a plurality of transistors (90,98,106,114) in response to one of said control voltages (D,E) being anywhere within said voltage range, said transistors forming first and second inverters (90,98;106,114) respectively coupled to said control voltages, such that outputs (G,F) of said first and second inverters (90-104,106-120) transition quickly in response to a transition of said first and second control voltages, respectively; and generating an output signal in response to said outputs of said first and second inverters; characterised by the step of maintaining the output of one of said inverters (106-120) above a desired bias voltage, such that said one inverter quickly adjusts said output of said one inverter away from said bias voltage in response to a transition of a respective one of said control voltages (E). The method of claim 8, wherein said step of maintaining current comprises the step of maintaining current through a p channel field effect transistor (90,106) and through an n channel field effect transistor (98,114) together forming one of said inverters. The method of claim 9, wherein said step of maintaining current comprises the step of maintaining current through the channel of said p channel field effect transistor (90,106) being over twice as wide as the channel of said n channel field effect transistor (98,114). The method of any one of claims 8 to 10, wherein said step of generating first and second control voltages (D,E) comprises the step of generating said first and second control voltages with a differential amplifier (30-56) coupled to said input signal and to a reference voltage (VBB1).
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TEXAS INSTRUMENTS INC; TEXAS INSTRUMENTS INCORPORATED
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TEN EYCK TIMOTHY A; TEN EYCK, TIMOTHY A.
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EP-0489567-B1
| 489,567 |
EP
|
B1
|
EN
| 19,950,823 | 1,992 | 20,100,220 |
new
|
F21V1
| null |
F21V1
|
F21V 1/14
|
Universal foldable lamp shade overshade
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A universal foldable lamp shade overshade (1⊘) which includes a uniformly pleated rectangular sheet (12) of thin, somewhat rigid yet bendable material having a plurality of side-by-side slender elongated panels integrally connected one to another in accordion fashion along a fold line between each panel. A hole is formed through each panel adjacent its upper end (24) through which a draw string (14) is positioned in in-and-out fashion through alternate holes. The side margins (28 and 3⊘) of the pleated sheet are connected to form a somewhat tubular member which is sized, when reduced in circumference at its upper end (24) by tightening the drawstring (14), to be held in place primarily by gravity over and substantially covering a lamp shade (L).
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This invention is generally related to lamp shades, and more particularly to a removable, universal, foldable lamp shape overshade. The construction of conventional lamp shades is well known and typically require replacement long before the lamp itself is either worn or desired to be replaced for decorative considerations. However, in replacing a conventional lamp shade, both size and decorative considerations become somewhat restrictive in selecting a replacement. Additionally, seasonal or festive considerations may make it desirable to temporarily alter the appearance of one or more lamp shades in a room or home setting. One such device for accomplishing this is disclosed in U.S. Patent 4,731,715 to Anderson which is directed to a conformable covering fabricated from a rectangular swath of cloth which may be fitted over a conventional lamp shade. Other uniquely constructed lamp shades and lamp shade covers are as follows: Gottlieb3,161,358 Washick3,385,963 Weisbrod4,055,760 Gall4,354,222 Payne4,625,268 Naumoff, et al.4,727,461 However, none of these references are of a nature similar to that of the present invention. US-A-1 940 672 discloses a pleated lampshade that is gathered at the top by an elastic cord to sit on the flange of a conventional lampshade support and is spread and stiffened near the bottom by a circumferential fold running across the pleats and forcing them flat. US-A-1 929 315 discloses a lampshade that consists of a smooth inner layer and a pleated outer layer fastened together along substantially the whole of the inner fold of every pleat. The invention provides a universal foldable lamp shade overshade consisting essentially of: a uniformly pleated rectangular sheet of thin, bendable material; said pleated sheet defined by a plurality of side-by-side slender elongated rectangular panels integrally connected one to another in accordion fashion along a fold line between each two adjacent said pleated panels ending in an end panel at each end of said pleated sheet; a hole formed through each said panel uniformly positioned from, and close to, the upper margin of said pleated sheet; means for connecting said end panels together to form a generally tubular member; a drawstring extending through each said hole in alternate in-and-out fashion around said tubular member and exiting at each end of said drawstring from two adjacent said holes, said drawstring longer than the relaxed circumference of said tubular member; said tubular member having a relaxed circumference sized to fit around an upwardly tapering lamp shade; said tubular member reducible in circumference at its upper end by shortening said drawstring to provide an only means for hanging support of said tubular member in position over the lamp shade whereby said tubular member will rest over and substantially cover the lamp shade remaining thusly primarily by the force of gravity. It is possible to manufacture a universal, foldable lamp shade overshade according to the present invention from any convenient semi-rigid decorative material which is formed into a uniformly pleated rectangular sheet bendable primarily about the fold lines between each slender panel in accordion fashion. This structure preferably has sufficient pliability about the fold lines so as to conform to a broad range of lamp shade sizes of perimeters and lengths and shapes. Because the device is structured so as to rest atop a tapered lamp shade held thusly primarily by gravity, it preferably requires no additional connecting means between the device and the lamp shade. The lamp shade overshade may be fabricated from a virtually limitless selection of semi-rigid, bendable decorative materials. It is possible in accordancw with this invention to provide a universal lamp shade overshade which will decoratively cover a conventional lamp shade, thus providing a completely different decorative lamp shade appearance without the need for lamp shade replacement. It is also possible to provide a universal lamp shade overshade which is expandable to fit over and cover a very broad range of lamp shade sizes of perimeters and lengths and shapes. It is further possible to provide a universal lamp shade overshade which may substantially alter the decorative length configuration of a conventional lamp shade. It is further possible for the lamp shade overshade to be made compactly storable. In accordance with these and other objects which will become apparent hereinafter, the instant invention will now be described with reference to the accompanying drawings. Figure 1 is a perspective view of the preferred embodiment of the invention in its relaxed configuration. Figure 2 is an exploded view of the invention shown in Figure 1 fitted over a conventional lamp shade. Figure 3 is a section view in the direction of arrows 3-3 in Figure 1. Figure 4 is a section view similar to Figure 3 showing an alternate connecting means between the free side margins of the pleated rectangular sheet. Figure 5 is a view in the direction of arrows 5-5 in Figure 2. Figure 6 is a view similar to Figure 5 in conjunction with an irregularly shaped lamp shade. Figure 7 is an end view of the invention in its stored configuration and showing yet another configuration for connecting the side margins of the pleated sheet. Referring now to the drawings, and particularly to Figure 1, the preferred embodiment of the invention is shown generally at numeral 1⊘. This overshade 1⊘ is fabricated of a pleated sheet 12 formed of relatively stiff, yet foldable decorative material sufficiently rigid so as to maintain a free-standing shape as shown in Figure 1, yet sufficiently pliable so as to be expandable in accordion fashion. Referring additionally to Figure 3, edge panels 28 and 3⊘ of pleated sheet 12 are overlapped and adhered together along surface 32 by conventional adhesive, double-sided adhesive tape, or the like so as to form the generally tubular-shaped member depicted in Figure 1. A drawstring 14 formed of a length of thin, flexible cord material is positioned in in-and-out fashion through holes formed adjacent the upper margin 24 of the pleated sheet 12. The ends 2⊘ and 22 of drawstring 14 exit through adjacent holes at 16 and 18 so as to be tightenable and tieable after suitably reducing the circumference of the upper end 24 of the tubular-shaped pleated sheet 12. Alternately, the flexible cord 14 may be elastic and continuous. Referring additionally to Figure 2, the overshade 1⊘ is shown having drawstring 14 tensioned so as to have reduced the circumference of upper margin 24 ready for slidable fitting downwardly over a conventional lamp shade L. No further preparation is required to fit the device 1⊘ in snug position over and substantially or fully covering the lamp shade L. Because most lamp shades are tapered upwardly, coupled with the tensioning and securing of drawstring 14, the device 1⊘ will remain in position decoratively covering the lamp shade L, aided primarily by the force of gravity and surface friction between the inner surface of the device 1⊘ and the outer surface of lamp shade L. Referring now to Figure 4, an alternate embodiment of the connecting means between the edge panels 28 and 3⊘ of the pleated sheet 12 is there depicted at 1⊘. This connecting means is in the form of a U-shaped metal or plastic clip 36 having opposing inwardly projecting barbs 38 and 4⊘ which pierce through the corresponding layers of overlapping panel material to secure and maintain the tubular shape. Referring now to Figures 5 and 6, the compliability of the embodiments 1⊘ and 1⊘ of the invention around irregular shaped lamp shades L and L each having its own distinctively shaped upper and lower margins N and M or N and Ml is there shown. Thus, from the standpoint of both size and shape accommodation, either embodiment of the invention 1⊘ or 1⊘ is fully capable of expanding as required and exhibiting sufficient pliability so as to generally maintain the overall shape of the lamp shade L or L. Moreover, the length of the tubular member 12 may be selected so as to be substantially longer than the height of the lamp shade and drawstring 14 may be tensioned such that either the upper margin 24 or the lower margin 26 may extend either above, or below, the upper or lower margins, respectively of a lamp shade. Because of the relatively stiff nature of the pleated sheet, the overall tubular shape, in the form of a truncated cone as in Figure 2, will uniformly extend the existing shape of the lamp shade itself so as to alter the decorative impact thereof. Referring lastly to Figure 7, the invention is shown in another alternate form at 1⊘ in its fully folded or stored configuration. In this embodiment 1⊘, the same pleated sheet 12 is adhered along overlapping edge panels 28 and 3⊘ and the panel adjacent to each so as to increase the overall strength of the tubular shape.
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A universal foldable lamp shade overshade (10, 10', 10'') consisting essentially of: a uniformly pleated rectangular sheet (12) of thin, bendable material; said pleated sheet defined by a plurality of side-by-side slender elongated rectangular panels integrally connected one to another in accordion fashion along a fold line between each two adjacent said pleated panels ending in an end panel (28, 30) at each end of said pleated sheet (12); a hole formed through each said panel uniformly positioned from, and close to, the upper margin (24) of said pleated sheet (12); means for connecting said end panels together to form a generally tubular member (12); a drawstring (14) extending through each said hole in alternate in-and-out fashion around said tubular member and exiting at each end of said drawstring from two adjacent said holes (16, 18), said drawstring longer than the relaxed circumference of said tubular member (12); said tubular member (12) having a relaxed circumference sized to fit around an upwardly tapering lamp shade (L, L'); said tubular member reducible in circumference at its upper end by shortening said drawstring (14) to provide an only means for hanging support of said tubular member (12) in position over the lamp shade (L, L') whereby said tubular member (12) will rest over and substantially cover the lamp shade (L, L'), remaining thusly primarily by the force of gravity. A universal foldable lamp shade overshade (10, 10', 10'') as set forth in Claim 1, wherein: said connection means is adhesive. A universal foldable lamp shade overshade (10, 10', 10'') as set forth in Claim 1, wherein: said connecting means is a self-engaging barbed clip (36). A universal foldable lamp shade overshade (10, 10', 10'') as set forth in any one of Claims 1 to 3, wherein: said tubular member (12) is sized to expand and fit over a wide range of circumferences of lamp shades (L, L'). A universal foldable lamp shade overshade (10, 10', 10'') as set forth in any one of Claims 1 to 4, wherein: said tubular member (12) has a length substantially longer than the height of the lamp shade (L, L'). A universal foldable lamp shade overshade (10, 10', 10'') as set forth in any one of Claims 1 to 5, wherein: said tubular member (12) is sufficiently compliant along said fold lines to conform around non-circular lamp shades (L, L'). A universal foldable lamp shade overshade (10, 10', 10'') as set forth in any one of Claims 1 to 6, wherein: said tubular member (12) is collapsible along said fold lines into a compressed configuration for storage. A universal foldable lamp shade overshade (10, 10', 10'') as set forth in any one of Claims 1 to 7, wherein: said drawstring (14) is elastic. In combination, a lamp shade and a lamp shade overshade (10, 10', 10'') cooperatively structured to loosely fit over and be supported only by said upwardly tapered lamp shade (L, L'), said lamp shade overshade consisting essentially of: a uniformly pleated rectangular sheet (12) of thin, bendable material; said pleated sheet defined by a plurality of side-by-side slender elongated rectangular panels integrally connected one to another in accordion fashion along a fold line between each two adjacent said pleated panels ending in an end panel (28, 30) at each end of said pleated sheet (12); a hole formed through each said panel uniformly positioned from, and close to, the upper margin (24) of said pleated sheet (12); means for connecting said end panels together to form a generally tubular member (12); a drawstring (14) extending through each hole in alternate in-and-out fashion around said tubular member and exiting at each end of said drawstring from two adjacent said holes (16, 18), said drawstring longer than the relaxed circumference of said tubular member (12); said tubular member (12) having a relaxed circumference sized to fit around said lamp shade (L, L'); said tubular member (12) reducible in circumference at its upper end by shortening said drawstring (14) to provide an only means for supporting said tubular member (12) in position over said lamp shade (L, L') whereby said tubular member (12) substantially covers the lamp shade (L, L'), remaining thusly primarily by the force of gravity.
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HYLAND BARBARA B; HYLAND JOSEPH F; HYLAND, BARBARA B.; HYLAND, JOSEPH F.
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HYLAND BARBARA B; HYLAND JOSEPH F; HYLAND, BARBARA B.; HYLAND, JOSEPH F.
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EP-0489568-B1
| 489,568 |
EP
|
B1
|
EN
| 19,950,329 | 1,992 | 20,100,220 |
new
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C04B41
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C04B41
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C04B41, C04B32, E04G23
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C04B 41/52, C04B 41/65, C04B 41/70, C04B 41/50F2
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Posttreatment of concrete for corrosion inhibition
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A method of posttreating a concrete structure to provide corrosion inhibiting properties by heating the structure to remove water entrapped therein, then cooling the structure under a maximum temperature gradient conditions of + 2°C/in. thickness, applying an aqueous solution of corrosion inhibitor and then an aqueous wash thereto.
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The present invention is directed to a method of rehabilitating and stabilizing salt contaminated concrete structures. It is well known that reinforced concrete structures, such as bridges, parking garages, and the like are highly susceptible to corrosion and degradation from commonly applied chloride deicing salts. It is believed that a large percentage of all bridge decks in the United States and in other countries which have cold climates are seriously deteriorated because of corrosion of the reinforcing steel which is part of their structure. This corrosion is usually caused by chloride ions that have penetrated the concrete as a result of repeated application of deicing salts. In the case of concrete parking structures, automobiles carry salt contaminated ice and snow to the structure and, while parked, allow the contaminated ice and snow to melt and concentrate on the concrete structure. In all cases accumulation of corrosion products around the reinforcing steel causes cracks to develop in the concrete cover. This allows even more rapid intrusion of additional chloride solution and, thereby, accelerates corrosion and spalling of the concrete structure. If corrosion and spalling is allowed to continue, the metal reinforcements, as well as the surrounding concrete, deteriorate to a point which requires substantial removal and replacement of the entire structure. This is a difficult and costly endeavor. Several methods have been suggested to ameliorate the condition of concrete structures which have undergone or are susceptible to corrosion deterioration. For example, low permeability overlays have been applied to deteriorated structures. In such instances, spot repairs of severely deteriorated concrete is first accomplished. However, large areas of chloride-contaminated concrete remain in place and, although slowed, corrosion and deterioration continue to occur. Thus, this method alone does not address the need for a long-term rehabilitation procedure. A rehabilitation technique which is often used involves scarifying the top portion of a bridge deck or the like prior to application of a new overlay. Scarification to a level within 1.3 cm (0.5 inch) of the embedded reinforcement metal elements removes a major amount of contaminated concrete, permits impregnation of corrosion inhibiting agents to the concrete around the steel reinforcements and then application of a new overlay concrete structure. A preferred mode requires removal of the concrete surrounding the steel reinforcements prior to applying a new overlay. These methods are not cost-effective and are, therefore, only viewed as a secondary means to the complete removal and replacement of the concrete structure. In an attempt to offer a more cost effective method to nullify the effects of chlorides and other corrosion elements to concrete structures and to cause the resultant structure to exhibit long-term effectiveness, impregnation of salt-contaminated, but structurally sound structures, with corrosion resisting materials has been proposed. Impregnation to a depth sufficient to encapsulate the reinforcement was thought to provide the long term protection. Impregnation with polymers such as methyl methacrylate, or water tolerant monomers and/or corrosion inhibitors, have been attempted but have been found to be costly, difficult to apply and have detrimental effects with respect to the resultant concrete properties. Prior impregnation techniques have been found difficult to carry out in an effective manner. It is well known that concrete is a porous structure. The pores contain residual water from that used during hydration of the cement as well as rain water and the like which has penetrated into the pores over a period of time. Thus, impregnation of organics or even aqueous solutions into such already occupied pores has been found to be extremely difficult. It has been previously proposed that impregnation be carried out by first heating the concrete structure to drive off the water contained in the pores followed by application of the impregnating solution. However, when this method has been previously used the resultant structure showed extensive cracking which not only weakened the structure but also made it more susceptible to attack by subsequently applied chloride salts. There is the need for a process which can provide a feasible and effective means of arresting corrosion of reinforcement in sound but corrosive salt-contaminated concrete without causing detrimental effects to the other desired concrete properties such as strength, permeability freeze/thaw properties and structural soundness. Further, there is a need to provide a process of posttreating a sound concrete structure to insure its ability to withstand the corrosive forces of subsequently applied corrosive causing agents, such as chloride salts. The present invention provides a process of posttreating concrete structures to substantially arrest corrosion of the metal reinforcing elements contained therein without detrimentally effecting the concrete structure. Specifically, the present invention is directed to a posttreatment (with respect to the formation of the concrete structure) process of heating a concrete structure to an elevated temperature of at least about 100°C, cooling the structure under controlled conditions to maintain a temperature differential between the structure's upper surface and a predetermined depth of 0.8°C/cm (2°C/inch) or less of concrete thickness, and then impregnating the concrete with an aqueous solution of a corrosion controlling agent. The resultant structure is capable of withstanding corrosive attack over a sustained period of time and does not cause deleterious effects to its structural integrity. The present invention is directed to posttreatment of sound concrete formations to inhibit future corrosion of the metal reinforcement therein and deterioration of the surrounding concrete. The corrosive element normally causing the problem to reinforced concrete formations are chloride ions which interact with the metal of the reinforcement and cause its deterioration. The chloride ions may be supplied by conventional application of deicing salts, such as alkali or alkaline earth metal chlorides. The chloride ions may also be supplied by environmental means especially when the concrete structure is located near salt-water bodies. In addition, corrosive salt may be supplied by secondary means, such as by vehicles which have salt-laden ice or snow thereon which, when parked, melts and is redeposited on the concrete structure (such as parking garages and the like). In all cases, the process of the present invention is directed to enhancing structurally sound concrete formations. That is, formations which have not had sufficient deterioration to make them susceptible to normal usage. The concrete formation may be only recently formed or may be laden with chloride or other corrosive salt provided that corrosion of the reinforcements has not advanced to the point of unsafe condition. Concrete formations most appropriate for application of the present process are bridge decks and parking garage structures formed from reinforced concrete. Depending on the size of the structure and the equipment, the present process can be applied to the entire structure or to sections of the structure in a continuous or discontinuous manner. The process involves initially heating the structure to be treated. A temperature of at least about 100°C, (preferably from about 100°C to about 110°C) at a predetermined depth (thickness) of the concrete structure is normally sufficient although somewhat lower or higher temperatures may be satisfactory. It is not necessary to protect (and thereby treat) the entire structure's thickness. Normally, treatment to a depth where the reinforcement metal (e.g. rebars) is located or a depth of about half of the thickness is sufficient in most instances. The temperature of the structure (both for heating and for cooling, as described below), can be readily monitored by placement of at least one thermocouple or the like temperature measuring means on the upper surface, the lower surface and at the predetermined depth of the concrete structure to which protection is desired. It is understood that as the structure reaches the temperature of 100°C or greater at the predetermined depth, the upper surface (to which heat is being applied) will be at a higher temperature while the lower surface will be at a lower temperature. Prior to initiating actual heating, the structure should be treated to provide an efficient and effective process. The structure, as discussed above, should have temperature monitoring means, such as thermocouples, applied to the upper surface and into the structure to the predetermined depth (e.g. to the level of the rebars or the middle of the structures thickness or the like). Optionally temperature monitoring means can also be applied to the underside surface of the structure. Further, in order to efficiently and effectively heat the concrete structure, an overstructure should be constructed to concentrate the heat onto the defined surface. Normally sections of a structure are treated due to the large area of an entire structure, such as a bridge deck or parking garage. The overstructure need not be elaborate but merely provides a means of concentrating the heat and not allowing it to merely dissipate to the surrounding environs. A metal tube and fiberglass insulating panel overstructure will provide the needed heat concentration. The super structure should have means which allow air to escape and thus carry out the moisture laden air developed within the environ of the overstructure. This can be readily done by having the side panels of the insulating superstructure extend to a point above the upper surface of the concrete structure. The overstructure may also be made mobile so that it can be readily moved from section to section of the concrete structure being treated. Still further, the periphery of the treated structural area should be insulated. Exposed edges should be insulated with glass batting or the like. Areas of the concrete structure which are adjacent to the area being treated should have their surfaces insulated. The insulated surface may extend at least about two feet from the treated structure but the exact amount is not critical provided it permits a gradual gradient of temperature between the treated and adjacent untreated portion. Optionally, insulation may be also applied to the underside of the treated and adjacent areas of the structure. Prior to treatment, the area to be treated may be scored to increase the surface area and thereby provide greater heating ability as well as greater ability to absorb the subsequently applied corrosion control solution, as more fully described below. The scoring of the surface is especially useful when treating structures which have an upper surface which is substantially not horizontal. In such instances, the scoring should be perpendicular to the slope of the upper surface. With the canopy or superstructure over the concrete structure to be treated and the insulation in place, as described above, the structure is heated with the aid of any conventional high capacity heat source. The specific capacity will depend upon the size of structure being treated at any one time. Conventional units having capacities of up to 176 kW (600,000 BTU/hr) and greater are available. Such sources of heat include, for example, portable oil fired heaters or gas heaters. In certain instances, the heaters may be modified to adjust the volume of air entering the unit and thereby increase the temperature rise capacity of a given unit. The concrete structure is heated in a gradual manner. The rate of heating is not critical. Heating at rates of up to about 110 W/m²°C (20 BTU per hour-sq.ft.-degree F) (preferably from about 11-110 W/m²°C (2 - 20 BTU per hr.sq.ft.-deg.F.)) is satisfactory. Heating is normally done in a continuous manner until the desired concrete temperature is reached. At this point in time, the upper surface is at the highest temperature, (normally about 110-140°C), while the bottom surface is at the lowest temperature of the slab (normally from slightly above ambient when not insulated to about 60-100°C when insulated). The internal temperature of the concrete structure at the predetermined thickness depth between upper and lower surfaces should be at about 100°C, as stated above. Once the structure has reached the desired temperature at the predetermined thickness or depth, heating is stopped and cooling of the structure is allowed to commence under controlled conditions. It has been unexpectedly found that the cooling profile of the upper portion of the concrete structure has been found to be critical in providing a structure having ultimate beneficial effects. The upper portion is meant herein and in the appended claims to be the structure's thickness above the predetermined depth. When the heat source is stopped, the temperature profile of the upper surface rapidly decreases with time giving up heat both to the adjacent atmosphere above the surface and to the concrete mass below. The temperature profile at the predetermined depth and at the lower surface normally continues to rise for a short period of time and then commence cooling. The temperature gradient throughout the thickness of the concrete structure being treated from the upper surface to at least the predetermined thickness must not be greater than 0.8°C/cm (2°C/inch) thickness. That is, the internal temperature should not be allowed to exceed 0.8°C/cm (2°C/inch) gradient with respect to the upper surface (which, after an initial period, will be cooler than the internal temperature). Thus, initially there is a negative gradient as the upper surface is hotter than that of the predetermined depth. Within a short period the upper surface temperature falls below the predetermined depth temperature. The upper surface must not be allowed to cool at a rate which would allow it and the intervening concrete thickness to surpass the 0.8°C/cm (2°C/inch) temperature differential. The peripheral insulation material and the insulating superstructure initially applied not only helps in heating the structure more efficiently but also aids in controlling the cooling within the required limits and not to permit large temperature differentials between the structure and the surrounding atmosphere. Further, the heater can be intermittently used to maintain the air above the structure at a suitable temperature to also aid in controlling the cooling within the required limits. It is further preferred that the temperature gradient between the internal predetermined level and the lower exposed surface of the concrete structure be maintained at less than about 5.9°C/cm (15°C/inch) of thickness although it has been found that this lower thickness gradient is not critical and may be varied to a greater or lesser degree without causing adverse effects on the resultant structure. The structure should be allowed to cool to within about 20°C of ambient temperature, preferably within 10°C of ambient and most preferably ambient temperature. After the structure has substantially cooled, a solution of a suitable concrete structure corrosion inhibiting agent should be applied to the upper surface. The inhibiting agent can be selected from commonly known compounds and compositions which are known to counteract and/or inhibit corrosion of reinforced concrete structures by chloride. Examples of such agents include alkali and alkaline earth metal nitrites and, preferably, calcium nitrite. The corrosion inhibiting agent should be applied as aqueous solution having the agent in concentration of from about 5 up to about 20 wt. percent, preferably from about 10 up to about 15 wt. percent are normally satisfactory. Very high concentrations (greater than 25 wt. percent) should be avoided. The corrosion inhibiting agent should be applied in amounts to provide an effective dosage to counter the chloride corrosion agent already present and to provide a residual amount to inhibit future corrosion. The particular dosage will, therefore, depend on the concrete structure being treated and can be readily determined by the field engineer. Normally, dosages of from about 0.5% s/s to 5% s/s and preferably from about 1% s/s to 3% s/s provide satisfactory long term inhibiting properties to concrete structures. Where s/s is solids of agent per unit of solid cement contained in the composition being treated. The corrosion inhibiting agent containing aqueous solution is readily applied to substantially horizontal surfaces by damming the periphery of the upper surface and ponding the solution on the surface. Sloped surfaces can be treated by spraying the surface or, as discussed above by applying the solution to grooved surface such that the solution is trapped in the grooves. The solution is applied over a period of time (usually 4-24 hours) until the rate of absorption of the solution into the prior dried concrete is minimal. Solutions having concentrations of about 10 - 15 wt. percent inhibiting agent provide most effective dosage application in a reasonable period (normally 4 - 24 hrs). The entire surface should be kept wet with the application solution for a time until the rate of its absorption into the concrete is minimal. When the upper surface had not cooled to ambient temperature, the solution should be at a temperature of about i.e. ± 10°C (preferably ± 2°C) of the upper surface temperature of the structure. Following application of the corrosion inhibiting solution, as described above, water should be applied to the concrete upper surface to force the corrosion inhibiting solution further into the structure's thickness and away from the structure's upper surface region. If the inhibiting agent is allowed to remain in concentrated form at the upper surface and the thickness immediately adjacent thereto ( the upper surface region ), the concrete may exhibit poor freeze-thaw properties which will result in spalling of the concrete. The amount of flush water used will vary with the particulars of the structure as, for example, its porosity, the amount of corrosion inhibitor applied, the depth of the rebars and the like. Flush water in the amount of from about 0.1 to 10 times the amount of corrosion inhibiting agent containing solution is normally satisfactory. The above steps provide a means of enhancing the corrosion inhibiting characteristics of a reinforced concrete structure without causing reduced physical and structural characteristics of the resultant structure, as are commonly observed with respect to presently treated structures. In addition to the above, one may subsequently apply a low permeability overlay to the concrete structure to further reduce the rate at which any corrosive chloride or other agent can impregnate the structure. Such low permeability overlays are well known and include application of polymer concrete overlay, low-permeability concrete composition overlay or application of a membrane/concrete overlay to the existing and now treated structure. The present process provides a means for readily impregnating a reinforced concrete structure with a corrosion inhibiting agent, for arresting the corrosive effect of the chloride already contained in the concrete structure, for inhibiting future corrosion by subsequently applied corrosive agents (like deicing chloride salts) and to provide a sound reinforced concrete structure for an extended period of time. The present process unexpectedly provides the above benefits without causing detrimental effects to the resultant structure (such as cracking, spalling, poor freeze-thaw performance and the like). The following is given as an illustrative example of the subject process. It is not meant to be a limitation on the invention as defined by the appended claims. All parts and percentages are by weight unless otherwise stated. EXPERIMENTAL TESTINGAn existing bridge specimen which was tested consisted of a three year old typical slab and girder bridge type construction used in highways in the United States. The bridge specimen used for this study was a full-scale composite steel girder-reinforced concrete deck highway bridge simply supported on a 14.6 m (48 ft) span. The overall dimensions of the bridge specimen were 14.6 m (48 ft) long by 6.2 m (20.5 ft). wide carried by three W36 x 150 steel girders located at the center and 1.1 m (3.5 ft) from each edge. Two types of bridge deck construction schemes were used along the length of the bridge. On the northern half of the bridge, the deck consisted of 19 cm (7-1/2-in.)-thick cast-in-place slab with two courses of #4 reinforcing bars at 22.2 cm (8.75 inches) cc in both directions in the center portion and 12.1 cm (4.75 inches) cc in both directions at the portions extending outside the girders to the edge. A 5 cm (2 inch) clear concrete cover was over the upper rebars. The design strength of the concrete was 28 MPa (4000 psi). The southern half of the bridge consisted of six precast, transversely prestressed panels, 10 cm (4 in.) thick, spanning between girders (41 MPa (6000 psi) concrete) upon which is layed a 8.9 cm (3-1/2 in.) topping of 28 MPa (4000 psi) concrete having a single course of No. 4 reinforcing bars at 22.2 cm (8.75 inches) cc in both directions. The overhangs were cast-in-place 28 MPa (4000 psi) concrete. The precast, prestressed panels were made using 41 MPa (6000 psi) concrete. The data collected during testing consisted of temperature readings and deflection measurements. Temperature was measured using thermocouples connected to a digital readout device. Temperature values were recorded for the hot air heating the bridge deck, the ambient temperature and the temperature at various locations in the bridge deck. Using the cast-in-place concrete slab section (northern half) of the bridge as the test specimen, thermocouples were placed middistance between the exterior and interior girders at top surface/mid depth/and bottom surface. The bridge deck was observed for cracks and other deteriorations prior to treatment. All cracks were marked. The test portion was covered by a hood consisting of a light steel frame covered by insulated panels which was easily assembled at the test site. Approximately, a 13 mm (0.5 inch) gap was provided all around the heated area between the hood and the like concrete surface in order to allow the hot air to escape thus preventing excessive build up inside the hood. The hood was also equipped with a portable oil-fired forced fan heater having a 176 kW (600,000 BTU/Hr) capacity. The extended edges of the bridge were wrapped with insulation. The heating was commenced using a hot air temperature profile of 13W/m² (5 BTU/hr.-sq.ft.deg.F) and was continued for about 13 hours and then shut off. The temperature profile during heating was measured and given in three hour intervals in Table I below. HeatingLocation Time 3 hr 6 hr 9 hr 12 hr Hood Air194°C221°C238°C243°C Top Surface127°C149°C155°C155°C Mid-Depth49°C77°C94°C105°C Bottom Surface38°C54°C71°C88°C Ambient35°C32°C29°C32°C The mid-depth and bottom surface continued to rise for approximately 1.5 hours after heating stopped to a maximum temperature of 110°C and 94°C, respectively. The upper surface and hood air temperatures quickly dropped and were monitored to have the upper surface to mid-depth temperature be maintained at a maximum differential of 6°C or less than 0.8°C/cm (2°C/inch) thickness. After 41 hours the hood was completely removed and the slab was examined for cracks. Only a few minute cracks of the order of 0.005 in. wide or less were observed and then only between already existing cracks. These cracks became almost undetectable upon complete cooling. In any case the observed cracks were not of a structural nature and would have no effect on the structural performance and serviceability of the bridge structure. Impregnation of the dried concrete slab with a 15 percent solution of calcium nitrite was conducted by covering the surface with approximately 2.5 to 3.8 cm (1 to 1-1/2 in.) of the solution for approximately twenty four hours. At that time, the excess solution was removed and the concrete surface ponded with water for three days and then removing the water. Upon completion of the posttreatment procedure, cores were taken at different locations on the treated area and on the untreated area for strength testing. Testing of the cores in compression did not reveal any damage to the integrity, strength and load carrying capacity of the concrete as a result of the posttreatment procedure. The strength of the concrete in both the treated and untreated areas of the slab as indicated by the core tests was in range from 32 to 34.5 MPa (4600 to 5000 psi).
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A process of inhibiting corrosion in a concrete structure having an upper surface, a lower surface, and a concrete composition therebetween which has reinforcement metal embedded therein, which process comprises a) heating at least a portion of the concrete structure to at least about 100°C at a predetermined depth of the structure's thickness; b) cooling the concrete structure at a rate to maintain a temperature gradient from the upper surface to the predetermined depth of up to +0.8°C/cm (+2°C per inch); c) applying an aqueous solution of a corrosion inhibiting agent to the upper surface of said structure for a sufficient time to provide a corrosion inhibiting amount of said agent to said structure; and d) applying an aqueous wash to the upper surface of the structure to remove the agent from the upper surface region of the structure. A process according to claim 1 wherein the temperature gradient during step (b) is initially a negative gradient (upper surface hotter than predetermined depth) and subsequently a positive gradient, and the cooling is continued at least until the upper surface reaches ambient temperature. A process according to claim 1 or 2 wherein the structure's exposed surfaces adjacent to the treated portion are insulated. A process according to claim 1, 2 or 3 wherein the predetermined depth is directly above the level of the reinforcement metal. A process according to any one of the preceding claims wherein the predetermined depth is from 0.25 to 0.5 of the structure's total thickness from the upper surface. A process according to any one of the preceding claims wherein the corrosion inhibiting agent comprises calcium nitrite. A process according to any one of the preceding claims wherein the structure is heated at a rate of up to about 110 W/m²°C (20 BTU/hr.-sq.ft.-deg.F.); the exposed peripheral surfaces surrounding the treated structure are insulated; the corrosion inhibiting agent solution's temperature is substantially equal to the upper surface temperature; and the aqueous wash is applied to the upper surface. A process according to any one of the preceding claims wherein the corrosion inhibiting solution is an aqueous solution comprising from 5 to 20 wt. percent calcium nitrite. A process according to claim 8 wherein the dosage of calcium nitrite applied to the structure is from 0.5% s/s to 5% s/s, where s/s is the solids of agent per unit solid of cement. A process according to any one of the preceding claims wherein the aqueous wash is applied and causes the corrosion inhibiting agent to move to the interior thickness of the structure.
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GRACE W R & CO; W.R. GRACE & CO.-CONN.
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COGLIANO JOSEPH ALBERT; ROSENBERG ARNOLD MORRY; COGLIANO, JOSEPH ALBERT; ROSENBERG, ARNOLD MORRY
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EP-0489573-B1
| 489,573 |
EP
|
B1
|
EN
| 19,950,920 | 1,992 | 20,100,220 |
new
|
B01D61
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B01D69, C10G31, C10G73, C10G21
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C10G31, B01D61, B01D69, C10G73
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C10G 31/11, B01D 69/12D, B01D 61/02
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Separation of hydrocarbon dewaxing and deasphalting solvents from dewaxed and/ or deasphalted oil using interfacially polymerized membrane
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Hydrocarbon solvents used for the dewaxing and/or deasphalting of oils can be recovered by the selective permeation of said solvents through an interfacially polymerized membrane under reverse osmosis conditions.
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Description of the InventionHydrocarbon solvents used for dewaxing and/or deasphalting oils can be recovered by the selective permeation of the solvent through an interfacially polymerized membrane under reverse osmosis conditions. The hydrocarbon solvents which can be received are the C₃ to C₆ aliphatic alkanes and alkenes, i.e., propane, propylene, butane, butene, hexane, hexene, heptane, heptene and mixtures thereof, preferably the C₃-C₄ alkanes and alkenes and mixtures thereof, most preferably propane, butane and mixtures thereof. These solvents are employed for the dewaxing and/or deasphalting of hydrocarbon oils, e.g., lubes and specialty oils, transformer oils, refrigerator oils, turbine oils, as well as the dewaxing of fuels fraction such as diesel, and jet. The hydrocarbon oils can come from any natural or synthetic source. Mineral oil distillates or hydrocracked oils ranging from light fuels fractions to Bright Stocks are dewaxed and/or deasphalted by the techniques known in the art. Similarly oils obtained by the isomerization of natural slack waxes or Fischer-Tropsch waxes as well as oils obtained from tar sands, coal liquification, and shale can be subjected to treatment as needed. The C₃ to C₆ hydrocarbon solvents are recovered for use by the selective permeation of the solvent through an interfacially polymerized membrane. The membranes are prepared by depositing an aqueous (or conversely non-aqueous) solution of a first reactant component on the microporous backing support layer, draining off the excess quantity of this first solution and then applying a second reactant component in the form of a non-aqueous (or conversely aqueous) solution. The two components interact and polymerize at the interface between the aqueous phase and the non-aqueous phase to produce a highly crosslinked thin polymer layer on the microporous ultrafiltration support backing layer. In this invention the membranes are generally prepared by reacting multi-functional amino compounds dissolved in water with a second polyfunctional agent dissolved in organic solvents. The amino compounds can be aliphatic, alicyclic or aromatic. The polyfunctional agents with which the amines are reacted can include di- and tri- acid halides, acid anhydrides, aliphatic and aromatic diisocyanates, thioisocyanates, haloformates and sulfonyl halides. Backings which can be used include nylon (e.g., nylon 66), cellulose, polyester, teflon, polypropylene and other insoluble polymers. Background of the InventionThe separation and recovery of C₃-C₆ hydrocarbon dewaxing and/or deasphalting solvents from dewaxed and/or deasphalted oils is an important process consideration. It is uneconomical to simply discard the solvents after one use and similarly, in most applications their continued presence in the product oil can give rise to product quality concerns. Such solvents have been recovered by simple distillation as well as by the simple expedient of permitting the normally gaseous solvents such as propane and butane merely vaporize. Such processes are not efficient requiring the expenditure of considerable energy to affect the distillates and, in the case of propane and butane, the recompression of the solvents before reuse is possible. The recovery of such solvents by more energy efficient means has been explored. The use of membranes to effect the separation has generated much interest. See U.S. Patent 4,595,507 and U.S. Patent 4,617,126. Interfacially polymerized membranes were initially discovered in the 1970's for use in water desalination (see In situ-formed Condensation Polymers for Reverse Osmosis Membranes: Second Phase , North Star Research Institute, prepared for Department of the Interior, July 1974, available from NTIS, report #PB-234 198; Continued Evaluation of In Situ-formed Condensation Polymers for Reverse Osmosis Membranes , Midwest Research Institute, prepared for Office of Water Research and Technology, April 1976, available from NTIS, report #PB-253 193; Interfacially Synthesized Reverse Osmosis Membrane , U.S. Patent 4,277,344, July 7, 1981, assn. to Film Tec Corporation). Prior art only describes the use of these membranes for the separation of aqueous solutions by reverse osmosis. Interfacially polymerized membranes are composed of a highly crosslinked and generally insoluble condensation polymer which is formed in situ on a micro-porous film. Most of these membranes are formed with di- or polyamines which are reacted with multi-functional iso-cyanates or acid chlorides. Amines react very readily with both of these reactants. Several of these membranes have been commercialized for water desalination purposes by companies such as UOP, Film Tec and Desalination Systems Inc. All of the commercial membranes use a polysulfone ultrafiltration membrane (0.02 to 0.1 micron pore size) for the microporous support film. Prior art does describe the use of some other microporous support films such as polyvinylchloride ultrafiltration membranes. These membranes are formed by using the following procedures. A thin layer of a dilute solution of one component, usually an aqueous solution of the amine, is put on one side of the microporous support film. A thin layer of a dilute solution of the second component, usually in a water immersible solvent, is then put on top of the water solution layer. The order of applying the solutions can be reversed. The two components react at the water/solvent interface forming a thin (less than 1 micron thick) highly crosslinked polymer layer. This polymer layer is the active layer of the membrane at which separation occurs. Some examples of formulations mentioned in the prior art are reacting polyethylenimine with toluene diisocyanate, reacting polyethylenimine with isophthaloyl dichloride and reacting m-phenylene diamine with trimesoyl chloride. These membranes exhibit high salt rejections from water (>95%). EP-A-0 013 834 describes the sequential permeation under different pressures of a hydrophilic, water-containing regenerated cellulose membrane with solvents of decreasing polarity. A typical preconditioning sequence is: water-methanol-MEK-pentane-propane. The said membrane is selectively permeable to a dewaxing solvent of a mixture comprising dewaxed oil and dewaxing solvent. EP-A-0 427 452 of earlier priority date (cited under Article 54(3)EPC) describes a process for separating ketonic and aromatic dewaxing solvents from dewaxed oil using a membrane including a polyimine layer which has been cross-linked on a porous support layer with a cross-linking agent, e.g. polyisocyanate. EP-A-0 421 676 of earlier priority date (cited under Article 54(3)EPC) similarly describes a process for separating ketonic and aromatic dewaxing solvents from dewaxed oil using an interfacially polymerised membrane e.g. of polyimine prepared on a support layer from a multifunctional amino reactant and a polyfunctional agent reactant, e.g. a diisocyanate. The present invention provides a method for separating hydrocarbon solvents selected from C₃ to C₆ aliphatic alkanes and alkenes and mixtures thereof used for dewaxing and/or deasphalting oils from said dewaxed and/or deasphalted oil by contacting the dewaxed and/or deasphalted oil containing said hydrocarbon solvent with a membrane under reverse-osmosis conditions, whereby said solvent is selectively permeated through the membrane, characterised in that the said membrane is an interfacially-polymerized cross-linked membrane on a microporous ultrafiltration support backing, said interfacially-polymerized membrane comprising the reaction product of a multi-functional amino compound dissolved in water with a polyfunctional amine-reactive agent dissolved in an organic solvent. In the method of the invention, the interfacially polymerized membranes are prepared by reacting multi-functional amino reactants dissolved in water with polyfunctional amine-reactive agent reactants dissolved in organic solvents. The interfacially polymerized membrane is produced on a non-selective, microporous ultrafiltration support layer which is inert in the organic media to which it will be exposed. This support layer is selected from nylon, cellulose, polyester, teflon (polytetrafluoroethylene), polypropylene, polyethylene terephthalate, ultrafiltration membranes having pores in the range 0.02 to 0.1 microns. A few examples of multi-functional amino group reactants include polyethylenimine, polyvinylamine, polyvinylanilines, polybenzylamines, polyvinylimidazolines, amine modified polyepihalohydrins, and other amine containing polymers, m-phenylene diamine, p-phenylene diamine, triaminobenzene, piperazine, piperidine, 2,4-bis (p-aminobenzyl) aniline, cyclohexane diamine, cycloheptane diamine, and mixtures thereof. The polyfunctional agents that the amines are reacted with can include di- and tri- acid halides, (e.g., chlorides), polyfunctional acid anhydrides, aliphatic and aromatic diisocyanates, polyfunctional thioisocyanates, haloformates (e.g., chloroformates) and sulfonyl halides (e.g., sulfonyl chlorides), and mixtures thereof. A few examples of these agents are trimesoyl chloride, cyclohexane-1,3,5 tricarbonyl chloride, isophthaloyl chloride, terephthaloyl chloride, diisocyanatohexane, cyanuric chloride, diphenylether disulfonyl chloride, oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, fumaryl chloride, glutaconyl chloride, phthalic anhydride, ethylene diisocyanate, propylene diisocyanate, benzene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, methylene bis (4-phenylisocyanate), ethylene thioisocyanate, toluene thioisocyanate, naphthalene thioisocyanate, ethylene bischloroformate, propylene bischloroformate, butylene bischloroformate, 1,3-benzenedisulfonyl chloride, 1,4 benzene disulfonyl chloride, 1,3-naphthalene disulfonyl chloride and 1,4-naphthalenedisulfonyl chloride, and mixtures thereof. A crosslinked membrane is used in the present invention to ensure stability. A crosslinked polymeric film is formed if these membranes are prepared with one of the reactants being at least trifunctional. The degree of crosslinking is primarily controlled by the concentration of the reactant solution with higher concentrations leading to higher degrees of cross-linking. In general the interfacially polymerized membranes are produced using 0.1 to 10 wt% aqueous solutions of the amines, preferably 0.25 to 5 wt% aqueous solutions of the amines; and 0.1 to 5 wt% non-aqueous solutions of the poly-functional agents, preferably 0.15 to 0.5 wt% non-aqueous solution of the poly-functional agent. Following the sequential deposition of the two solutions, the resulting film can be heated to promote crosslinking of any unreacted amine. This post heating step can be at a temperature of about 60 to 150°C, preferably 80 to 120°C for from 1 to 20 minutes. The concentrations of components used and drying/cross-linking times and temperatures will be selected from the above ranges by the practitioner in response to the membrane casting procedures actually employed and the casting machines or other mechanisms or equipment used. The C₃-C₆ and mixtures thereof hydrocarbon dewaxing and/or deasphalting solvents are selectively permeated through the interfacially polymerized membranes under reverse osmosis conditions. Reverse osmosis conditions include contacting the then, interfacially polymerized crosslinked face of the membrane with the raffinate phase, extract phase, or both, preferably extract phase at a temperature between about -24 to 200°C, preferably 40 to 150°C and under an applied pressure sufficient to overcome the osmotic pressure. Pressures on the order of 0 to 6.90 MPa (0 to 1000 psig) can be used, preferably about 2.76 to 4.14 MPa (400 to 600 psig). The separation process could employ the interfacially polymerized membrane in the form of a spiral wound element. Fabrication of a spiral wound element would employ adhesives as disclosed in U.S. Patents 4,464,494 and 4,582,726. Examples Two interfacially polymerized membranes were prepared designated Membrane A and Membrane B. The membranes were prepared as follows: Membrane A:·Dissolve 4.00 grams of phenylene diamine (PDA) from Aldrich in 100 grams of deionized water. ·Dissolve 0.15 grams of trimesoyl chloride (TMC) from Aldrich in 100 grams of hexane. ·Install a disc of the 0.04 µm Ultipor nylon 66 membrane in a wash coat cell, leave one side of the membrane exposed. ·Pour the PDA solution over the exposed side of the membrane. ·Drain off excess solution for one minute. ·Pour the TMC solution over the exposed side. ·Drain off the excess solution for one minute. ·Bake the nylon membrane in an oven at 110°C for 10 minutes. Membrane BDissolve 0.50 grams of PEI in 100 grams of deionized water. Dissolve 0.50 grams of TDI in 100 grams of toluene. Install a disc of the 0.04 µm Ultipor nylon 66 membrane in a wash coat cell, leave one side of the membrane exposed. Pour the PEI solution over the exposed side of the membrane. Drain off excess solution for one minute. Pour the TDI solution over the exposed side. Drain off the excess solution for one minute. Bake the nylon membrane in an oven at 110°C for 10 minutes. PEI= polyethylenimine (Aldrich #18, 197-8R) TDI= toluene diisocyanate (BASF) These membranes were evaluated for the separation of propane from a deasphalted oil. The oil was a Singapore 2500 Neutral deasphalted oil. The feeds used to evaluate Membrane A and B ranged from 8-19.6 wt% oil. The results are presented below. Membrane A B B Temperature °C:606060 Feed Pressure, psi (MPa)950 (6.55)450 (3.10)600 (4.14) Permeate Pressure, psi (MPa)350 (2.41)350 (2.41)350 (2.41) Feed Oil Concentration, wt%81319.6 Performance Flux, L/M²-Day510,00020,950130,500 Oil Rejection, %297365
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A method for separating hydrocarbon solvents selected from C₃ to C₆ aliphatic alkanes and alkenes and mixtures thereof used for dewaxing and/or deasphalting oils from said dewaxed and/or deasphalted oil by contacting the dewaxed and/or deasphalted oil containing said hydrocarbon solvent with a membrane under reverse-osmosis conditions, whereby said solvent is selectively permeated through the membrane, characterised in that the said membrane is an interfacially-polymerized cross-linked membrane on a microporous ultrafiltration support backing, said interfacially-polymerized membrane comprising the reaction product of a multi-functional amino compound dissolved in water with a polyfunctional amine-reactive agent dissolved in an organic solvent. The method of claim 1 wherein the multifunctional amino group reactant is selected from polyethylenimine, polyvinylamine, polyvinylaniline, polybenzylamine, polyvinylimidazolines, amine modified polyepihalohydrines, m-phenylenediamine, p-phenylenediamine, triaminobenzene, piperazine, piperidine, 2,4-bis-(p-aminobenzyl) aniline, cyclohexane diamine, cycloheptane diamine and mixtures thereof. The method of claim 1 or claim 2 wherein the polyfunctional amine-reactive agent is selected from di- and tri- acid halides, polyfunctional acid anhydrides, aliphatic diisocyanates, aromatic diisocyanates, polyfunctional thioisocyanates, haloformates, and sulfonylhalides and mixtures thereof. The method of any one of claims 1 to 3 wherein the multifunctional amine compound in water is at a concentration of 0.1 to 10 wt.%. The method of any one of claims 1 to 4 wherein the polyfunctional agent reactant in organic solvent is at a concentration of 0.1 to 5 wt.%. The method of any one of claims 1 to 5 wherein the backing is selected from nylon, cellulose, polyester, polytetrafluoroethylene, polypropylene, polyethylene, polyethylene terephthalate ultrafiltration membranes. The method of claim 6 wherein the ultrafiltration membrane support layer has pores in the range 0.02 to 0.1 microns (0.02 to 0.1 µm). The method of any preceding claim wherein the hydrocarbon dewaxing and/or deasphalting solvent is selected from propane, propylene, butane, butene, hexane, hexene and mixtures thereof.
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EXXON RESEARCH ENGINEERING CO; EXXON RESEARCH AND ENGINEERING COMPANY
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CHEN TAN-JEN; CHEN, TAN-JEN
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EP-0489574-B1
| 489,574 |
EP
|
B1
|
EN
| 19,960,124 | 1,992 | 20,100,220 |
new
|
C08F6
| null |
C08F6
|
C08F 6/04
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A process for the supercritical mixed-solvent separation of polymer mixtures
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A supercritical separation process is proposed for polymers, utilizing mixed solvents. Such a process can be used to remove light end, or heavy end, or generate bulk fractions of low polydispersity. Three modes of operation are proposed: increasing solvent capacity, decreasing solvent capacity, and single-vessel multistage separation.
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Polymerization reactions usually lead to products of varying polydispersity, which means that such polymeric products contain a range of components, from low to high molecular weight. The quality of a final polymeric product (polymer for short) to a large extent depends on how broad its molecular weight distribution is. Usually, the broader the distribution, the lower the value. Hence, a common challenge in polymer manufacturing is to make the molecular weight distribution as narrow as possible. Since controlling the polymerization reaction conditions has only a limited effect on the molecular weight distribution, a separation process called fractionation is needed to narrow down the polymer weight distribution by separating either the light and/or heavy fractions from the bulk product, downstream of the polymerization reactor. The fractionation approaches disclosed in the prior art (see U.S. 3,969,196; U.S. 3,294,772; U.S. 2,457,238; Krukonis, V. POLYMER NEWS, 11, 7-16, 1985; McHugh, M.A. and Krukonis, V.J. SUPERCRITICAL FLUID EXTRACTION: Principles and Practice, Butterworths, 1986, pages 143-180; Kumar, S.K. et al. FLUID PHASE EQUILIBRIA, 29, 373-382, 1986; Kumar, S.K. et al. MACROMOLECULES, 20, 2550-2557, 1987; McHugh, M.A. and Krukonis, V.J. in Encycl. Polym. Sci. Eng. 16, 368-399, 1989) are based on a general concept of using supercritical fluids as solvents. According to the present invention there is provided a process for fractionating a polydisperse polymer by molecular weight, comprising contacting said polymer with a solvent having at least one antisolvent component and at least one cosolvent component, said components being chosen according to their selectivity and capacity for the polymer fractions at a given fractionation temperature and pressure, said process being operated at a temperature at which at least one of said components is above its critical temperature. In the present invention, the solvent is a supercritical fluid containing at least two components, antisolvent and cosolvent. The key advantage of this invention is a higher degree of flexibility in selecting separation conditions and, hence, a better extraction efficiency. The solvent is a homogeneous solution before adding the polymer. Adding the polymer to the solvent converts the solvent solution to a two-phase mixture. One of the phases is polymer rich in polymer fraction of relatively high molecular weight (heavies). The other phase is both rich in solvent and polymer fractions of relatively low molecular weight (lights). That is, the solvent extracts the lights and rejects the heavies. After a period of time the heavies and lights each coalesce separately so that phases disengage. The polymer is separated from each phase by conventional means. The temperature range is from 10 to 300°C, and the pressure range is from a few tens (e.g. 20) to a few thousand bar (for example up to 3000 bar, but is typically up to a few hundred bar, e.g. 500) . Specific choices will depend on the polymer to be separated and solvent components. The advantage of this process is the flexibility in selecting the operating conditions; not only temperature and pressure but also the solvent composition. The present invention uses a mixed extraction solvent where at least one component has relatively low capacity (antisolvent) and at least one component has relatively high capacity (cosolvent). This way, in addition to pressure and temperature, the solvent composition can be used to control overall capacities, selectivities and yields. Hence, the present invention has the advantage of enhanced flexibility of fine tuning the operating variables to focus the separation on either the light end, or the heavy end, or the bulk fractions. In the present invention, the following definitions are used. The solvent capacity is the amount of polymer which can be dissolved in solvent. The capacity is to be high during the extraction step because the higher the capacity the less solvent is needed to extract a given amount of polymer. However, the capacity should be low during the solvent recovery step. The solvent selectivity on the other hand is a measure of how sharp the separation is, and it varies from 1 (no separation) to infinity (perfect separation). For example, if two components are to be separated, the selectivity equal to 1 suggests that the solvent extract has exactly the same composition as the initial feed; the selectivity equal to a very high number suggests that the solvent extract contains only one component and rejects completely the other component. In practice, a selectivity of two to ten may be quite acceptable, a selectivity higher than ten is considered to be very good. In summary, for the extraction step, high capacity coupled with high selectivity is desired. It is desirable to be able to vary and control capacity and selectivity, for example, to fine tune the separation, to generate reflux, or to recover the extract from solvent by drastically reducing its capacity. In this invention, this can be accomplished by varying the solvent composition because the antisolvent is a low-capacity component while the cosolvent is a high-capacity component. Examples of antisolvents of the present invention include: Carbon dioxide, C₁-C₃ alkanes and alkenes, nitrous oxide, sulfur hexafluoride, noble gases (xenon, etc.), halogenated hydrocarbons. Examples of co-solvents of the present invention include: C₃+ alkanes, alkenes, cyclics, alcohols, carboxylic acids, esters, ketones, amines, tetrahydrofurane, halogenated hydrocarbons (e.g., carbon tetrachloride, chloroform), formamide, dimethylformamide. Solvent selection will depend on a temperature region required for a specific polymer. For example, typically, polymers will be fractionated above their glass-transition temperatures but below their thermal-decomposition temperatures. The solvent (mixture of antisolvent and cosolvent) should be selected in such a way that the fractionation temperature be supercritical or near-critical with respect to its critical temperature. This implies that the critical temperatures of mixed solvent candidates must be known approximately. For example, they can be estimated from the critical temperatures of the pure solvent components. The reason that the solvent should be supercritical or near-critical is that its supercritical and near-critical capacities (from zero to high) and selectivities (from one to high) can be easily varied over broad ranges, and hence allow for a great degree of flexibility. This is in contrast to subcritical capacities and selectivities. A preliminary group of possible solvent candidates, selected based on their critical temperatures and pressures, can be further narrowed down on the basis of their specific capacity/selectivity characteristics, which have to be either measured (conventional techniques) or estimated from established thermodynamic models. Polymers means mixtures containing compounds having similar chemical composition and structure but differing in molecular weight. Since molecular weight can continuously vary within a characteristic range for specific polymers, we say that polymers are POLYDISPERSE. For the present invention, a polymer is defined as a polydisperse mixture with molecular weight in the range between around 200 to a few hundred thousand gram/mole. In the preferred embodiment, the present invention includes polymers, solid or liquid, composed of free molecules, that is molecules that are not covalently bonded to each other, and hence free to be solubilized. The criteria will be solubilities in solvents (defined earlier): if the polymer molecules are free to move into the solvent phase, such a polymer is included in the present invention. Specific examples of polymer classes suitable for the present invention include polyolefins, polydienes, polystyrenes, and random alternating, block and graft copolymers thereof, and mixtures thereof. Example 1 presents polymeric feed and extract compositions in terms of six arbitrarily chosen pseudo-components having different average molecular weights. This is given for the feed and the extract. The focus of the separation in this case is on removing the light end components (500, 1k, and 2k components having an average MW of approximately 1.6k, in contrast to 18.5k for the bulk polymer). This example shows that the extract, obtained with the yield of 1.3 wt%, is rich in components 500, 1k, 2k, and contains a little of 3k but practically no 8k and 20k. This means that the main result of such a separation process is removal (extraction) of the very light components from the heavy bulk components. Example 1. Example of Polymer Feed and Extract Compositions in Weight Fractions on a Solvent-Free Basis.Feed Extract (1.3 wt%) 500.0007.0380 1k.0093.4240 2k.02.4093 3k.02.1274 8k.05.0003 20k.90.0000 (MW)W18.5k1.6k Predicted at 200°C, 200 bar, 15 wt% polymer, 15 wt% C₂, 70 wt% C₆ polymer = polyolefin C₂ = ethylene (antisolvent) C₆ = 1-hexene (cosolvent) 500 = pseudocomponent having molecular weight of 500 1k = pseudocomponent having molecular weight of 1,000 Similarly, 2k = 2000 ; etc. Extract yield = 1.3 wt% (MW)w = weight average molecular weight In the next three examples, we will discuss the effects of antisolvent, pressure, and temperature on the solvent capacity and selectivity. In these examples, ethylene is antisolvent and hexene is cosolvent. Example 2 illustrates the antisolvent effect. For five different antisolvent concentrations (C₂ Wt% of 10, 15, 20, 30, 85), this example gives the distribution coefficients (K's, the ratios of weight percent in the extract phase to the raffinate phase), capacity, yield, and selectivities along the 2k/3k and 3k/8k lines. We focus on changes in capacity and selectivities; we observe that capacity decreases but selectivities,increase upon increasing the antisolvent concentration. This will allow for a considerable degree of flexibility to control the separation (capacity and selectivity) by varying the antisolvent concentration. It is this effect that provides basis for the present invention. Example 2. Example of Antisolvent Effect On Separation: Solvent Capacity, Selectivity, and Extract YieldC₂ Wt% 10 15 20 30 85 K(500).827.791.732.545.16E-1 K(1K).449.395.323.158.58E-4 K(2k).132.987E-1.627E-1.134E-1.79E-9 K(3k).388E-1.246E-1.122E-1.113E-2.1E-13 K(8k).855E-4.238E-4.338E-5.483E-8.5E-38 K(20k).36E-10.14E-11.98E-14.63E-21<.1E-50 Capacity Wt%.29.25.20.10<.1E-4 Yield Wt%1.51.31.0.5<.1E-2 2k/3k Selectivity3.44.05.111.9 .8E+5 3k/8k Selectivity4541034 3609 .2E+6 .2+25 Capacity decreases, selectivity increases with increasing C₂ Wt% Predicted at 200°C, 200 bar, 15 wt% polymer, 85 wt% C₂+C₆ Polymer = feed in Example 1 C₂ = ethylene (antisolvent) C₆ = 1-hexene (cosolvent) K(500) = weight distribution coefficient of pseudocomponent having molecular weight of 500 K(1k) = weight distribution coefficient of pseudocomponent having molecular weight of 1k = 1000, Similarly, K(2k) is mol. wt. 2,000 ; etc. Distribution coefficient = wt% in light phase / wt% in heavy phase Capacity - solubility of polymer in light phase Yield - yield of the extracted polymer 2k/3k Selectivity = K(2k)/K(3k), 'relative volatility' of 2k/3k 3k/8k Selectivity = K(3k)/K(8k), 'relative volatility' of 2k/3k Example 3 illustrates the pressure effect. For five different pressures (100, 200, 250, 300 bar), this example gives the distribution coefficients (K's, the ratios of weight percent in the extract phase to the raffinate phase), capacity, yield, and selectivities along the 2k/3k and 3k/8k lines. We focus on changes in capacity and selectivities; we observe that capacity increases but selectivities decrease upon increasing pressure. This example shows an additional degree of flexibility to control the separation (capacity and selectivity) by varying the process pressure. Example 3. Example of Pressure EffectPressure Bar 100 200 250 300 K(500).514.791.836.861 K(1k).134.395.465.511 K(2k).904E-2.987E-1.144.180 K(3k).612E-3.246E-1.445E-1.636E-1 K(8k).871E-9.238E-4.126E-3.347E-3 K(20k).81E-23.14E-11.97E-10.128E-8 Capacity Wt%.085.25.30.34 Yield Wt%0.51.31.61.8 2k/3k Selectivity154.03.22.8 3k/8k Selectivity.7E+61033353183 Capacity increases , selectivity decreases with increasing C₂ Wt% Predicted at 200°C, 15 wt% polymer, 15 wt% C₂, 70 wt% C₆ Polymer = feed in Example 1 C₂ = ethylene (antisolvent) C₆ = 1-hexene (cosolvent) K(500) = weight distribution coefficient of pseudocomponent having molecular weight of 500 K(1k) = weight distribution coefficient of pseudocomponent having molecular weight of 1k = 1000, Similarly, K (2k) is mol. wt. 2,000 ; etc. Distribution coefficient = wt% in light phase / wt% in heavy phase Capacity = solubility of polymer in light phase Yield = yield of the extracted polymer 2k/3k Selectivity = K(2k)/K(3k), 'relative volatility' of 2k/3k 3k/8k Selectivity = K(3k)/K(8k), 'relative volatility' of 2k/3k Example 4 illustrates the temperature effect. For two different temperatures (200°C and 220°C), at two different pressures, this example gives the distribution coefficients (K's, the ratios of weight percent in the extract phase to the raffinate phase), capacity, yield, and selectivities along the 2k/3k and 3k/8k lines. We focus on changes in capacity and selectivities; we observe that capacity decreases but selectivities increase upon increasing temperature at low pressures (100 and 200 bar). However, the opposite is true at higher pressures (250 and 300 bar); capacity increases but selectivities decrease upon increasing temperature. This example shows that the temperature effect is the most difficult to predict, and will depend on the pressure range for a specific antisolvent/cosolvent pair. Example 4. Example of Temperature EffectPressure Bar 100 200 250 300 Temperature °C 200 220 200 220 K(500).514.471.791.834 K(1k).134.104.395.431 K(2k).904E-2.503E-2.987E-1.115 K(3k).612E-3.244E-3.246E-1.308E-1 K(8k).871E-9.65E-10.238E-4.422E-4 K(20k).81E-23.11E-25.14E-11.56E-11 Capacity Wt%.085.069.25.27 Yield Wt%0.5.371.31.4 2k/3k Selectivity15214.03.7 3k/8k Selectivity.7E+6.4E+71033730 Capacity increases with decreasing temperature at low pressures Capacity decreases with decreasing temperature at high pressures Predicted for 15 wt% polymer, 15 wt% C₂, 70 wt% C₆ Polymer = feed in Example 1 C₂ = ethylene (antisolvent) C₆ = 1-hexene (cosolvent) K(500) = weight distribution coefficient of pseudocomponent having molecular weight of 500 K(1k) = weight distribution coefficient of pseudocomponent having molecular weight of 1k = 1000, Similarly, K (2k) is mol. wt. 2,000 ; etc. Distribution coefficient = wt% in light phase / wt% in heavy phase Capacity = solubility of polymer in light phase Yield = yield of the extracted polymer 2k/3k Selectivity = K(2k)/K(3k), 'relative volatility' of 2k/3k 3k/8k Selectivity = K(3k)/K(8k), 'relative volatility' of 2k/3k All these examples are related to a fractionation where the light extract phase is light-end-rich while the heavy phase is bulk-polymer-rich. The invention will be further illustrated with reference to the accompanying drawings, in which : Figure 1 shows a separation of increasing capacity mode, to remove the light-end fractions from the bulk polymer. Figure 2 shows a multiple-vessel separation of decreasing capacity mode, to remove the heavy-end fractions from the bulk polymer. Figure 3 shows a single-vessel multistage separation, to fractionate the bulk polymer in a continuous process. In the embodiment of the present invention shown in Figure 1, the objective is to remove light-end fractions of progressively increasing molecular weight. In this application, a batch of polymer is treated with a solvent of a gradually increasing capacity. This can be accomplished, for example, by gradually increasing pressure, increasing/decreasing temperature, or gradually increasing the cosolvent-to-antisolvent ratio. An alternative application, utilizing a decreasing capacity mode, is illustrated with an example shown in Figure 2. Upstream of the separator I, the polymer is mixed with the solvent to form one phase. Next, the solvent capacity is gradually decreased to precipitate fractions of progressively decreasing molecular weight in the successive stages. This can be accomplished, for example, by gradually decreasing pressure, decreasing/increasing temperature, or gradually decreasing the cosolvent-to-antisolvent ratio. This ratio can be varied either within the main solvent stream or, better, by adding the antisolvent at the top of the vessel (e.g., column) to generate reflux. For a single-stage separator, the objective will be to remove the very heavy end from the bulk polymer. For a multistage separation, the light phase in the last stage will become light-end-rich. Usually, this mode of operation requires complete, or almost complete, solubility of the bulk polymer at the maximum capacity conditions upstream of separator I. Finally, a single-vessel multistage separation is proposed and illustrated with an example in Figure 3. Here, a desirable concentration gradient along the column is created by a reflux forming device at the top of the column (although reflux can also be formed outside of the column and recycled). Such a device will reduce the solvent capacity by either local addition of antisolvent or local temperature swing (usually decrease). In this example, Figure 3, both solvent and polymer feed flow continuously through the column. The overhead product stream is rich in lights whereas the bottoms product stream is rich in heavies. In all the application examples solvent can be recovered by conventional means, which usually involve a step reduction of its capacity, for example a combination of temperature and pressure swing that will result in polymer precipitation (phase separation from the solvent), and recycled. Such a recovery of a light component from a heavy component is a conventional chemical engineering operation. The present invention can have numerous process applications. For example, high-pressure manufactured polyolefins can be fractionated with the mixed solvents composed of monomers and co-monomers. Also, specialty polymeric materials, where low polydispersity is required, can be made this way. Selection of specific solvent components is dependent on their critical points, selectivity and capacity. The present invention is uniquely suited for fractionating high-molecular weight mixtures, such as, polymers. Compared to molecular distillation, temperatures are quite low and hence thermally sensitive materials can be treated. Compared to liquid solvent fractionation, solvent recovery is more efficient, residual solvent levels are much lower, selectivities with respect to MW are much higher, but selectivities with respect to chemical functionalities can be lower (this can be refined with specifically interacting solvent modifiers). Compared to liquid chromatography, continuous operation and scale-up are possible and operating costs are expected to be much lower.
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A process for fractionating a polydisperse polymer by molecular weight comprising contacting said polymer with a solvent having at least one antisolvent component and at least one cosolvent component, said components being chosen according to their selectivity and capacity for the polymer fractions at a given fractionation temperature and pressure, said process being operated at a temperature at which at least one of said components is above its critical temperature. The process of claim 1 wherein said temperature is from 10 to 300°C. The process of claim 1 or claim 2 wherein said pressure is from 20 to 3000 bar (2000 to 300,000 kPa). The process of any one of claims 1 to 3 wherein said polymer has a backbone or main-chain acyclic carbon polymer. The process of claim 4 wherein said main-chain or backbone acyclic carbon polymer is selected from the group consisting of polyolefins, polydienes, poly(styrenes), and random alternating, block and graft copolymers thereof, and mixtures thereof. The process of any one of claims 1 to 5 wherein said antisolvent is selected from the group consisting of carbon dioxide, C₁-C₃ alkanes and alkenes, nitrous oxide, sulfur hexafluoride, noble gases and halogenated hydrocarbons. The process of any one of claims 1 to 6 wherein said cosolvent is selected from the group consisting of C₃+ alkanes, alkenes, cyclics, alcohols, carboxylic acids, amines, esters, ketones, tetrahydrofurans, halogenated hydrocarbons, formamide, and dimethylformamide.
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EXXON RESEARCH ENGINEERING CO; EXXON RESEARCH AND ENGINEERING COMPANY
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RADOSZ MACIEJ; RADOSZ, MACIEJ
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EP-0489576-B1
| 489,576 |
EP
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B1
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EN
| 19,990,331 | 1,992 | 20,100,220 |
new
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G06F3
| null |
H04N5, G06Q10, G11B27, G06F3, G06T11, G06T13, G09G5
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S11B27:36, G06Q 10/00F, G11B 27/34, G06F 3/048A1, H04N 5/222, S11B27:031, G06F 3/048A1E, G11B 27/034
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Computer controlled display apparatus
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Apparatus and methods are described to provide a multi-dimensional user interface for use in audio visual production. A display system including a central processing unit (CPU) (22) is coupled through appropriate input/output (I/O) circuitry (32) to input devices, such as a keyboard (38), a digital pad (36) and/or a track ball (40) as well as a display device (50). The CPU is further coupled to a hard disk drive (30) for the storage of programs and data, and is also coupled to a network through which the CPU may communicate with a variety of system resource devices such as editors, music synthesizers (55), graphics generators, scheduling resources, audio enhancement resources, etc. A user viewing the interface on the display may utilize one of the input devices, such as by way of example, the keyboard, to select, incorporate or otherwise integrate the various system resources to develop a unified multi-media production. The user interface includes a control frame (150) which in practice substantially fills all of the display screen of the display and is consistent for all user applications. The control frame is comprised of control panels (152, 190, 170) which surround a variety of subwindows (200, 215) and acts as a consistent control area for all users of the interface. Once defined, elements may be selectively placed on an event horizon bar (220) in the control frame. The placement of an element on the event horizon results in the display of timing data for the element, relative to other elements on the event horizon.
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This invention relates to displaying, manipulating, and selecting multi-media or computer stored information in a window environment of a computer display system. More particularly, this invention relates to an improved user interface to provide a unified operator interface for a wide range of systems which must be coordinated and monitored in a multi-media production system.Videotape editing environments have evolved from providing simple editing cuts to the incorporation of full featured graphics, film to tape and other processes to complete a video production. Consequently, computer controlled editing systems and integration methods have been used to incorporate and integrate various production media resources such as special effects, music, graphics or the like. However, due to the nature of film and video production, a variety of resources must be integrated, scheduled and coordinated with one another to obtain a completed product.Historically, humans have interfaced with computers through a system of discrete commands which typically comprise a combination of both text and mathematical symbolic characters. Examples of such systems are numerous and include the programming languages of Fortran, Algol, Basic, etc., which transform a given set of user commands into machine executable object code. However, the ease with which a user becomes proficient in programming or interacting with a computer-based system is generally a function of how close the system models the logical thought of the user himself. If the user is able to enter commands in the order in which he would find most logically appropriate, rather than having to transpose his desired command into the code of a programming language, greater user efficiency in using the system is achieved.A number of systems which have been developed to reduce the learning or acclimatization period which a user must go through to become proficient in the interaction with the computer system are referred to as object oriented systems . A common object oriented interface approach utilizes multiple windows displayed on a cathode ray tube (CRT) in which combinations of text and graphics are used to convey information. Each window may take the form of an object such as a file folder, different operating environment, pages or layered bit maps to provide a separate display of video information in independent screen regions. (See, for example, Robson Object Oriented Software Systems , Byte, August, 1981; United States Patents Nos. 4,414,628, 4,533,910, 4,450,442, 4,555,775 and 4,622,545; and L. Tesler, The Small Talk Environment Byte, August 1981, Volume 6, No. 8).The use of modern computer systems incorporating object oriented window environments may be applied to multi-media production methods, such as videotape editing, audio mixing, etc. However, one unique problem associated with multi-media production is the necessity to provide the ability for a diversity of media professionals to collaborate and exchange project data in a consistent interface environment. By providing a consistent user interface, media professionals such as special effects engineers, animation specialists, music composers, and the like may provide both real time and non-real time input to exchange necessary project data, and effectively coordinate the production of the entire media work. Accordingly, one of the requirements of any common multi-media user interface is the ability to integrate multi-media types, and to provide the operator with the ability to manage large quantities of information in an understandable and efficient manner. The user interface must be intuitive and flexible to accommodate a variety of operator editing styles and personalities. For example, a music composer who thinks typically in terms of scores, notes and related music timing, should be able to work in that environment using a standard user interface, and not be required to work in terms of video time code or other non-music related external standards. Similarly, the film production director or special effects engineer should be able to utilize the user interface in a manner consistent with their work environment, which may, by way of example, be illustrated through the use of video time code signals (and not music).This invention provides a computer controlled display system including at least one central processing unit, said CPU being coupled to a display for displaying data, and user input means, said display system being further coupled to a plurality of system resources having defined attributes, said display system comprising: means for generating a user interface for display by said display, said user interface including a display of representations of resources coupled to said display system with which a user interacts through said user input means, said representations of said resources being arranged in a plural dimensional venue, a venue being a space in which representations of resources reside, which may be viewed using said user interface from a plurality of view ports such that viewing said representations of said resources from different view ports results in the display of different attributes of said resources.A system for generating a multi-dimensional user interface for use in audio visual production is disclosed hereinbelow. A display system including at least one central processing unit (CPU) may be coupled through appropriate input/output (I/O) circuitry to input devices, such as a keyboard, digital pad and/or track ball. The CPU may be further coupled to a hard disk drive for the storage of programs and data, and may also be coupled to a network through which the CPU may communicate with a variety of system resource devices such as editors, music synthesizers, graphics generators, scheduling resources, audio enhancement resources, etc. The CPU is also coupled to a display device (for example, a CRT) on which the user interface is displayed to the user. A user viewing the interface on the display may utilize one of the input devices, such as by way of example, the keyboard, to select, incorporate or otherwise integrate the various system resources to develop a unified multi-media production.In preferred embodiments, the user interface includes a control frame which in practice substantially fills all of the display screen of the display. The control frame is comprised of control panels which surround a variety of subwindows, and acts as a consistent control area for all users of the interface. The control frame may include a construction area for all users of the interface. The control frame may include a construction area which corresponds typically to a front view port looking towards a three-dimensional element which is a representation of a resource. The control frame may further include a top view port which illustrates the time relationship between the various resources in a venue . Effectively, the control frame provides a two-dimensional window to selectively view a three-dimensional element .In preferred embodiments, a user specifies mandatory and optional attributes which an element must have, and defines the element representing the resource within the construction area of the control frame. Once defined, the element may be selectively dragged down to an event horizon bar at which time, time data is displayed in the time view port of the control frame. Using the interface, elements may be created, edited, bundled, integrated and rearranged along the event horizon.An embodiment of the invention will now be described, by way of example only, with reference to the accompanying drawings in which:Figure 1 is a conceptual illustration of an integrated multi-media user interface for integrating and manipulating a variety of multi-media functions.Figure 2 is a functional block diagram showing one possible data processing system embodying this invention.Figure 3 is a conceptual illustration of the use of venues to represent data sets of resources available to a user.Figure 4 conceptually illustrates the use of venues and view ports by the user interface. Figure 5 is a conceptual illustration of an element representing a resource, as viewed in three dimensions utilizing the user interface.Figure 6 is a front view of a user display system utilizing the multi-media user interface.Figure 7 is the same view as Figure 6 except that the element attributes window opened for venue selection.Figure 8 is the same view as Figure 7 further illustrating the user interface in the display of a plurality of elements and venues selected for the production of a multi-media work.Figure 9 is the same view as Figure 8 further illustrating the element attribute block opened and venue and resource selection.The detailed descriptions which follow are presented largely in terms of graphics interfaces, algorithms, and in symbolic representations of operations of data bits within a computer display system. These algorithmic descriptions and representations are the means used by those skilled in the data processing arts to most effectively convey the substance of their work to others skilled in the art.An algorithm is here, and generally, conceived to be a self-consistent sequence of steps leading to a desired result. These steps are those requiring physical manipulations of physical entities. Usually, though not necessarily, these entities take the form of electrical or magnetic signals capable of being stored, transferred, combined, compared, and otherwise manipulated. It proves convenient at times, principally for reasons of common usage, to refer to these signals as bits, values, elements, symbols, icons, characters, terms, numbers, windows or the like. It should be borne in mind, however, that all of these similar terms are to be associated with the appropriate physical entities and are merely convenient labels applied to these entities.The manipulations performed are often referred to in terms, such as adding or comparing, displaying, etc. which are commonly associated with mental operations performed by human operator. No such capability of a human operator is necessary, or desirable in most cases, in any of the operations described herein which perform part of the described embodiment of the present invention. In the present case, the operations are machine operations. Useful machines for performing such operations include general purpose digital computers or other similar devices. In all cases, there should be borne in mind the distinction between the method operations of operating a computer and the method of computation itself. This invention relates to method steps for operating a computer graphics system and processing electrical or other physical signal representing physical entities.This invention also relates to apparatus for performing these operations. This apparatus may be specially constructed for the required purposes, or it may comprise a general purpose computer selectively activated or reconfigured by a computer program stored in the computer. The algorithms and displays presented herein are not inherently related to any particular computer or other apparatus. Various general purpose machines may be used with programs in accordance with the teachings herein, or it may prove convenient to construct more specialized apparatus to perform the required method steps. The required structure for an embodiment of such a machine will appear from the description below. In addition, this invention is not described with reference to any particular programming language. It will be appreciated that a variety of programming languages may be used to implement this invention as described herein. The following detailed description will be divided into several sections. The first of these will treat a general system arrangement for generating computer graphics. Subsequent sections will deal with such aspects as the general conceptual definition of a venue and resource , and the structure in operation of the multi-media user interface.In addition, in the following description, numerous specific details are set forth such as functional blocks representing data processing devices, window configurations, etc. in order to provide a thorough understanding of this invention. However, it may be obvious to one skilled in the art that this invention may be practised without these specific details. In other instances, well known circuits are structures are not described in detail in order not to obscure the present invention unnecessarily.Referring now to Figure 1, an embodiment of this invention is conceptually illustrated. As previously discussed, there is provided an integrated user interface, such that media professionals may utilize a common interface and integrate various production processes such as animation, special affects, editing, mixing and production scheduling. Through the use of the user interface, a variety of resources may be accessed in the production of a feature film, videotape of the like. Unlike prior art systems in which separate special effects production facilities, live action facilities and music score editing facilities are required to work independently, and then be integrated at some later date, there is provided a new editing facility to permit an operator to interact with each of the resources comprising a multi-media production and generate a final completed work. As will be described more fully below, this facility accesses, arranges and coordinates these various production resources through the use of an integrated user interface.Referring now to Figure 2, one possible computer graphics system employing the teachings of this invention is shown. As illustrated, the graphics system includes a computer 20, which comprises six major components. The first of these is a central processing unit (CPU) 22 which is coupled to a memory 24. The CPU 22 and the memory 24 are further coupled to a user interface circuit 26 and a disk input/output (I/O) circuit 28, for communicating with a hard disk drive 30 for mass storage of data. The computer 20 further includes a serial input/output (I/O) circuit 32 for communication with serial devices over line 34, such as by way of example a digitizing pad 36, a keyboard 38, and track ball input device 40. The computer system 20 further includes a network interface circuit 42, which is coupled to a network 44 and a gateway circuit 48, which permits the computer system 20 to communicate with other communication systems over telephone lines, optical fibres and the like.In addition, a display monitor 50 is illustrated which is used to display an integrated user interface, and is coupled to the user interface circuit 26. As also illustrated, a variety of resource devices such as a video tape recorder (VTR) 52, a music synthesizer 55, an audio tape recorder 60 and a production switcher 62 are coupled to the network interface circuit 42 over the network 44, through device translators 64, 66, 68 and 70, respectively. As will be described more fully bellow, the arrangement illustrated in Figure 2 permits data from resources such as the VTR 52, the music synthesizer 55 and the audio tape recorder 60 to be coupled to the user interface. A user viewing the interface on the display 50 may utilize one of a variety of input devices, such as by way of example, the keyboard 30 or the track ball 40 to select, incorporate and otherwise integrate the various system resources to develop a unified multi-media production. It will be appreciated that the embodiment illustrated with reference to Figure 2 is only one possible embodiment of many. For example, although only one computer 20 is shown, embodiments may include multiple CPU's and/or computers coupled to the network 44. Each of these CPU's and/or computers coupled to the network 44 may execute separate programs, and support different versions of the user interface. Alternatively, it is contemplated that the use of multiple computers and/or CPU's may support a system of distributed computing, wherein multiple versions of the user interface may be supported concurrently, each of the multiple user interfaces executing different processes but having access to a common data base of resources. As such, it will be noted that the embodiment shown in Figure 2 is a simplified embodiment for purposes of illustration, and is not meant to limit this invention's utility. Referring now to Figure 3, the described embodiment of this invention conceptually permits a variety of media resources such as special effects 90, editing sequencer 92 and video resources 95 to be viewed by a user 100 through a view port , relative in time, along an event horizon . As will be described, a view port provides a perspective view of data contained in a venue , wherein a venue may include in a plurality of resources such as audio resources 102, video resources 95, etc. Referring now to Figure 4, the concept of venues is described in relation to three-dimensional space. The venue concept allows the user 100 to view data represented in alternative view ports of a venue. Relationships between a variety of resources are apparently based on the view which the user 100 chooses. As illustrated in Figure 4, a venue is a three-dimensional space in which object elements reside. An element is a three dimensional representation of a resource coupled to, for example, the network 44 depicted in Figure 2. Depending on the view port which is chosen, the elements identify themselves in various ways. For example, in Figure 4, element 110 may comprise a graphics resource, element 114 may represent an audio resource, element 116 may represent a textual planning resource, and element 118 may represent a music or other audio resource. Viewing a venue through a top view port reveals the relative placement of the various elements in time, both the duration of time that an element represents (such as a film take ) and the relationship between the resources to a reference time, which may be a recording machine, finished film or other multi-media piece. Viewing the right side view port reveals versions of the elements, for example, the audio element 118 includes two versions, namely, a version 120 and a version 122, along with the relative time lengths of the versions. In addition, it should be noted that the user interface permits the use of multiple venues, wherein some or all of the venues may share the same time period, and each venue includes its own elements.For sake of example, assume that the elements illustrated in Figure 4 represent resources for the production of a soap opera. In this example, assume that a production crew photographed a variety of scenes, transferred these scenes to video tape, and that these scenes comprise scene 1, take 1, etc.As shown in Figure 5, viewing an element through the front view port reveals the type of resource through the use of an icon label. For example, in the case of an audio resource, the icon label may comprise a graphic representation of a musical note. In addition, the various versions are illustrated, as in the case of the element 118 in Figure 4, by darkened lines traversing the longitudinal length of the rectangular element image. With respect to Figure 5, the version may be activated, and thereby run, by placing a cursor on the screen of the display 50 over one of the activation buttons 130 on the element, and providing an activation signal, such as for example from a mouse , to run that particular version of the resource. Returning to the present example of a soap opera production, the versions 120 and 122 of the audio element 118 as shown in Figure 4 and the versions 135 of the element 140 shown in Figure 5 may comprise musical options for use during the particular time associated by the length of the elements. Similarly, if the resource comprises scenes, then, as is common in the industry, each of these scenes may have associated time codes (such as SMPTE) which comprise the time in and out for each scene. Accordingly, by viewing the element representing the resource in terms of time, the time length of each scene would be represented on the element by the length of the particular version lines, for example the lines 135, or alternatively, by the duration lines 140 defining the beginning and end time of each scene of the resource.Referring now to Figure 6, the integrated user interface of this invention will be described. As shown in Figure 6, the user interface includes a basic control frame 150 which in practice fills substantially all of the display screen of the display 50 as depicted in Figure 2. The control frame 150 is the primary context for interacting with the user interface and is, primarily, comprised of four control panels which surround a variety of subwindows. Three of the panels are visible to the user at all times, and the bottom panel (not shown) is displayed on an as needed basis. The mode specific action panel 152 comprises, in the displayed embodiment, a plurality of direct action buttons, or icons, which change with the program mode. As shown in the illustration of Figure 6, the mode specific action panel 152 comprises a visual element 155, an aural element 158, a text element 162, a graphic element 164, and a process element 166. Although buttons 155, 158, 162, 164 and 166 are illustrated in Figure 6, it will be appreciated that the mode specific action panel buttons/icons change to support and reflect the current activities of the user for a particular venue.The control frame 150 further includes a major mode panel 170, which comprises an edit button 172, a graphics button 174, an audio button 176, a plan button 180, and a set up button 182. It will be noted that although throughout this description icons, buttons, and the like are described, that the reference to buttons, icons, etc. represents any class of displayed items which result in some executable action when chosen by a user. Therefore, although an edit button 172 is disclosed as part of the control frame 150, it will be appreciated to one skilled in the art that the edit button 172 may comprise an icon in the form of some edit feature or the like which achieves the same result. In the presently preferred embodiment, the buttons comprising the major mode panel 170 are always present for the user no matter which venue or other option is selected. In general, the major code panel 170 permits a user to access different venues than the venue currently displayed. The specific buttons/icons used in the major mode panel 170 are a function of the particular project in which the user interface is implemented. A menu bar panel 190 generally displays labels for pull down menus. Standard labels such as organize , modify , etc. are provided and are present no matter which venue or resource is accessed. Other context specific menu labels will be displayed, e.g. element , edit style , utilities , setup , etc are provided for specific applications.The application specific construction area 200 comprises an application area of the display for a selected program mode, and is available for subwindows, user views in the display of other elements of work such as time lines, scripts, scores, preview monitors, etc. As shown in Figure 6, the construction area 200 is designated as a resource manager. As will be described, a top view port 215 is also provided in the control frame 150. As previously illustrated in Figure 4, elements representing resources may be viewed and operated upon by appropriately selecting a view port. Although the control frame 150 displays objects in two dimensions, by appropriately selecting the view port, the elements may be viewed from all three dimensions. The elements directly represent the objects that make up a production, such as scripts, segments of video tape, score, scenes, director notes, sound tracks, etc., and are identified by an icon on the front face of the element as previously described with respect to Figure 5. Elements can be viewed from the front, side, or from the top, or in multiple views. As previously discussed with reference to the concept of resources , the front view of the element displays the icon label and the type of element may be determined from the icon as on its face (see Figure 5). Viewing an element from the top view port illustrates the relative length in time the elements may have. A view from a side port illustrates any different versions and their relative lengths. The element/resources may comprise several individual elements, and may be bundled into a new compound element much like current users may group graphical elements using a graphics editor.Referring once again to Figure 6, the top view port 215 is used to position elements relative to time by placing them on a time line. As will be described in more detail below, placing an element on a bar referred to as the event horizon 220 integrates the element into the overall time line for the production and results in the display of time data in the area identified in Figure 6 as 218. Moving an element from the construction region 200 to the event horizon 220 results in the element being assigned a time assignment in the view port 215. It will be noted that the view port 215 corresponds to the top view port of an element in the three-dimensional representation of resources described with reference to Figure 4.Referring now to Figure 7, assume for sake of example that a user desires to define an element using the user interface. An element attribute box 250 is displayed by the computer 20 depicted in Figure 2 once a selection identified as element 252 is chosen by a user. Although in the presently preferred embodiment, the element 252 comprises a pull down menu (not shown) having a plurality of items for selection, conceptually the element 252 is selected by a user through the use of a cursor control device (see for example, United States Patent Reissue No. 32633). Although a cursor control device, such as a mouse may be used to selected the element 252, it will be appreciated that the actual selection may be made using a variety of display input devices known in the art. It will also be appreciated to one skilled in the art, that other mechanisms for selecting the element 252 the like are known. Accordingly, the particular mechanism for selecting functions, items, icons and the like within the control frame 150 will not be described in detail.Once the element 252 is selected, the computer 20 depicted in Figure 2 displays the element attribute box 250 as shown in Figure 7. A user then either selects from a preprinted list of elements, or defines elements within the element attribute box 250, the nature of the resource required for the particular production. Examples of such element attributes which a user may select include, but are not limited to the following:VISUAL ELEMENT ATTRIBUTESLABEL: User Supplied Element identification (e.g.: Video Tape Recorder, etc.) SOURCE DEVICE Assignment of device: (e.g.: P1, P2, RECORD, etc.)IDENTIFICATION: Alpha-Numeric material Identification: e.g.: reel number, reel label, etc. lab roll number, etc.SCENE/TAKE INFORMATION: Content Scene and Take identification. Scene Take file name.CODES: Time Code and type. Origin Time Code and type. User bit Time Code. User bits. Content. Frame Numbers. Edge Numbers Code NumbersNOTES: Associated Text Notes For Reel &/or ContentPRIORITY: User assigned Priority levels for different versionsPROCESSING PATH: Information on any previous Processing that applies to this material. (e.g: DUB LEVEL, COLOUR CORRECTION, ETC.)AUDIO ELEMENT ATTRIBUTESLABEL: User supplied Element identificationSOURCE DEVICE: Type and Assignment of device. (e.g. ATR, DISC, ETC.) P1, P2, RECORD, ETC.IDENTIFICATION Alpha-Numeric material identification (e.g. Reel number, Reel label etc. Sound Roll Number, Label).SCENE/TAKE # Content Scene and Take identification.CODES; Time Code and Type. Origin Time Code and type. User bit Time Code contents. Frame NumbersTRACKS Number and Numbers of Source TrackNOTES: Associated Text Notes. For Reel &/or ContentPRIORITY: User assigned Priority levels for different versionsPROCESSING PATH: Information on any previous Processing that applies to this material. (e.g. Dub level, Equalization, etc)TEXT ELEMENT ATTRIBUTESLABEL: User supplied Element identification.NAME: Title of Text type and Document. (SCRIPT, OPENING TITLE, CHARACTER GENERATOR, ETC)REVISION: The current Text revision level relevant previous revision informationFILE TYPES: The Names and Types of files as the material exists in useable form.ASSOCIATED DATA: Any previous data files associated with creating the current file.PROCESSING PATH: Information on any previous Processing that applies to this material.GRAPHIC ELEMENT ATTRIBUTESLABEL: User supplied Element identificationTITLE: A user supplied description of the Graphic element REVISION: The current Graphic revision level and relevant previous revision information.FILE TYPES: The Names and Types of files as the material exists in useable form now.ASSOCIATED DATA: Any previous data files associated with creating the current file.PROCESSING PATH: Information on any previous Processing that applies to this materialPROCESSING ELEMENT ATTRIBUTESLABEL: User Supplied Element identification.DEVICE IDENTIFICATION: Effects Device identificationASSIGNMENT PATH: Video and/or Audio routing assignments (e.g. CROSSPOINTS, KEY CHANNELS, ETC.)UP LOAD/DOWN LOAD: File input/output for created effects save and recall.CODES: Time Line Code and type. Effects durations. Effects Source codes. Effects Edge Numbers for optical printer outputs. PROCESSING: Effects types. (e.g. CUTS, FADES, DISSOLVES, WIPES, KEYS, DME, ETC.)Once the element attributes have been defined, the computer 20 illustrated in Figure 2 utilizes appropriate network connections over the network 44 to the various resources, such as the VTR 52, music the synthesizer 55, the Audio tape recorder 60, the Production switcher 62, etc. to access the resource via the user interface. Accordingly, a direct connection via the computer 20 has been created between the user interface comprising the control frame 150 as displayed on the display 50, and the particular element/resource coupled through the network interface 42. Referring to Figure 7, within the top view port 215, time elements corresponding to the particular resource have additional information that is revealed in the time line associated with the top view port 215. Tracking buses 265 provide additional information regarding the recording of audio channels 1 to 4, and a video channel 1. In practice, a source tape machine (not shown) supplies audio to a tape record machine wherein the channels are coupled to one another. It has been found that it is quite useful to display audio channels in the time view port 215, in order to correlate the audio channel and time interval versus resource.Once the element attributes have been defined, an element representing a resource is created based upon those attributes, and displayed within the construction area 200 of the control frame 150. Referring now to Figure 8, the user interface is illustrated wherein a plurality of elements identified as Record VTR 300, Scene I 310, Scene II 312, Dissolve 314, Open Title 316, and Key 320 are shown. As illustrated in Figure 8, an element such as Record VTR 300 includes an icon image (for example, the planet Earth in Figure 8) which describes some aspect of the element for identification purposes. Viewing elements disposed in the construction area 200 normally correspond to viewing a venue and associated resources through a front view port as shown previously with respect to Figure 4. An element, for example, Record VTR 300, may be moved within the construction region 200 at will by a user through the use of an appropriate command sequence, or by simply dragging the element around the construction area using a cursor control device such as a mouse. However, once an element such as Scene I 310 is brought, dragged, or otherwise manipulated downward to the event horizon 220, the element is automatically given time significance which is represented along the time lines of the top view port 215.As illustrated in Figure 8, the event horizon 220 comprises a horizontal bar with arrows 221 and 222 at each of its opposite ends. By placing a cursor (not shown) over the arrows 221 or 222, and presenting the computer 20 with an activation signal, resource elements such as Scene I 310, Scene II 312, Dissolve 314, etc. may be moved left or right, respectively, and other elements may be viewed which are currently not visible on the event horizon 220 in the control frame 150. The use of the arrows 221 and 222 permits a user to scan through elements disposed on the event horizon 220 and view the elements not only in relative position, but in relative time. This view corresponds to that of a user 100 in Figure 3 scanning the resources in that Figure, such as special effects 90, editing 92, video 95, etc. In addition, it will be appreciated that the relative position of the element may be changed by simply dragging an element such as Scene I 310 off the event horizon 220, moving other elements into that time slot along the event horizon 220 and replacing Scene I 310 at some other location along the event horizon 220. A redistribution of the element's relative position along the event horizon 220 would correspond in Figure 4 to, for example, swapping the element 110 for the element 116 and vice versa.Once an element is placed upon the event horizon 220, position data relative in time to other elements is illustrated along the time lines of the top view port 215 as shown. Conceptually, the reader is directed to Figure 4 which illustrates in three dimensions the placements of elements relative to one another in time. However, due to the limitations of the display 50 depicted in Figure 2, the time view port 215 is utilized to display time along the ± Y direction, with time being To being at the lower portion of the display as illustrated in Figure 8. In addition, as shown in Figure 8, the number of versions, of, for example, Scene I 310, is also displayed as versions 351 to 354. It will be appreciated by the reader that the display of an element such as Scene I 310 corresponds to the prior description of a resource having multiple versions which may be activated by selecting (for example, by placing a cursor over the version 354 and providing an activation signal) a version such that the version is run within the window of the Scene I 310. Accordingly, a user may view the entire version of Scene I which has been selected, within the icon window comprising the scene. In general, in the present and preferred embodiment, and throughout this specification, placing a cursor over an icon or other executable function and double clicking using a cursor control device such that two consecutive signals are provided to the computer 20 depicted in Figure 2, executes the function which has been selected, and, more particularly, reveals any attributes and/or contents of the icon. Double clicking on a time function such as the time block 400 for Scene I (Figure 8) may be configured such that time code (i.e. SMPTE) is displayed. More particularly, in the present example, SMPTE time code for the beginning and end of each version within Scene I 310 may be displayed within the time line view port 215.Referring now to Figure 9, the control frame 150 is illustrated in which a new Scene I 400 has been dragged upward into the construction area 200. As illustrated in Figure 9, once an element, in the present example Scene I 400, is moved off of the event horizon 220, timing information viewed through the top view port 215 corresponding to Scene I 400 is no longer displayed. Elements such as Scene II 404, Dissolve 406, Open Title 408 or Key 410 may be repositioned along the event horizon 220 and/or modified in terms of time sequence as viewed through the top view port 215, relative to one another. Alternatively, and as shown in Figure 9, the element attribute box 250 may be selected and the attributes of Scene I 400 may be modified, or an entirely new element may be defined, to replace Scene I 400 along the event horizon 220.It will be appreciated that a user utilizing the interface defines elements in the construction area 200 by specifying attributes of the element in the element box 250. In addition, multiple elements may be created within the construction area 200. The created elements may then be selectively dragged to the event horizon 200 in an arrangement and order selected by the user. It will further be appreciated from the above discussion by one skilled in the art that the user interface permits the utilization of resources within the system illustrated in Figure 2, permits selective modification of the resources, and through the use of the interface provides a consistent interface for the production of an audio visual work. The user interface through the use of the common control frame 150 as displayed on the display 50, allows artists, musicians, and other media professionals to create, modify, and rearrange resources comprising a production with flexibility heretofore unknown in the art. The concept of venues, and the ability to operate on resources in three dimensions, provide a user with flexibility not present in any prior user interface for computer display systems, we well as multi-media production systems known in the past.This embodiment of the invention has been described and illustrated with reference to the figures as applied to a display 50, and using input devices, such as the digital pad 36, the trackball 40 and the keyboard 38 as shown in Figure 2. However, numerous other display devices and input mechanisms may be used. For example, embodiments of this invention may be practised using what are known as virtual reality input devices, such as but not limited to, a data input glove, a body glove input device, etc. In addition, embodiments of this invention may utilize eye goggle displays which are worn by a user and coupled to the computer display system via fibre optics, wires and the like. When embodiments of this invention utilizes a virtual reality system, the user interface would be viewed by a user through input goggles as being suspended in space. Interaction with the interface by the user may be done using an input glove or other virtual reality device worn by the user. Accordingly, it will be appreciated that the user interface is not limited to conventional input or display devices. The reader is referred to the following references for a further description of existing and proposed virtual reality systems. Computerised Reality Comes of Age, NASA Tech Briefs, page 10, August 1990 (Vol. 14, number 8); Iwata, Artificial Reality with Force - Feedback; Development of Desktop Virtual Space with Compact Master manipulator, ACM SIGGRAPH, August 1990 (Volume 24. number 4); Nash, Our Man in Cyberspace Checks out Virtual Reality, Compterworld, October 15, 1990; Daviss, Grand Illusions, Discover, June 1990.At least preferred embodiments of this invention provide a multi-media user interface with may be utilized by a variety of multi-media professionals in the production of film or tape works. Unlike prior art window based display systems, a three-dimensional representation (known as an element ) of information to be manipulated is provided. Each element comprises a three dimensional representation of a resource . A resource is a three dimensional object which may have data represented in either two or three-dimensional form. A window comprises a venue which may be configured for specific activities, such as music production, special effects, scheduling and the like. However, the user interface shares common fundamental tools and the same data base, such that each media professional, such as a videotape editor, audio editor, producer, etc. may utilize the interface in a consistent manner.While this invention has been described in conjunction with a few specific embodiments identified in Figures 1 to 9, it will be apparent to those skilled in the art that many alternatives, modifications and variations as may fall within the scope of the invention as defined by the appended claims.
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A computer controlled display system including at least one central processing unit (CPU) (22), said CPU being coupled to a display (50) for displaying data, and user input means (36, 38, 40, 41), said display system being further coupled to a plurality of system resources (90, 92, 95, 102) having defined attributes, said display system comprising: means for generating a user interface for display by said display, said user interface including a display of representations (300, 310, 312, 314, 316, 320) of resources coupled to said display system with which a user interacts through said user input means, said representations of said resources being arranged in a plural dimensional venue, a venue being a space in which representations of resources reside, which may be viewed using said user interface from a plurality of view ports (200, 215) such that viewing said representations of said resources from different view ports results in the display of different attributes of said resources.A system as claimed in claim 1 wherein said representations of said resources are arranged in said venue such that each of said resources is disposed relative to one another in time and space within said venue.A system as claimed in claim 2 further including manipulation means coupled to said user input means for selectively positioning said representations of said resources within said venue.A system as claimed in claim 1, claim 2 or claim 3 wherein said means for generating a user interface includes means coupled to said CPU for generating and displaying a control frame (15) using said display to display selected view ports of a venue, said control frame including a plurality of command options (152, 190, 170) which may be selected by said user using said user input means.A system as claimed in claim 4 wherein said control frame further includes a event horizon bar (220), such that the placement of a representation of a resource on said bar results in timing data being displayed in said control frame.A system as claimed in 5 wherein said representations of said resources may be selectively placed on said event horizon bar (220), thereby altering the relative placement of said representations in said venue in time and space.A system as claimed in any one of claims 4 to 6 wherein said control frame further includes a first area (200) for defining said attributes of said resources and displaying said representations of said resources once said attributes are defined.A system as claimed in claim 7 wherein said first area displays said representations of said resources in a venue initially from a first view port.A system as claimed in claim 8 wherein said user may selectively change view ports from said first view port by selecting one of said command options.A system as claimed in any one of claims 7 to 9 wherein said control frame further includes a second area (215) for displaying said top view port of said venue, such that timing data representing relative time associated with said resources is displayed in said second area.A system as claimed in any one of claims 4 to 10 wherein selecting an Element command option results in the display of an element attribute box (250) for defining said resource attributes.A system as claimed in any one of claims 4 to 11 wherein said command options of said control frame further includes a plurality of mode specific action options (152) on the periphery of said control frame.A system as claimed in any one of claims 4 to 12 wherein said command options of said control frame further includes a plurality of major mode options (17) on the periphery of said control frame.A system as claimed in any one of the preceeding claims wherein said venue is three-dimensional and each of said representations of said resources is three dimensional.A system as claimed in claim 14 wherein said venue may be viewed from six view ports, namely, atop (215), left, right, rear, bottom and front (200) view port.A system as claimed in claim 15 wherein viewing said venue from the top view port (215) reveals the relative positions of each of said three dimensional representations of said resources relative in time to one another.A system as claimed in claim 15 or claim 16 wherein viewing said venue from the front view port (200) reveals an icon identifying the type of resource each of said representations represent.A system as claimed in any one of claims 15 to 17 wherein viewing said venue from a side view port reveals versions (120, 122; 135) of said resource and the lengths of said versions relative to one another.A system as claimed in claim 18 wherein viewing said venue from the front view port further reveals version activation buttons (130; 350, 351, 352, 353, 354), one of said buttons for each of said versions, such that said user, using said user input means may selectively activate said versions.A system as claimed in claim 19 wherein in the event said user activates one of said versions, said version is executed within said representation of said resource, and may be viewed through said front view port of said venue on said display.A system as claimed in any one of claims 15 to 20, when appendant to claim 8, wherein said first view port initially displayed comprises the front view port.
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SONY ELECTRONICS INC A DELAWAR; SONY ELECTRONICS INC. (A DELAWARE CORPORATION)
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BERGER ROBERT J; DUFFY ROBERT; LANGFORD TED ELLIS; MACKAY MICHAEL T; BERGER, ROBERT J.; DUFFY, ROBERT; LANGFORD, TED ELLIS; MACKAY, MICHAEL T.
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EP-0489577-B1
| 489,577 |
EP
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B1
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EN
| 19,950,322 | 1,992 | 20,100,220 |
new
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C07C259
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A61K31, C07C237
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C07D295, C07C237, C07C311, C07D209, A61P35, A61K31, C07K5, C07D213, C07C233, A61P43, C07C55, C07D265, C07D307, C07D239, A61K38, C07C259
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C07K 5/06A1B2, C07K 5/06C1, C07C 259/06, C07C 311/46, C07C 55/02, K61K38:00, M07D209:20, C07D 209/20, C07C 237/22, M07C101:14
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Peptidyl derivatives
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Compounds of formula (I): are described wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R¹ represents an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group;R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, aralkoxy, or aralkylthio group, or an amino (-NH₂), substituted amino, carboxyl (-CO₂H) or esterified carboxyl group; R³ represents a hydrogen atom or an alkyl group;R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents a group -[Alk]nR⁶ where Alk is an alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group], n is zero or an integer 1, and R⁶ is an optionally substituted cycloalkyl or cycloalkenyl group; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. The compounds are metalloproteinase inhibitors and in particular have a selective gelatinase action, and may be of use in the treatment of cancer to control the development of tumour metastasises.
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This invention relates to a novel class of peptidyl derivatives, to processes for their preparation and to their use in medicine. Background to the InventionIn normal tissues, cellular connective tissue synthesis is offset by extracellular matrix degradation, the two opposing effects existing in dynamic equilibrium. Degradation of the matrix is brought about by the action of proteinases released from resident connective tissue cells and invading inflammatory cells, and is due, in part, to the activity of at least three groups of metalloproteinases. These are the collagenases, the gelatinases (or type-IV collagenases) and the stromelysins. Normally these catabolic enzymes are tightly regulated at the level of their synthesis and secretion and also at the level of their extracellular activity, the latter through the action of specific inhibitors, such as α₂-macroglobulins and TIMP (tissue inhibitor of metalloproteinase), which form inactive complexes with metalloproteinases. The accelerated, uncontrolled breakdown of connective tissues by metalloproteinase catalysed resorption of the extracellular matrix is a feature of many pathological conditions, such as rheumatoid arthritis, corneal, epidermal or gastric ulceration; tumour metastasis or invasion; periodontal disease and bone disease. It can be expected that the pathogenesis of such diseases is likely to be modified in a beneficial manner by the administration of metalloproteinase inhibitors and numerous compounds have been suggested for this purpose [for a general review see Wahl, R.C. etal Ann. Rep. Med. Chem. 25, 175-184, Academic Press Inc., San Diego (1990)]. Certain hydroxamic acid peptidyl derivatives [see for example European Patent Specifications Nos. 214639, 231081, 236872 and 274453 and International Patent Specifications Nos. WO90/05716 and WO90/05719], have been described as collagenase and/or stromelysin inhibitors. We have a now found a new class of peptidyl derivatives, members of which are metalloproteinase inhibitors and which, in particular, advantageously possess a potent and selective inhibitory action against gelatinase. There is now much evidence that metalloproteinases are important in tumour invasion and metastasis. Tumour cell gelatinase, in particular, has been associated with the potential of tumour cells to invade and metastasise. Tumour invasion and metastasis is the major cause of treatment failure for cancer patients, and the use of a selective gelatinase inhibitor such as a compound of the present invention which is capable of inhibiting tumour cell invasion can be expected to improve the treatment of this disease. Thus according to one aspect of the invention we provide a compound of formula (I) wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R¹ represents a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group; R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, aralkoxy, or aralkylthio group, or an amino (-NH₂), substituted amino, carboxyl (-CO₂H) or esterified carboxyl group, provided that R² is not an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R³ represents a hydrogen atom or an alkyl group; R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents a group -[Alk]nR⁶ where Alk is an alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group], n is zero or an integer 1, and R⁶ is an optionally substituted cycloalkyl or cycloalkenyl group; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. It will be appreciated that the compounds according to the invention can contain one or more asymmetrically substituted carbon atoms, for example those marked with an asterisk in formula (I). The presence of one or more of these aysmmetric centres in a compound of formula (I) can give rise to stereoisomers, and in each case the invention is to be understood to extend to all such stereoisomers, including enantiomers and diastereoisomers, and mixtures, including racemic mixtures, thereof. In the formulae herein, the ∼line is used at a potential asymmetric centre to represent the possibility of R- and S- configurations, the line and the ------- line to represent an unique configuration at an asymmetric centre. In the compounds according to the invention, when the group R represents an esterified carboxyl group, it may be for example a group of formula - CO₂R⁸ where R⁸ is a straight or branched, optionally substituted C₁₋₈alkyl group such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl group; a C₆₋₁₂arylC₁₋₈alkyl group such as an optionally substituted benzyl, phenylethyl, phenylpropyl, α-naphthylmethyl or β-naphthylmethyl group; a C₆₋₁₂aryl group such as an optionally substituted phenyl, α-naphthyl or β-naphthyl group; a C₆₋₁₂aryloxyC₁₋₈alkyl group such as an optionally substituted phenyloxymethyl, phenyloxyethyl, α-naphthyloxymethyl or β-naphthyloxymethyl group; an optionally substituted C₁₋₈alkanoyloxyC₁₋₈alkyl group, such as a pivaloyloxymethyl, propionyloxyethyl or propionyloxypropyl group; or a C₆₋₁₂aroyloxyC₁₋₈alkyl group such as an optionally substituted benzoyloxyethyl or benzoyloxypropyl group. Optional substituents present on the groups R⁸ include for example one or more halogen atoms such as fluorine, chlorine, bromine or iodine atoms, or C₁₋₄alkyl, e.g. methyl or ethyl, or C₁₋₄alkoxy, e.g. methoxy or ethoxy, groups. In general, when the group R represents an esterified carboxyl group, it may be a metabolically labile ester of a carboxylic acid. When the groups R¹ and/or R² in compounds of formula (I) each represents an optionally substituted alkyl or alkenyl group, it may be, for example, a straight or branched C₁₋₆ alkyl or C₂₋₆alkenyl group, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, ethenyl, 1-propenyl, 1-butenyl or 2-butenyl group optionally substituted by one or more C₁₋₆alkoxy, e.g. methoxy, ethoxy or propoxy, C₁₋₆alkylthio, e.g. methylthio, ethylthio or propylthio, C₆₋₁₂arylC₁₋₆alkoxy, e.g. phenylC₁₋₆ alkoxy such as benzyloxy, aralkylthio, e.g phenylC₁₋₆alkylthio such as benzylthio, amino (-NH₂), substituted amino, [such as -NHR⁹, where R⁹ is a C₁₋₆ alkyl e.g. methyl or ethyl], C₆₋₁₂arylC₁₋₆alkyl, e.g. phenylC₁₋₆alkyl, such as benzyl, C₆₋₁₂aryl, e.g. phenyl, C₃₋₈cycloalkyl, e.g. cyclohexyl, or C₃₋₈cycloalkylC₁₋ ₆alkyl, e.g. cyclohexylmethyl group], carboxyl (-CO₂H) or -CO₂R⁸ [where R⁸ is as defined above] groups. Aryl groups represented by R¹ and/or R² in compounds of formula (I) include C₆₋₁₂ aryl groups such as phenyl or α- or β-naphthyl groups. Aralkyl groups represented by R¹ and/or R² include C₆₋₁₂arylC₁₋₆alkyl groups such as phenylC₁₋₆alkyl, or α- or β-naphthylC₁₋₆alkyl, for example benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, α- or β-naphthylmethyl, naphthylethyl, naphthylpropyl naphthylbutyl or naphthylpentyl groups, provided that R² is not an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group. When the group R¹ in compounds of formula (I) is a heteroaralkyl group, it may be for example a C₃₋₆heteroarylC₁₋₆alkyl group, such as an optionally substituted pyrrolylmethyl, furanylmethyl, thienylmethyl, imidazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyrazolylmethyl, pyrrolidinylmethyl, pyridinylmethyl, pyrimidinylmethyl, morpholinylmethyl, or piperazinylmethyl group. Heteroarylthioalkyl groups represented by R¹ include C₃₋₆heteroarylthioC₁₋ ₆alkyl groups such as optionally substituted pyrrolylthiomethyl, furanylthiomethyl, oxazolylthiomethyl, thiazolylthiomethyl, pyrazolylthiomethyl, pyrrolidinylthiomethyl, pyridinylthiomethyl, pyrimidinylthiomethyl, morpholinylthiomethyl, or piperazinylthiomethyl groups. Optional substituents which may be present on heteroaralkyl or heteroarylthioalkyl groups represented by R¹ include those discussed below in relation to R¹ and/or R² when these groups are for example aralkyl or aralkylthioalkyl groups. Cycloalkyl groups represented by the group R² in compounds according to the invention include C₃₋₈cycloalkyl groups such as cyclopentyl or cyclohexyl groups. When R² is a cycloalkylalkyl group it may be for example a C₃₋₈cycloalkylC₁₋ ₆alkyl group such as a cyclopentylC₁₋₆alkyl or cyclohexylC₁₋₆alkyl group, for example a cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, or cyclohexylbutyl group. When R² is an aralkoxy or an aralkylthio group it may be for example a C₆₋ ₁₂arylC₁₋₆alkoxy or C₆₋₁₂arylC₁₋₆alkylthio group such as a phenylC₁₋ ₆alkoxy or phenylC₁₋₆alkythio group, e.g. a benzyloxy, phenylethoxy, phenylpropoxy, phenylbutoxy, benzylthio, phenylethylthio, phenylpropylthio or phenylbutylthio group. The cycloalkyl, cycloalkylalkyl, aryl, aralkyl, aralkoxy or aralkylthio groups represented by R¹ and/or R² in compounds of formula (I) may each optionally be substituted in the cyclic part of the group by one, two or more substituents [R¹⁰] selected from halogen atoms, e.g. fluorine, chlorine, bromine or iodine atoms, or C₁₋₆alkyl, e.g. methyl or ethyl, C₁₋₆alkoxy e.g. methoxy or ethoxy, C₂₋₆alkylenodioxy, e.g. ethylenedioxy, haloC₁₋₆alkyl, e.g. tri-fluoromethyl, C₁₋₆alkylamino, e.g. methylamino or ethylamino, C₁₋ ₆dialkylamino, e.g. dimethylamino or diethylamino, amino (-NH₂), nitro, cyano, hydroxyl (-OH), carboxyl (-CO₂H), -CO₂R⁸, where R⁸ is as defined above, C₁₋₆alkylcarbonyl, e.g. acetyl, sulphonyl (-SO₂H), C₁₋ ₆alkylsulphonyl, e.g. methylsulphonyl, aminosulphonyl (-SO₂NH₂), C₁₋₆ alkylaminosulphonyl, e.g. methylaminosulphonyl or ethylaminosulphonyl, C₁₋₆dialkylaminosulphonyl e.g. dimethylaminosulphonyl or diethylaminosulphonyl, carboxamido (-CONH₂), C₁₋₆alkylaminocarbonyl, e.g. methylaminocarbonyl or ethylaminocarbonyl, C₁₋₆dialkylaminocarbonyl, e.g. dimethylaminocarbonyl or diethylaminocarbonyl, sulphonylamino (-NHSO₂H), C₁₋ ₆alkylsulphonylamino, e.g. methylsulphonylamino or ethylsulphonylamino, or C₁₋₆dialkylsulphonylamino, e.g. dimethylsulphonylamino or diethylsulphonylamino groups. It will be appreciated that where two or more R¹⁰ substituents are present, these need not necessarily be the same atoms and/or groups. The R¹⁰ substituents may be present at any ring carbon atom away from that attached to the rest of the molecule of formula (I). Thus, for example, in phenyl groups any substituents may be present at the 2-, 3-or 4-, 5- or 6- positions relative to the ring carbon atom attached to the remainder of the molecule. When the group R² in compounds of formula (I) is a substituted amino group, this may be for example a group -NHR⁹ where R⁹ is as defined above. Esterified carboxyl groups represented by R² include groups of formula-CO₂R⁸ where R⁸ is as defined above. When the groups R³ and R⁴ in compounds of formula (I) are alkyl groups, they may be for example C₁₋₆alkyl groups such as methyl or ethyl groups. When the group Alk is present in compounds of formula (I) it may be a straight or branched C₁₋₆alkyl, e.g. methyl, ethyl, n-propyl i-propyl, n-butyl, i-butyl, n-pentyl or n-hexyl or C₂₋₆alkenyl e.g. ethenyl or 1-propenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups where R⁷ is a hydrogen atom or a C₁₋₆alkyl group such as a methyl group. The group R⁶ in compounds of formula (I) may represent a C₃₋₈cycloalkyl, e.g. cyclopentyl or cyclohexyl, or C₃₋₈cycloalkenyl e.g. cyclopentenyl or cyclohexenyl, group optionally substituted by one, two or more C₁₋₆alkyl, e.g. methyl or ethyl, C₁₋₆alkoxy, e.g. methoxy or ethoxy, C₁₋₆alkylthio, e.g. methylthio, or hydroxyl groups. When X in the compounds of formula (I) represents a substituted amino group it may be for example a group of formula -NR¹¹R¹², where R¹¹ and R¹², which may be the same or different, is each a hydrogen atom (with the proviso that when one of R¹¹ or R¹² is a hydrogen atom, the other is not) or an optionally substituted straight ot branched alkyl group, optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- or aminocarbonyloxy [-NHC(O)O-] groups or R¹¹ and R¹², together with the nitrogen atom to which they are attached, may form an optionally substituted C₃₋₆cyclic amino group optionally possessing one or more other heteroatoms selected from -O- or - S-, or -N(R⁷)- groups. When R¹¹ and/or R¹² is an alkyl group it may be for example a C₁₋₆alkyl group such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, or t-butyl group, optionally interrupted by one or more -O- or -S- atoms, or - N(R⁷)- or aminocarbonyloxy groups and may be for example a methoxymethyl, ethoxymethyl, ethoxymethyl, ethoxyethyl or ethylaminocarbonyloxymethyl group. The optional substituents which may be present on such groups include hydroxyl (-OH), carboxyl (-CO₂H), esterified carboxyl (-CO₂R⁸), carboxamido (-CONH₂), substituted carboxamido, e.g. a group -CONR¹¹R¹² where NR¹¹R¹² is as defined herein, amino (-NH₂), substituted amino, for example a group of formula -NR¹¹R¹², or aryl, e.g. C₆₋₁₂ aryl such as phenyl, optionally substituted by one, two or more R¹⁰ substituents selected from those listed above in relation to the group R². Particular examples of cyclic amino groups represented by -NR¹¹R¹² include morpholinyl, imidazolyl, piperazinyl, pyrrolyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolidinyl, pyridinyl and pyrimidinyl groups. When the group X is a substituted hydroxyl group it may be for example a group -OR¹¹ where R¹¹ is as defined above, other than a hydrogen atom. Salts of compounds of formula (1) include pharmaceutically acceptable salts, for example acid addition salts derived from inorganic or organic acids, such as hydrochlorides, hydrobromides, hydroiodides, p-toluene sulphonates, phosphates, sulphates, perchlorates, acetates, trifluoroacetates, propionates, citrates, malonates, succinates, lactates, oxalates, tartrates and benzoates. Salts may also be formed with bases. Such salts include salts derived from inorganic or organic bases,. for example alkali metal salts such as sodium or potassium salts, alkaline earth metal salts such as magnesium or calcium salts, and organic amino salts such as morpholine, piperidine, dimethylamine or diethylamine salts. When the group R in compounds of the invention is an esterified carboxyl group, it may be a metabolically labile ester of formula -CO₂R⁸ where R⁸ may be an ethyl, benzyl, phenylethyl, phenylpropyl, α- or β-naphthyl, 2,4-dimethylyphenyl, 4-t-butylphenyl, 2,2,2-trifluoroethyl, 1-(benzyloxy)benzyl, 1-(benzyloxy)ethyl, 2-methyl-1-propionyloxypropyl, 2,4,6-trimethylbenzoyloxymethyl or pivaloyloxymethyl group. In the compounds of formula (I) the group R¹ may in particular be a C₁₋₆alkyl group such as a methyl group, an aralkyl group such as benzyl group, an arylthioalkyl group such as a phenythiomethyl group or a heteroarylthioalkyl group such as thienylthiomethyl, pyridinylthiomethyl or pyrimidinylthiomethyl group or is especially a hydrogen atom. The group R² may be in particular an optionally substituted C₁₋₆alkyl, C₃₋ ₈cycloalkyl, C₃₋₈cycloalkylC₁₋₆alkyl, C₆₋₁₂aryl, C₆₋₁₂arylC₁₋₆alkoxy or C₆₋ ₁₂aralkylthio group and, especially, a C₆₋₁₂arylC₁₋₆alkyl group. Particular types of these groups are optionally substituted C₃₋₆ alkyl, such as n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl or i-pentyl; cyclopentyl; cyclohexyl; cyclopentylC₁₋₆alkyl, such as cyclopentylC₃₋₆alkyl, e.g. cyclopentylpropyl, cyclopentylbutyl, or cyclopentylpentyl; phony; α- or β-naphthyl; phenylC₁₋₆alkoxy, e.g. phenylethoxy, phenylpropoxy or phenylbutoxy; phenylC₁₋₆ alkylthio, e.g. phenylethylthio, phenylpropylthio or phenylbutylthio; and, especially, phenylC₁₋₆alkyl such as phenylC₃₋₆alkyl e.g. phenylpentyl; or α- or β-naphthylC₁₋₆alkyl such as α- or β-naphthylC₃₋₆alkyl, e.g. α- or β-naphthylpropyl, naphthylbutyl or naphthylpentyl. Each of these cycloalkyl or aryl groups may be substituted, by one two or more substituents R¹⁰ described above. The groups R³ and R⁴ in compounds of formula (I) may each in particular be a methyl group, or, especially, a hydrogen atom. The group R⁵ in compounds of formula (I) may be in particular a group - AlkR⁶, where R⁶ is an optionally substituted cycloalkyl or cycloalkenyl group. Thus, the group R⁵ in compounds of formula (I) may be an optionally substituted C₃₋₈cycloalkylC₁₋₆alkyl [e.g. cyclopentylC₁₋₆alkyl such as cyclopentylmethyl or cyclopentylethyl, or cyclohexyC₁₋₆alkyl such as cyclohexylmethyl or cyclohexylethyl], C₃₋₈cycloalkenylC₁₋₆alkyl [e.g. cyclopentenylC₁₋₆alkyl such as cyclopentenylmethyl or cyclohexenylC₁-₆alkyl such as cyclohexenylmethyl], cycloalkylC₁₋₃alkoxyC₁₋₃alkyl [e.g. cyclopentylmethoxymethyl, cyclohexylmethoxymethyl] C₃₋₈cycloalkenylC₁₋ ₃alkoxyC₁₋₃alkyl [e.g. cyclopentenylmethoxymethyl or cyclohexenylmethoxymethyl] C₃₋₈cycloalkylC₁₋₃alkylthioC₁₋₃alkyl [e.g. cyclopentylmethylthiomethyl or cyclohexylmethylthiomethyl] or C₃₋ ₈cycloalkenylC₁₋₃alkylthioC₁₋₃alkyl [e.g. cyclopentenylmethylthiomethyl or cyclohexenylmethylthiomethyl], C₃₋₈cycloalkyC₁₋₃alkylaminoC₁₋₃alkyl [e.g. cyclopentylmethylaminomethyl, or cyclohexylmethylaminomethyl] or C₃₋ ₈cycloalkenylC₁₋₃alkyaminoC₁₋₃alkyl [e.g. cyclopentenylmethylaminomethyl or cyclohexenylmethylaminomethyl] group. The group X in compounds of formula (I) may be in particular an amino (-NH₂) or -NR¹¹R¹² group. Particular -NR¹¹R¹² groups are -NHR¹² groups. Groups of this type include those where R¹² is a C₁₋₆alkyl group, for example a methyl, ethyl, or n-propyl group, optionally interrupted by one or more -O- or -S- atoms or -N(R⁷) [e.g. -NH- or -N(CH₃)-] or aminocarbonyloxy groups and optionally substituted by a hydroxyl, carboxyl, carboxyalkyl, e.g. carboxymethyl, carboxamido, amino, -NR¹¹R¹², [for example di-C₁₋ ₆alkylamino such as dimethylamino, C₁₋₆alkylamino such as methylamino, or C₃₋₆ cyclic amino such as morpholinyl, pyrrolidinyl or pyridinyl] or phenyl optionally substituted by one, two or more R¹⁰ substituents. A particularly useful group of compounds according to the invention is that of formula (I) wherein R⁵ is a AlkR⁶, group, where Alk is a C₁₋₆ alkyl and R⁶ is a cycloalkyl or cycloalkenyl group. Another particularly useful group of compounds according to the invention is that of formula (I) where R² is an optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, aryl, aralkoxy or aralkylthio group. A further particularly useful group of compounds of formula (I) are those wherein X is an amino or substituted amino group. In general, in compounds of formula (I) the groups R¹, R³ and R⁴ is each preferably a hydrogen atom. In a further preference, the group R in compounds according to the invention is a -CONHOH or a -CO₂H group or a metabolically labile ester thereof. In a particular preference, however, R is a -CONHOH or a -CO₂H group An especially useful group of compounds according to the invention has the formula (Ia) wherein R, R², R⁵ and X are as defined for formula (I); and the salts, solvates and hydrates thereof. A particularly useful group of compounds of formula (Ia) are those wherein R represents a -CONHOH or -CO₂H group; R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkoxy or aralkylthio group; R⁵ represents a group -AlkR⁶, where Alk is a C₁₋₆ alkyl group and R⁶ is a cycloalkyl or cycloalkenyl group; X is an amino (-NH₂) or substituted amino group; and the salts, solvates and hydrates thereof. Particularly useful compounds of formula (Ia) are those wherein R⁵ is a group -AlkR⁶, and R⁶ is an optionally substituted cyclohexyl group. Compounds of this type in which R⁵ is a cyclohexylC₁₋₆alkyl group, particularly a cyclohexylmethyl group, are especially useful. Other useful compounds of formula (Ia) include those wherein R² represents a C₃₋₆alkyl group, particularly an iso-butyl or n-pentyl group, or a cycloalkylC₃₋₆alkyl group, particularly a cyclohexylpropyl, cyclohexylbutyl or cyclohexylpentyl group, or especially an optionally substituted phenylC₂₋ ₆alkyl group particularly an optionally substituted phenylpentyl group. Optional substituents on the phenyl group may be one, two or more R¹⁰ groups as defined for compounds of formula (I). In the compounds of formula (Ia) X may be a -NH₂ group or a group-NR¹¹R¹² as defined for compounds of formula (I). An especially useful group of compounds according to the invention has the formula (Ia) wherein R² is an optionally substituted phenylC₃₋₆alkyl group, R⁵ is a cyclohexylmethyl group; and X is a amino (-NH₂) or NR¹¹R¹² group. Compounds of this type wherein X is -NH₂ or -NHR¹² are particularly useful. In the compounds of formulae (I) and (1a), when the group R⁵ is a cycloalkylC₁₋₆alkyl group then the chiral centre to which this group is attached preferably has a S-configuration. Particularly preferred compounds according to the invention include: [4-(N-Hydroxyamino)-2(R)-cyclohexylmethylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-N-(Hydroxyamino)-2R-isobutylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-pentylsuccinyl]-L-β-cycohexyalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-isoamylsuccinyl]-L-β-cycohexylalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-isobutyisuccinyl]-L-β-cyclohexylalanine amide; [[4-Hydroxy-2(R)-isobutylsuccinyl]-L-β-cyclohexyalanine]-(N-2-phenylethyl) amide; and [[4-Hydroxy-2(R)-isoamylsuccinyl]-L-β-cyclohexyalanine]-(N-2-phennylethyl) amide. Compounds of general formula (I) may be prepared by any suitable method known in the art and/or by the following process. It will be appreciated that where a particular stereoisomer of formula (I) is required, the synthetic processes described herein may be used with the appropriate homochiral starting material and/or isomers may be resolved from mixtures using conventional separation techniques e.g. hplc Thus for example a compound of formula (I) with S stereochemistry at the chiral centre adjacent to the substituent R⁵ may be prepared using an appropriate homochiral starting material and the techniques described in the Examples. Thus in a second aspect the invention provides a process for preparing a compound of formula (I) in which -CO₂R is -CO₂H may be prepared from a corresponding ester of formula (I) using conventional procedures, depending on the nature of the ester group. Thus, for example, a compound of formula (I) may be prepared by hydrolysis of the corresponding ester, using for example an acid or base optionally in a solvent. Thus for example a compound of formula (I) with S stereochemistry at the chiral centre adjacent to the substituent R⁵ may be prepared using an appropriate homochiral starting material and the techniques described in the Examples. The compounds according to the invention may be prepared by the following processes. In the description and formulae below the groups R, R¹, R², R³, R⁴, R⁵ and X are as defined above, except where otherwise indicated. It will be appreciated that functional groups, such as amino, hydroxyl or carboxyl groups, present in the various compounds described below, and which it is desired to retain, may need to be in protected form before any reaction is initiated. In such instances, removal of the protecting group may be the final step in a particular reaction. Suitable amino or hydroxyl protecting groups include benzyl, benzyloxycarbonyl or t-butyloxycarbonyl groups. These may be removed from a protected derivative by catalytic hydrogenation using for example hydrogen in the presence of a metal catalyst, for example palladium on a support such as carbon in a solvent such as an alcohol e.g. methanol, or by treatment with trimethylsilyl iodide or trifluoroacetic acid in an aqueous solvent. Suitable carboxyl protecting groups include benzyl groups, which may be removed from a protected derivative by the methods just discussed, or alkyl groups, such as a t-butyl group which may be removed from a protected derivative by treatment with trifluoroacetic acid in an aqueous solvent. Other suitable protecting groups and methods for their use will be readily apparent. The formation of the protected amino, hydroxyl or carboxyl group may be achieved using standard alkylation or esterification procedures, for example as described below. Thus according to a further aspect of the invention a compound of formula (I) may be prepared by coupling an acid of formula (II) or an active derivative thereof, with an amino of formula (III) followed by removal of any protecting groups. Active derivatives of acids for formula (II) include for example acid anhydrides, or acid halides, such as acid chlorides. The coupling reaction may be performed using standard conditions for amination reactions of this type. Thus, for example the reaction may be achieved in a solvent, for example an inert organic solvent such as an ether e.g. a cyclic ether such as tetrahydrofuran, an amide e.g. a substituted amide such as dimethylformamide, or a halogenated hydrocarbon such as dichloromethane at a low temperature, e.g. -30°C to amibient temperature, such as -20°C to 0°C, optionally in the presence of a base, e.g. an organic base such as an amino, e.g. triethylamine or a cyclic amino such as N-methylmorpholine. Where an acid of formula (II) is used, the reaction may additionally be performed in the presence of a condensing agent, for example a diimide such as N,N'-dicyclohexylcarbodiimide, advantageously in the presence of a triazole such as I-hydroxybenzotriazole. Alternatively, the acid may be reacted with a chloroformate for example ethylchloroformate, prior to reaction with the amino of formula (III). Free hydroxyl or carboxyl groups in the starting materials of formulae (II) [where R is -CONHOH or CO₂H] and (III) may need to be protected during the coupling reaction. Suitable protecting groups and methods for their removal may be those mentioned above. It will be appreciated that where a particular steroisomer of formula (I) is required, this may be obtained by resolution of a mixture of isomers following the coupling reaction of an acid of formula (II) and an amino of formula (III). Conventional resolution techniques may be used, for example separation of isomers by Chromatography e.g. by use of high performance liquid chrormatography. Where desired, however, appropriate homochiral starting materials may be used in the coupling reaction to yield a particular stereo isomer of formula (I). Thus, in particular process a compound of formula (Ia) may be prepared by reaction of a compound of formula (IIa) with an amino of formula (IIIa) as described above Intermediate acids of formula (II) wherein R is a carboxyl or esterified carboxyl group may be prepared by hydrolysing a corresponding ester of formula (IV) where R¹³ is an alkyl group, for example a methyl or t-butyl group, using for example trifluoroacetic acid, or, when R¹³ is a methyl group using enzymatic hydrolysis, such as for example with α-chymotrypsin, in an aqueous solvent. In this reaction, enzymatic hydrolysis (for example as more particularly described in the Examples herein) usefully provides a method of isomer selection. The ester of formula (IV) may be prepared by esterification of the corresponding acid of formula (V) using an appropriate acyl halide, for example an acyl chloride in a solvent such as an alcohol, e.g. methanol at a low temperature, e.g. around O°C. Acids of formula (V) may be prepared by alkylation of a compound of formula (VI) with an appropriate halide, e.g. a compound R²Hal, where Hal is a halogen atom such as a chlorine or bromine atom in the presence of a base, for example an alkoxide such as sodium ethoxide in a solvent such as an alcohol, e.g. ethanol at ambient temperature, followed by decarboxylation using for example concentrated hydrochloric acid at an elevated temperature, e.g. the reflux temperature. Intermediates of formula (VI) are either known compounds or may be prepared by methods analogous to those used for the preparation of the known compounds. Intermediate acids of formula (IV) wherein R is a -CONHOH group or a protected derivative thereof may be prepared by reaction of an anhydride of formula (VII) with a hydroxylamine such as O-benzylhydroxylamine in a solvent such as tetrahydrofuran at a low temperature, e.g. around -20°C, followed where desired by removal of the protecting group as described above. The intermediate anhydrides of formula (VII) may be prepared for example by heating for example at the reflux temperature, a diacid of formula (V) where R is -CO₂H with an acyl chloride such as acetyl chloride. The homochiral acids of formula (IIa) may be prepared according to another feature of the invention by oxidation of an oxazolidinone of formula (VIII) (where Ph is a phenyl group) using an oxidising agent such as peroxide, e.g. hydrogen peroxide in a solvent such as an ether e.g. a cyclic ether such as tetrahydrofuran, at a low temperature, e.g. around 0°C followed by treatment with a base, such as lithium hydroxide, at an elevated temperature. The compounds of formula (VIII) are novel, particularly useful, intermediates for the preparation of stereoisomers of formula (Ia). The compounds of formula (VIII) may be prepared by reaction of an acyl halide RCH₂CH(R²)COHal (where Hal is a halogen atom such as chloride, bromine or iodine atom) with a solution of (S)-4-(phenylmethyl)-2-oxazolidinone in the presence of a base such as n-butyl lithium in a solvent such as tetrahydrofuran at a low temperature, e.g. around -78°C. Acyl halides RCH₂ CH)(R²)COHal may be prepared by treatment of the corresponding known acids RCH₂CH(R²)CO₂H with conventional halogenating agents for example thionyl halides under standard reaction conditions. In another process according to the invention, a compound of formula (I) where R is a carboxyl group may be prepared by decarboxylation of a corresponding compound of formula (IX). The reaction may be achieved using standard conditions, for example by heating a compound of formula (IX) in an inert solvent, such as an aromatic hydrocarbon, e.g. xylene, at the reflux temperature. The intermediate acids of formula (IX) may be prepared by reaction of a protected acid of formula (X) where R is a protected carboxyl group such as a benzyloxycarbonyl group and Z¹ is a protecting group such as a benzyl group with an amino of formula (III) using reagents and conditions as described above for coupling compounds of formula (II) and (III), followed by removal of the protecting groups. The intermediates of formula (X) may be prepared by treatment of an appropriate malonic ester RCH₂CO₂Z¹ with a halide of formula (XI) (where Hal is a halogen atom, e.g. a chlorine or bromine atom) in the presence of a base such as potassium t-butoxide in a solvent such as dimethylformamide at ambient temperature. Halides of formula (XI) may be prepared by halogenation and subsequent decarboxylation of a di-acid of formula (XII). using for example a halogenating agent such as bromine in a solvent such as diethyl ether at ambient temperature, followed by heating of the resulting halogenated intermediate in a solvent such as an aromatic hydrocarbon e.g. xylene, at the reflux temperature. Intermediates of formula (XII) may be prepared by hydrolysis of the corresponding di-alkylester (e.g. the dimethyl or diethyl ester) using a base such as sodium or potassium hydroxide in a solvent such as an alcohol e.g. methanol at the reflux temperature. The di-alkyl ester starting materials are either known compounds or may be prepared by methods analogous to those used for the preparation of the known compounds, for example as described in the Examples herein. Compounds of formula (I) may also be prepared by interconversion of other compounds of formula (I). Thus, for example, a compound of formula (I) wherein R is a -CONHOH group may be prepared by reaction of a corresponding acid of formula (I) wherein R is a -CO₂H group or an active derivate thereof (for example an acid chloride or an acid anhydride) with hydroxylamine or an O-protected derivative or a salt thereof. The reaction may be performed using the reagents and conditions described above in the preparation of compounds of formula (I) from the starting materials of formulae (II) and (III). In another interconversion process, compounds of formula (I) wherein R is - CO₂H and/or X contains a -CO₂H group may be prepared by hydrolysis of the corresponding esterified compounds (for example where R is a -CO₂R⁸ group and/or X contains a similar group) using conventional procedures, for example by treatment with a base, e.g. an alkali metal hydroxide such as lithium hydroxide in a solvent such as an aqueous alcohol, e.g. aqueous methanol, or by treatment with an acid such as a mineral acid, e.g. hydrochloric acid in the presence of a solvent, e.g. dioxan. Similarly esters of formula (I), for example where R is a CO₂R⁸ group and/or X contains a -CO₂R⁸ group may be prepared by reaction of the corresponding acids, where R is a -CO₂H group and/or X contains a -CO₂H group or an active derivative thereof, with an alcohol R⁸OH using standard conditions. The compounds according to the invention are potent and selective inhibitors of gelatinase. The activity and selectivity of the compounds may be determined by the use of appropriate enzyme inhibition test for example as described in Example A hereinatter. In our tests using this approach, compounds according to the invention have been shown to inhibit gelatinase with Ki values in the picomolar-nanomolar range and to have around a 40 fold or greater selectivity for gelatinase over stromelysin, and around a 20-fold or greater selectivity for gelatinase over collagenase. The ability of compounds of the invention to prevent tumour cell invasion may be demonstrated in a standard mouse model. Thus, briefly, nude mice may be inoculated with a tumour cell line showing gelatinase - dependent invasion and the ability of compounds according to the invention to reduce subsequent lung tumour colonisation may be evaluated in accordance with standard procedures. In out tests, compounds according to the invention, when administered intravenously at 1mg/kg to mice in the above model have reduced lung tumour colonisation to negligable levels. The compounds according to the invention can be expected to be of use to prevent tumour cell metastasis and invasion. The compounds may therefore be of use in the treatment of cancer, particularly in conjunction with radiotherapy, chemotherapy or surgery, or in patients presenting with primary tumours, to control the development of tumour metastasises. Particular cancers may include breast, melanoma, lung, head, neck or bladder cancers. For use according to this aspect of the invention, the compounds of formula (I) may be formulated in a conventional manner, optionally with one or more physiologically acceptable carriers, diluents or excipients. Thus according to a further aspect of the invention we provide a pharmaceutical composition comprising a compound of formula (I) and a pharmaceutically acceptable diluent, carrier or excipient. In a still further aspect the invention provides a process for the production of a pharmaceutical composition comprising bringing a compound of formula (I) into association with a pharmaceutically acceptable diluent, carrier or excipient. Compounds for use according to the present invention may be formulated for oral, buccal, parental or rectal administration or in a form suitable for nasal administration or administration by inhalation or insufflation. For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g. pregelatinised maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g. lactose, microcrystalline cellulose or calcium hydrogen phosphate); lubricants (e.g. magnesium stearate, talc or silica); disintegrants (e.g. potato starch or sodium glycollate); or wetting agents (e.g. sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents, emulsifying agents, non-aqueous vehicles; and preservatives. The preparations may also contain buffer salts, flavouring, colouring and sweetening agents as appropriate. Preparations for oral administration may be suitably formulated to give controlled release of the active compound. For buccal administration the compositions may take the form of tablets or lozenges formulated in conventional manner. The compounds of formula (I) may be formulated for parental administration by injection e.g. by bolus injection or continuous infusion. Formulations for injection may be presented in unit dosage form. The compositions for injection may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilising and/or dispersing agents. Alternatively, the active ingredient may be in powder form for constitution with a suitable vehicle, e.g. sterile pyrogen-free water, before use. The compounds of formula (I) may also be formulated in rectal compositions such as suppositories or retention enemas, e.g. containing conventional suppository bases such as cocoa butter or other glycerides. In addition to the formulations described above the compounds of formula (I) may also be formulated as a depot preparation. Such long acting formulations may be administered by implantation or by intramuscular injection. For nasal administration or administration by inhalation the compounds for use according to the present invention are conventiently delivered in the form of an aerosol spray presentation for pressurised packs or a nebuliser, with the use of suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. The compositions may, if desired, be presented in a pack or dispenser device which may contain one or more unit dosage forms containing the active ingredient. The pack or dispenser device may be accompanied by instructions for admininstration. The doses of compounds of formula (I) used to control the development of tumour metastasises will vary depending on the condition of the patient to be treated but in general may be in the range around 0-5mg to 50mg/kg body weight, particularly from about 1mg to 40mg/kg body weight. Dosage units may be varied according to the route of administration of the compound in accordance with conventional practice. Description of Specific EmbodimentsThe invention is further illustrated in the following non-limiting Examples. In the Examples, the following abbreviations are used: RT -room temperature DCCI -N,N'-dicyclohexylcarbodiimide DMF -dimethylformamide THF -tetrahydrofuran TFA -trifluoroacetic acid RPHPLCreverse phase high performance liquid chromatography HOBT -N-hydroxybenzotriazole EXAMPLE 1[4-(N-hydroxyamino)-2(R)-cyclohexylmethylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amide (I)(R,S)-Cyclohexylmethyl succinic acidSodium ethoxide was prepared by adding sodium metal (2.5g, 108mmoL) to anhydrous ethanol (150ml) under nitrogen. Triethyl 1,1,2-ethanetricarboxylate (26.6g, 25ml, 108mmoL) was added and the mixture stirred at room temperature for 20 minutes. Cyclohexylmethyl bromide (19.12g, 15ml, 108mmoL) was added dropwise over 1 hour and the solution raised to reflux overnight. The precipitated sodium bromide was filtered off and the filtrate concentrated in vacuo. The residue was treated with cold H₂O (200ml) and extracted with diethyl ether (3 x 100ml). The organic layer was dried (Na₂SO₄) and concentrated to give a clear oil. (32.2g). Concentrated hydrochloric acid (200ml) was added to the crude tricarboxylate (32.2g) and the mixture brought to reflux. After 96 hours the reaction was cooled and poured into CH₂Cl₂ (200ml) and extracted. The organic layer was dried (Na₂SO₄) to give the diacid C a white solid (16.0g) ¹H NMR (CDCL₃) δ 0.85 (m, 2H), 1.2 (m, 5H), 1.65 (m, 6H), 2.5 (dd, 1H, J=4 and 16HZ) 2.70 (dd, 1H, J=9 and 16HZ), 2.95 (m, 1H). (R,S) Dimethyl cyclohexylmethyl succinateDAcetyl chloride (4.33g, 3.9ml, 55.2mmoL) was added to anhydrous methanol (50ml) at 0°C and the reaction stirred for 15 min. The reaction was allowed to come to and the diacid C (5.0g, 23.3mmoL) added. Following a 3 hour reflux the reaction was cooled and concentrated in vacuo to give a clear oil which was taken up in ethyl acetate (200ml), washed with saturated sodium bicarbonate, brine, and dried (Na₂SO₄). The solution was evaporated to dryness to afford the diester D as an oil (5.45g). ¹H NMR (CDCL₃) δ 0.85 (m, 2H), 1.2 (m, 6H), 1.65 (m, 5H), 2.42 (dd, 1H, J=6.0 Hz and 16HZ) 2.70 (dd, 1H, J=10.0 and 16HZ), 2.95 (m, 1H), 3.68 (s, 3H), 2.7 (s, 3H). Methyl (R)-2-Cyclohexylmethyl succinateEA solution of α-chymotrypsin (635mg) in H₂O (20ml) was treated with compound D (5.23g, 21.6mmoL) in H₂0 (75ml). A constant pH of 7.8 was maintained by titrating the reaction mixture with 0.1M NaOH using a pH-stat. After 24 hours the solution was washed with diethyl ether and the aqueous layer acidified to pH=2.0 with 1.0MHCL. The resultant solution was concentrated in vacuo to dryness. The residue was sonicated in the presence of diethyl ether and filtered. The ether layer was washed with brine, dried (Na₂SO₄) and concentrated to give the acid E as a clear oil (2.0g). ¹H NMR (CDCL₃) δ 0.9 (m, 2H), 1.25 (m, 6H), 1.65 (m, 5H), 2.42 (dd, 1H, J=5.5 and 17HZ) 2.70 (dd, 1H, J=8 and 17HZ), 2.95 (m, 1H), 3.7 (s, 3H) Methyl(R)-2-Cyclohexylmethyl-succinyl-L-β-cyclohexylalanine-N-(2-phenylethyl) amide(F)To a solution of the acid E (338mg, 1.48mmoL) in dry CH₂Cl₂ (20ml) was added 4-nitrophenol (227mg, 1.63mmoL) and DCCI (336mg, 1.63mmoL). After 1 hour the reaction was filtered, concentrated and dissolved in dry DMF (5ml). L-β-cyclohexylalanine-N-(2-phenylethyl) amide J (359mg, 1.63mmoL) in dry DMF (5ml) was added and the reaction left overnight at 60°C. DMF was removed in vacuo, and the residue dissolved in CH₂Cl₂ and poured into NaHCO₃ (aq). The organic layer was washed with 0.1MHCL and dried (Na₂SO₄). The residue was concentrated in vacuo and purified on silica gel (Merck 9385) using CH₂Cl₂/MeOH 95:5 to give 500mg of F. ¹H NMR (CDCL₃) δ 0.9 (m, 4H), 1.2 (m, 12H), 1.65 (m, 10H), 2.65 (m, 5H), 3.5 (m, 2H), 3.7 (s, 3H), 4.4 (m, 1H), 6.15 (d, 1H), 6.35 (m, 1H), 7.25 (m, 5H). [4-Hydroxy-2R-cyclohexylmethylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideGThe ester F (250mg, 0.5mmoL) in 1,4-dioxan (3ml) was added to 1.5M HCl (3ml). A further 2ml of 1,4-dioxan was added to obtain solution. The reaction was left at 50°C overnight. A further 1.0ml of 1.5M HCl was added followed by 1.0ml of 1,4-dioxan and the reaction left a further 6 hours at 50°C. The solvent was removed in vacuo, the residue dissolved in CH₂Cl₂ and purified on silica gel (Merck 9385) using CH₂Cl₂/MeOH 9:1 to give G as a clear oil (117mg). ¹H NMR (CDCL₃) δ 0.95 (m, 4H), 1.2 (m, 12H), 1.8 (m, 10H), 2.5 (m, 2H), 2.85 (m, 2H), 3.1 (2H, m), 3.5 (m, 1H), 4.45 (m, 1H) [4-(N-Benzyloxyamino)-2R-Cyclohexylmethylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideHThe acid G (117mg, 0.2 5mmoL) was dissolved in dry THF (10ml) and cooled to -20°C. Ethylchloroformate (27mg, 0.25mmoL) and N-methylmorpholine (25mg, 0.25mmoL) were added and the mixture stirred at -20°C for 1 hour. O-Benzylhydroxylamine (30.25mg, 0.25mmoL) was added and the reaction allowed to come to room temperature. Following an overnight reaction, the volatiles were removed under reduced pressure and the residue mixed with diethyl ether. A precipitate formed, the ether was decanted and the residue dissolved in methanol. The product (100mg) was shown to be homogenous on hplc (DYNAMAX C18) eluting with TFA/H₂O/CH₃CN (starting with 0.1:80:20 ending with 0.1:0:100 over 20 min). [4-(N-Hydroxyamino)-2R-cyclohexylmethyl succinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amide ICompound H (100mg) was dissolved in MeOH (20ml) and hydrogenolysed using 5% Pd-C and hydrogen gas. After 1 hour at RT the catalyst was removed by filtration and the product purified on RPHPLC using TFA/H₂O/CH₃CN (starting with 0.1:80:20 ending with 0.1:0:100 over 20 min) to give the titlecompound I (60mg). ¹H NMR (CD₃OD) δ 8.1-8.2 (1H, m), 7.1-7.4 (5H, m), 4.3-4.45 (1H, m), 3.4-3.5 (2H, m), 2.7-2.9 (3H, m), 2.40 (1H, dd), 2.30 (1H, dd), 0.8-2.0 (26H, m) L-β-cyclohexylalanine-N-(2-phenylethyl) amide(J)tBoc-β-cyclohexyl-L-alanine (1.35g, 5mmoL) was dissolved in dry CH₂Cl₂. 4-Nitrophenol (695mg, 5mmoL) was added followed by DCCI (1.03g, 5mmoL). After 1 hour at room temperature the reaction was concentrated in vacuo, ether was added and the solution filtered. The residue was concentrated in vacuo, dissolved in CH₂Cl₂ (10ml) and phenethylamine (690µl, 5.5mmoL) was added. The reaction was poured into NaHCO₃ and extracted with CH₂Cl₂ (3 x 20ml), was dried (Na₂SO₄) and concentrated in vacuo. Purification on silica gel (Merck 9385) using CH₂Cl₂→CH₂Cl₂/MeOH 85:15) gave a clean oil (900mg) which was dissolved in CH₂Cl₂/TFA (9:1) and left a RT for 30 min. The reaction was concentrated in vacuo, dissolved in CH₂Cl₂ (50ml) and poured into Na₂CO₃ (aq). The organic layer was separated, dried (Na₂SO₄) and concentrated in vacuo to give an oil which was purified on silica gel (Merck 9385) using CH₂Cl₂/MeOH/NEt₃ 96:3:1 to give the titlecompound J as an oil (500mg). ¹H NMR (CDCL₃) δ 0.95 (m, 2H), 1.25 (m, 6H), 1.55 (bs, 2H), 1.65 (m, 5H), 2.8 (t, 2H, J=6HZ), 3.4 (dd, 1H, J=3 and 10HZ), 3.5 (dd, 2H, J=6 and 12HZ), 7.2 (m, 5H) Example 2[4-N-(Hydroxyamino)-2R-isobutylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideR,S - Isobutylsuccinic acid KSodium ethoxide was prepared by adding sodium metal (2.5g, 108mmoL) to anhydrous ethanol (150ml) under nitrogen. Triethyl 1,1,2-ethanetricarboxylate (26.6g, 25ml, 108mmoL) was added and the mixture stirred at room temperature (RT) for 20 minutes. Isobutyl bromide (19.12g, 15ml, 108mmoL) was added dropwise over 1 hour and the solution raised to reflux overnight. The precipitated sodium bromide was filtered off and the filtrate concentrated in vacuo. The residue was treated with cold H₂O (200ml) and extracted with diethyl ether (3 x 100ml). The organic layer was dried (Na₂SO₄) and concentrated to give a clear oil (32.2g) which was refluxed with concentrated hydrochloric acid for 96 hours. On cooling, a white crystalline solid precipitated which was filtered, washed with ice cold water and dried in vacuo to give the titlecompound K (11.0g) ¹HNMR (CDCL₃) δ 0.85 (3H, d, J = 6Hz), 0.90 (3H, d, J=6Hz), 1.3-1.45 (1H, m), 1.55-1.75 (2H, m), 2.50 (1H, dd, J=6 and 18 Hz), 2.70 (1H, dd, J=9 and 18 Hz), 2.85-2.95 (1H, m). 3-(R,S)-Isobutylsuccinic anhydrideLThe diacid K (10.21g, 59mmoL) was treated with acetyl chloride (27ml, 376mmoL) under reflux for 2.1/2 hours. Volatiles were removed under reduced pressure to give the anhydride L (9.37g, 100%) as a brownish oil. ¹HNMR (CDCL₃) 0.95 (3H, d, J = 6Hz), 1.05 (3H, d, J=6Hz), 1.48-1.90 (3H, m), 2.65 (1H, dd, J=7 and 18Hz), 3.10 (1H, dd, J = 9 and 18 Hz), 3.15-3.25 (1H, m). [4-(N-Benzyloxyamino)-2 R,S-Isobutyl) succinic acidMO-Benzyl hydroxylamine (7.8g, 63.4mmoL) in dry THF (50ml) was added dropwise (over 1 hour) to a solution of the anhydride L (9.37g, 60.0mmoL) in dry THF (100ml) at -20°C. After stirring a further 1 hour, volatiles were removed in vacuo and the residue taken up in ethyl acetate. After washing with 1.0MHCL (x3), the organic phase was dried (MgSO₄) and evaporated to give a white solid. The crude solid was dissolved in hot diethyl ether and filtered. Colourless crystals of the acid M deposited on standing (6.7g, 41%). ¹HNMR (CDCL₃) δ 0.8-1.0 (6H, m), 1.2-1.4 (3H, m), 2.1-2.4 (2H, m), 2.8-3.0 (1H, m), 4.85 (2H, s), 7.3 (5H,bs), 8.6 (1H, bs). [4-(N-Benzyloxyamino)-2R,S-Isobutyl succinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideNThe acid M (502mg, 1.8mmoL) was dissolved in dry THF (20ml) and cooled to -20°C. Ethylchloroformate (245mg, 233µl, 1.8mmoL) and N-methyl morpholine was added and the suspension left for 1 hour at -20°C. A DMF solution (10ml) of L-β-Cyclohexylalanine-N-(2phenylethyl)amide J (500mg, 1.8mmoL) was added dropwise. Once the addition was completed the cooling bath was removed and the reaction allowed to warm up to room temperature overnight. The organic solution was poured into 10% HCl and extracted with ethyl acetate (x3). The organic layer was dried (MgSO₄) and concentrated in vacuo to give a solid. Purification on silica gel (Merck 9385) using CH₂Cl₂/MeOH 98:2 gave the titlecompound N as a mixture of diastereoisomers (200mg). ¹HNMR (CDCL₃) 0.7-2.0 (22H, m), 2.1-2.5 (1H, m), 2.6-2.9 (4H, m), 3.3-3.55 (2H, m), 4.35-4.55 (1H, m), 4.7-4.9 (2H,m), 6.1-6.4 (1H,m), 6.65-6.9 (1H, m) 7.05-7.4 (10H, m) 9.05-9.30 (1H,m). [4-(N-Hydroxyamino)-2,R,S-Isobutylsuccinyl)-L-β-cyclohexylalanine -N-(2-phenylethyl) amideThe mixture of diastereoisomers N was dissolved in degassed MeOH (20ml) and hydrogenolysed using 5% Pd-C and hydrogen gas. After 1 hour at RT the catalyst was filtered off and the product purified on RPHPLC using 0.1%TFA/H₂O→ 0.1%TFA/CH₃CN (43:57) isocratically. Peak 1 (elution time 11.2 min) and Peak 2 (elution time 14 min) was collected and dried to give 64mg and 56 mg of the titleisomers respectively. PEAK 1 ¹HNMR (CD₃OD) 0.8-1.0 (8H, m), 1.05-1.75 (14H, m), 2.1-2.4 (2H, m), 2.7-2.85 (3H, m), 3.35-3.50 (2H, m), 4.30 (1H, t, J=6Hz), 7.05-7.3 (5H, m) PEAK 2 ¹HNMR (CD₃OD) 0.8-1.8 (22H, m), 2.05-2.20 (1H, m), 2.35-2.5 (1H, m), 2.7-2.9 (3H, m), 3.35-3.5 (2H, m), 4.30-4.40 (1H, m), 7.1-7.35 (5H, m) The following compounds of Examples 3-4 were prepared in a similar manner to the compounds of Examples 1 and 2 using the appropriate analogous starting materials Example 3[4-(N-Hydroxyamino)-2R-N-pentylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideThe title compound was prepared following the general teaching of Example 2. ¹HNMR (CD₃OD) δ 7.15-7.35 (5H, mult), 4.35 (1H, t), 3.30-3.50 (2H, mult), 2.80 (2H, t), 2.70 (1H, mult), 2.15-2.40 (2H, 2dd), 0.90-1.80 (24H, mult). Example 4[4-(N-Hydroxyamino)-2R-isoamytsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amideThe title compound was prepared following the general teaching of Example 2 ¹HNMR (CD₃OD) δ 7.15-7.35 (5H, mult), 4.30 (1H, t), 3.30-3.50 (2H, mult), 2.80 (2H, t), 2.70 (1H, mult), 2.15-2.40 (2H, 2dd), 0.90-1.80 (24H, mult). Example 5(Comparative Example)Methyl-(2-methoxycarbonyl)-5-phenylpentanoate (I)Sodium methoxide was prepared by adding sodium metal (3.66g, 159mmol) to dry methanol (200ml) under nitrogen. Upon dissolution dimethyl malonate (20g, 17.3ml, 151mmol) was added dropwise followed by dropwise addition of 1-bromo-3-phenylpropane (30.1g, 23ml, 151mmol). The mixture was refluxed for 18 hours, cooled and partitioned between phosphate buffer (pH=6.5) and diethyl ether. The organic layer was separated, dried (MgS0₄) and concentrated invacuo. Purification on silica gel (Merck 9385), eluting with Et₂O/hexane (25:75) gave the compound I as a colourless oil (23.26g, 62%). ¹H NMR (CDCl₃) δ 7.2-7.45 (5H, m), 3.78 (6H, s), 3.45 (1H, t), 2.70 (2H, t), 1.95-2.15 (2H, m), 1.65-1.85 (2H, m). tert -Butyl-2(R,S)-bromo-5-phenylpentanoate (II)Methyl-(2-methoxycarbonyl)-5-phenylpentanoate (I), (8.43g, 33.7mmol) was dissolved in MeOH (40ml) and NaOH (3.37g, 84.25mmoL) dissolved in H₂O (10ml) was added. The mixture was refluxed for 18 hours, cooled, concentrated invacuo and addified to pH=1 using concentrated HCl. The aqueous solution was extracted with Et₂O (3 x 50ml), dried (MgSO₄) and concentrated invacuo to give a white solid (6.3g). The white solid was dissolved in diethyl ether and bromine (1.5ml, 28.2mmol) added dropwise. Decolourization occurred after 10 minutes and the reaction was stirred at room temperature for a further 2 hours. Water was added carefully and the product extracted into Et₂O (3 x 100ml), dried (MgSO₄) and concentrated invacuo. The residue was dissolved in xylene and refluxed for 24 hours. The solvent was removed under reduced pressure and the residue taken up in CH₂Cl₂ (50ml) and the solution was cooled to -40°C. Isobutene was condensed until the reaction volume doubled and concentrated H₂SO₄ (1ml) was added dropwise. The reaction mixture was allowed to warm to room temperature overnight and the mixture poured into aqueous NaHCO₃ (10%). The organic layer separated and dried (MgSO₄). Purification on silica gel (Merck 9385) eluting with Et₂O/hexane (2.5:97.5) gave the compound II (4.0g) as a solid. ¹H NMR (CDCl₃) δ 7.1-7.3 (5H, m ), 4.10 (1H, t), 2.65 (2H, t), 1.9-2.15 (2H, m), 1.55-1.90 (2H, m), 1.45 (9H, s). Benzyl-[2-benzyloxycarbonyl-3(R,S)-tert-butoxycarbonyl]-6-phenylhexanoate (III)Dibenzyl malonate (3.53g, 12.5mmol) was dissolved in DMF (20ml) and cooled to 0°C. Potassium t-butoxide (1.39g, 12.5mmol) was added as a solid and upon dissolution, tert-butyl-2(R,S)-bromo-5-phenylpentanoate (II) (3.90g, 12.5mmol) in dry DMF (10ml) was added dropwise over 30 minutes. The reaction was allowed to warm up to room temperature overnight and partitioned between EtOAC and saturated aqueous ammonium chloride. The organic layer was separated, dried (MgSO₄) and concentrated invacuo. The residue was purified on silica gel (Merck 9385) eluting with 10→15% Et₂O in hexane to give the compound (III) (4.9g). ¹H NMR (CDCl₃) δ 7.05-7.55 (15H, m), 5.1-5.2 (4H, m), 3.8 (1H, d), 3.05-3.15 (1H, m), 2.40-2.70 (2H, m), 1.45-1.80 (4H, m), 1.35 (9H, s). Benzyl-[2-benzyloxycarbonyl-3(R,S)-(3-phenylpropyl)] succinate (IV)Benzyl-[2-benzyloxycarbonyl-3(R,S)-tert-butoxycarbonyl]-6-phenylhexanoate (III) (4.9g, 9.5mmol) was dissolved in TFA/H₂O (10ml, 9.5:0.5v/v) and allowed to stand at 4°C for 2 days. The TFA was removed under reduced pressure and the residue partitioned between CH₂Cl₂ and H₂O. The organic layer was separated, dried (MgSO₄) and concentrated invacuo to give the compound (IV) (4.36g) as a white solid. ¹H NMR (CDCl₃) δ 7.0-7.35 (15H, m), 5.05-5.20 (4H, m), 3.82 (1H, d), 3.15-3.28 (1H, m), 2.38-2.58 (2H, m), 1.48-1.80 (4H, m). [4-Benzyloxy-3-benzyloxycarbonyl-2(R,S)-(3-phenylpropyl)succinyll-L-β-cyclohexylalanine-(N-2-phenylethyl) amide (V)Benzyl-[2-benzyloxycarbonyl-3(R,S)-(3-phenylpropyl)] succinate (IV) (2.3g, 5mmoL) was dissolved in dry DMF (20ml). To this was added HOBT (0.75g, 5mmoL), N-methylmorpholine (55µl, 5mmoL) and L-β-cyclohexylalanine-(N-2-phenylethyl) amide (J) (1.37g, 5mmoL). The solution was cooled to 0°C and DCCI (1.03g, 5mmoL) in dry DMF (10ml) was added over a ten minute period. The reaction mixture was allowed to warm up to RT overnight, poured into EtOAc and washed with 10%w/v citric acid. The organic layer was separated, washed with aqueous NaHCO₃ (10%w/v) and dried (MgSO₄). The solvent was removed invacuo to give an oily solid (3.4g) which was purified on silica gel (Merck 9385) using MeOH/CH₂Cl₂ (0.5→1% MeOH) to give the compound V as a glass. ¹H NMR (CDCl₃) δ 7.0-7.55 (20H, m), 6.2 (1H, t), 6.0 (1H, d), 5.0-5.2 (4H, m), 4.3-4.55 (1H, m), 3.8-3.94 (1H, m), 3.2-3.6 (2H, m), 2.7-2.9 (3H, m), 2.4-2.55 (2H, m), 0.7-2.0 (17H, m). [4-Hydroxy-2(R)-(3-phenylpropyl)succinnyl]-L-β-cyclohexylalanine-(N-2-phenylethyl) amide (VI)[4-Benzyloxy-3-benzyloxycarbonyl-2(R,S)-(3-phenylpropyl)succinyl]-L-β-cyclohexylalanine-(N-2-phenylethyl) amide (V) (340mg) was dissolved in MeOH and treated with hydrogen over Pdon C for 18 hours. The catalyst was filtered and the solvent removed under vacuum. The residue was taken up in neat xylene and heated under reflux for 15 minutes. The xylene was removed under vacuum to give a yellow gum which was purified on RPHLC using TFA/H₂O/CH₃CN (starting with 0.1:50:50 ending with 0.1:0:100 over 20 minutes) to give the compound (VI) PEAK 1 43.5mg and the other diastereoisomer PEAK 2 (47mg) ¹H NMR PEAK 1 (CD₃OD) δ 7.1-7.3 (10H, m), 4.32 (1H, dd), 3.25-3.45 (2H, m); 2.25-2.80 (7H, m), 0.8-1.8 (17H, m). ¹H NMR PEAK 2 (CD₃OD) δ 7.1-.7.25 (10H, m), 4.25-4.3 (1H, m), 3.25-3.50 (2H, m), 2.25-2.95 (&H, m), 0.7-1.85 (17H,.m). The following compounds of Examples 6-7 were prepared following the procedures of Example 5 and using the appropriate analogous starting materials. Example 6[4-Hydroxy-2(R)-isobutylsuccinyl]-L-β-cyclohexylalanine]-(N-2-phenylethyl) amide¹H NMR (CD₃OD) δ 7.10-7.60 (5H, m), 4.45 (1H, dd), 3.30-3.80 (2H, m), 2.35-3.10 (5H, m), 0.75-1.95 (22H, m). Example 7[4-Hydroxy-2(R)-isoamylsuccinyl]-L-β-cyclohexylalanine]-(N-2-phenylethyl) amide¹H NMR (CD₃OD) δ 7.15-7.45 (5H, m), 4.60 (1H, dd), 3.50-3.80 (2H, m), 2.90 (2H, t), 2.80 (1H, dd), 2.55 (1H, dd), 0.90-1.90 (24H, m).
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A compound of formula (I): wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R¹ represents a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group; R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, aralkoxy, or aralkylthio group, or an amino (-NH₂), substituted amino, carboxyl (-CO₂H) or esterified carboxyl group, provided that R² is not an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R³ represents a hydrogen atom or an alkyl group; R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents a group -[Alk]nR⁶ where Alk is an alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group], n is zero or an integer 1, and R⁶ is an optionally substituted cycloalkyl or cycloalkenyl group; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. A compound according to Claim 1 wherein R represents a -CONHOH or carboxyl (-CO₂H) group. A compound according to Claims 1 or 2 wherein R¹, R³ and R⁴ is each a hydrogen atom. A compound according to any of Claims 1-3 wherein R² is an optionally substituted alkyl, cycloalkyl, cycloalkylalkyl aryl, aralkoxy or aralkylthio group. A compound according to any of the preceding claims wherein R⁵ is a AlkR⁶ group where Alk is a C₁₋₆alkyl and R⁶ is a cycloalkyl or cycloalkenyl group. A compound according to any of the preceding claims wherein X is an amino or substituted amino group. A compound of formula (Ia) wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, aralkoxy, or aralkylthio group, or an amino (-NH₂), substituted amino, carboxyl (-CO₂H) or esterified carboxyl group; provided that R² is not an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R⁵ represents a group -[Alk]nR⁶ where Alk is an alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group], n is zero or an integer 1, and R⁶ is an optionally substituted cycloalkyl or cycloalkenyl group; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. A compound according to Claim 7 wherein R represents a -CONHOH or -CO₂H group;R² represents an optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkoxy or aralkylthio group; R⁵ represents a group -AlkR⁶, where Alk is a C₁₋₆alkyl group and R⁶ is a cycloalkyl or cycloalkenyl group; X is an amino (-NH₂) or substituted amino group; and the salts, solvates and hydrates thereof. A compound according to Claim 8 where R⁵ represents a cyclohexylC₁₋₆alkyl group. A compound according to Claim 9 where R⁵ represents a cyclohexylmethyl group. [4-(N-Hydroxyamino)-2(R)-cyclohexylmethylsuccinyl)-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-N-(Hydroxyamino)-2R-isobutylsuccinyl)-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-pentylsuccinyl]-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-isoamylsuccinyl)-L-β-cyclohexylalanine-N-(2-phenylethyl) amide; [4-(N-Hydroxyamino)-2R-isobutylsuccinyl)-L-β-cyclohexylalanine amide; [[4-Hydroxy-2(R)-isobutylsuccinyl]-L-β-cyclohexylalanine]-(N-2-phenylethyl) amide; [[4-Hydroxy-2(R)-isoamylsuccinyl]-L-β-cyclohexylalanine]-(N-2-phenylethyl) amide; and the salts, solvates and hydrates thereof. A pharmaceutical composition comprising a compound according to any one of Claims 1 to 11 and a pharmaceutically acceptable diluent, carrier or excipient. A process for preparing a compound of formula (I) as defined in Claim 1, the process comprising: (a) coupling an acid of formula (II) or an active and/or protected derivative thereof, with an amine of formula (III) or a protected derivative thereof followed by removal of any protecting groups; or (b) decarboxylating a compound of formula (IX) to produce a compound of formula (I) wherein R is a -CO₂H group; and/or (c) interconverting a compound of formula (I).
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CELLTECH LTD; CELLTECH LIMITED
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BEELEY NIGEL ROBERT ARNOLD; MILLICAN THOMAS ANDREW; MORPHY JOHN RICHARD; PORTER JOHN ROBERT; BEELEY, NIGEL ROBERT ARNOLD; MILLICAN, THOMAS ANDREW; MORPHY, JOHN RICHARD; PORTER, JOHN ROBERT
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EP-0489578-B1
| 489,578 |
EP
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B1
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EN
| 19,950,802 | 1,992 | 20,100,220 |
new
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G01V3
| null |
G01R33, G01V3, G01N24
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G01R 33/563C, S01R33:44A, G01V 3/32
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Apparatus and technique for NMR diffusion measurement
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A method for conducting borehole NMR measurements comprising the steps of: providing a magnetic field and a magnetic field gradient at a desired location along a borehole; carrying out at least one NMR experiment in the presence of the magnetic field gradient; sensing the diffusion effect on the decay of at least the first echo; and determining therefrom the diffusion coefficient. Apparatus for carrying out the method is also described.
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FIELD OF THE INVENTIONThe present invention relates to borehole measurements and more particularly to borehole measurements employing nuclear magnetic resonance (NMR). BACKGROUND OF THE INVENTIONThere are known in the patent literature various techniques for carrying out borehole measurements employing NMR. Particularly useful techniques and apparatus for carrying out such techniques are described in U.S. Patents 4,710,713, 4,717,877 and 4,717,878 of the present assignee which describe the use of a gradient magnetic field in borehole NMR measurements. U.S. Patent 4,933,638 describes a technique which is based thereon. It is known to carry out laboratory tests of the self-diffusion coefficient, i.e., the rate at which molecules of a material randomly travel within the bulk of the same material, on cores. Providing the cores for testing is a very expensive and time consuming process and is not suitable for sampling a large extent of a borehole. A representative listing of relevant publications in this field is set forth hereinbelow: J.H. Simpson and H.Y. Carr, Diffusion and Nuclear Spin Relaxation in Water, The Physical Review, 111, No. 5, Sept 1, 1958, p 1201 ff. D.C. Douglass and D.W. McCall, Diffusion in Paraffin Hydrocarbons, Journal of Physical Chemistry, 62, 1102 (1958); D.E. Woessner, N.M.R. Spin Echo Self Diffusion Measurements on Fluids Undergoing Restricted Diffusion, Journal of Physical Chemistry, 87, 1306 (1963); R.C. Wayne and R. M. Cotts, Nuclear Magnetic Resonance Study of Self-Diffusion in a Bounded Medium, Physical Review, 151, No. 1, 4 November, 1964; E. O. Stejskql and J.E. Tanner, Spin Diffusion Measurements: Spin Echoes in the Presence of a Time Dependent Field Gradient, The Journal of Chemical Physics, Vol. 42, No. 1, 288-292, 1 January, 1965. K.J. Packer and C. Rees, Pulsed NMR Studies of Restricted Diffusion, Journal of Colloid and Interface Science, Vol. 40, No. 2, August, 1972; C.H. Neuman, Spin echo of spins diffusing in a bounded medium, The Journal of Chemical Physics, Vol. 60, No. 11, 1 June, 1974; W.D. Williams, E.F.W. Seymour and R. M. Cotts, A Pulsed Gradient Multiple-Spin Echo NMR Technique for Measuring Diffusion in the Presence of Background Magnetic Field Gradients, Journal of Magnetic Resonance 31, 271 - 282, (1978); U.S. Patent 4,719,423 describes NMR imaging of materials for transport properties including diffusion coefficients. This patent relates to imaging of core samples and not in situ; P.T. Callaghan, D. Macgowan, K.J. Packer and F.O. Zelaya, High Resolution q-space Imaging in Porous Structure, submitted for publication in the Journal of Magnetic Resonance, 1990; U.S. Patent 4,350,955 of J.A. Jackson et al. and other publications of J.A. Jackson on the same general subject. SUMMARY OF THE INVENTIONThe present invention seeks to provide a technique and apparatus for conducting borehole NMR measurements of self-diffusion coefficient and the intrinsic transverse relaxation time. There is thus provided in accordance with a preferred embodiment of the present invention a technique for conducting borehole NMR measurements including the steps of providing a magnetic field gradient at a desired location along a borehole, carrying out at least one and preferably two or more NMR experiments in the presence of the magnetic field gradient, sensing the diffusion effect on the decay of at least the first echo and determining therefrom the diffusion coefficient. In accordance with one embodiment of the invention, the magnetic field gradient is constant over time. Alternatively, a switched magnetic field gradient may be provided. In accordance with one embodiment of the invention the step of carrying out at least one NMR experiment includes carrying out two NMR experiments such that they differ in at least one of the following parameters: 1. the time the molecules are allowed to diffuse, 2. the magnitude of the magnetic field gradient and 3. the time over which the pulses are applied if magnetic field gradient pulses are used. More particularly, the two experiments may differ only in the echo spacing. In such case, the T₂ (transverse relaxation time) and D (diffusion coefficient) can be extracted from the measured amplitudes and decay rates. Alternatively, when the gradients are constant and are themselves a function of the magnetic field strength, the two experiments may differ in the applied RF frequency. The difference in frequency is accompanied by a change in the magnetic field gradient strength. In an extension of the above-described technique, more than two such experiments can be conducted. Results of repeated experiments can then be integrated and averaged to enhance the signal-to-noise ratio and the two or more different experiments may be used for calculating the Diffusion Coefficient and the transverse relaxation time T₂. In another extension, several such experiments might all be combined into a single experiment by acquiring all the required data from the signals of a single excitation. This can be accomplished by changing the abovementioned parameters during a single sequence. As an illustrative example: the first few echoes are spaced by one fixed time interval, the next few by another, and so on. A single experiment with fixed parameters such as echo spacing, magnetic field gradient magnitude and duration may be carried out to give an upper bound to the diffusion coefficient value, a lower bound to T₂ or either T₂ or D when one of them is known a priori. In accordance with a preferred embodiment of the present invention, the diffusion coefficient D can be employed to determine at least one of the following petrophysical parameters: Water/hydrocarbon discrimination; Water and hydrocarbon saturation levels; Permeability; Pore size and pore size distribution; Oil viscosity; Formation form factor F, which is a measure of the average increase in electrical resistance due to the formation tortuosity; and q-space imaging of the formation. There is provided in accordance with the present invention an apparatus for conducting borehole NMR measurements; this apparatus is set out in independent claim 7. The methods described hereinabove are suitable for use in environments other than borehole environments and with materials other than those found in boreholes. The methods have the advantage that the material being tested may be located outside the testing apparatus. BRIEF DESCRIPTION OF THE DRAWINGSThe present invention will be understood and appreciated more fully from the following detailed description, taken in conjunction with the drawings in which: Fig. 1A is a block diagram illustration of apparatus for carrying out borehole diffusion coefficient determinations in accordance with a preferred embodiment of the present invention, wherein the magnetic field gradient is constant over time; Fig. 1B is a block diagram illustration of apparatus for carrying out borehole diffusion coefficient determinations in accordance with an alternative embodiment of the present invention, wherein the magnetic field gradient is pulsed. Figs. 2A and 2B are illustrations of RF pulses and echoes and Magnetic Field Gradient Sequences respectively which are employed in accordance with one embodiment of the present invention; Figs. 3A and 3B are illustrations of RF pulses and echoes and Magnetic Field Gradient Sequences respectively which are employed in accordance with one embodiment of the present invention. DETAILED DESCRIPTION OF A PREFERRED EMBODIMENTReference is now made to Fig. 1A, which illustrates, in relatively general form, apparatus for carrying out NMR borehole diffusion coefficient determinations in accordance with a preferred embodiment of the present invention. The apparatus includes a first portion 6, which is arranged to be lowered into a borehole 7 having a borehole longitudinal axis 8 in order to examine the nature of materials in the vicinity of the borehole lying in a region 9 of generally cylindrical configuration spaced from and surrounding the borehole. The first portion 6 preferably comprises a generally cylindrical permanent magnet 10, preferably having a circular cross - section and arranged along a permanent magnet longitudinal axis 11 which is preferably coaxial with the longitudinal axis 8 of the borehole. According to an alternative embodiment of the invention a plurality of permanent magnets 10 may be employed. Throughout the specification, the one or more permanent magnets 10 will be considered together and referred to as permanent magnet 10 and their common longitudinal axis will be identified as longitudinal axis 11. The first portion 6 also comprises one or more coil windings 16 which preferably are arranged on the permanent magnet surface such that each coil turn lies in a plane substantially parallel to a plane containing permanent magnet magnetization axis 12 and longitudinal axis 11. Specifically, the axis 13 of the coil windings 16 is substantially perpendicular to both longitudinal axis 11 of the borehole and axis 12 of the permanent magnet magnetization. The permanent magnet 10 and coil windings 16 are preferably housed in a non-conductive, non-ferromagnetic protective housing 18. The housing and its contents hereinafter will be referred to as a probe 19. The coil windings 16, together with a transmitter/receiver (T/R) matching circuit 20 define a transmitter/receiver (T/R) circuit. T/R matching circuit 20 typically includes a resonance capacitor, a T/R switch and both to-transmitter and to-receiver matching circuitry and is coupled to a RF power amplifier 24 and to a receiver preamplifier 26. All of the elements described hereinabove are normally contained in a housing 28 which is passed through the borehole. Alternatively some of the above elements may not be contained in the housing 28 and may be located above ground. Indicated by block 30 is control circuitry for the logging apparatus including a computer 32, which provides a control output to a pulse programmer 34 which receives an RF input from a variable frequency RF source 36. Pulse programmer 34 controls the operation of the variable frequency RF source 36 as well as an RF driver 38, which receives an input from variable frequency RF source 36 and outputs to RF power amplifier 24. The output of RF receiver preamplifier 26 is supplied to an RF receiver 40 which receives an input from a phase shifter 44. Phase shifter 44 receives an input from variable frequency RF source 36. Receiver 40 outputs via an A/D converter with a buffer 46 to computer 32 for providing desired well logging output data for further use and analysis. Some or all of the elements described hereinabove as being in block 30 are preferably disposed downhole. Alternatively such elements may be disposed in an above-ground housing. Reference is now made to Fig. 1B, which illustrates, in relatively general form, apparatus for carrying out NMR borehole diffusion coefficient determinations in accordance with an alternative preferred embodiment of the present invention. The apparatus includes a first portion 106, which is arranged to be lowered into a borehole 107 in order to examine the nature of materials in the vicinity of the borehole. The first portion 106 comprises a magnet or a plurality of magnets 108 which generate a preferably substantially uniform static magnetic field in a volume of investigation 109. The first portion 106 also comprises an RF antenna coil 116 which produces an RF magnetic field at the volume of investigation 109 which field is substantially perpendicular to the static magnetic field. A magnetic field gradient coil, or plurality of coils, 110 generates a magnetic field gradient at the volume of investigation 109. This additional contribution to the magnetic field has a field direction preferably collinear with the substantially uniform field and has a substantially uniform magnetic field gradient, which may or may not be switched on and off by switching the dc current flowing through the coil or coils 110. The magnet or magnets 108, antenna 116 and the gradient coil 110 constituting portion 106 are also referred to as a probe. The antenna together with a transmitter/receiver (T/R) matching circuit 120 typically include a resonance capacitor, a T/R switch and both to-transmitter and to-receiver matching circuitry and are coupled to an RF power amplifier 124 and a receiver preamplifier 126. A power supply 129 provides the dc current required for the magnetic field gradient generating coils 110. All the elements described hereinabove are normally contained in a housing 128 which is passed through the borehole. Alternatively, some of the above elements may be located above ground. Indicated in a block 130 is control circuitry for the logging apparatus which may be generally identical to that described above with reference to block 30 in connection with the embodiment of Fig. 1A, with the addition of a pulse programmer 146. Pulse programmer 146 controls the gradient coil power supply 129 enabling and disabling the flow of current, and hence the generation of field gradients, according to the commands of the computer 32. Some or all of the elements described hereinabove as being disposed in an above-ground housing, may instead be disposed below ground. Reference is now made to Figs. 2A and 2B which illustrate RF pulses and echoes and Magnetic Field Gradient Sequences respectively which are employed in accordance with one embodiment of the present invention. In this embodiment of the invention, the following operational steps take place: 1. A static magnetic field is applied to polarize the nuclear spins in the material at a given region of the borehole, thus creating bulk magnetization at the region of interest. The field and the collinear magnetization thus produced define a vertical direction. 2. A magnetic field gradient is applied at the region of interest. This gradient field might or might not be part of the static magnetic field of the first step. 3. An RF field is applied to the region of interest at a preselected frequency, duration and magnitude in order to cause at least part of the magnetization to lie in a horizontal plane, defined relative to the vertical axis. 4. A time interval t through which atoms and molecules of the material in the region of interest may diffuse within a fixed magnetic gradient field. 5. A refocusing RF pulse is applied to the region of interest. 6. Step 4 is repeated. 7. The NMR spin echo is acquired. 8. The diffusion coefficient D or an upper bound thereof, or the spin echo decay T₂ or a lower bound thereof is derived from the echo amplitude. 9. Steps 1 through 7 are repeated at least once, with different t or magnetic field gradient strength. 10. D and/or T₂ are derived from echo amplitudes of some or all of the experiments. It is appreciated that steps 4 through 7 may be repeated multiple times successively in order to obtain a sufficiently long echo amplitude train, from which the transverse relaxation time may more meaningfully be derived. It is further appreciated that step 8 is not required if both D and T₂ are unknown and neither could be considered as dominating the decay rate. Steps 9 and 10 are not required if either D or T₂ is known. In that case, the unknown T₂ or D can be derived from a single experiment. Likewise, no more than one experiment is required when either D or T₂ is known to substantially dominate the decay of the echo amplitude. The advantage of repeating the experiment and integrating the measurement readings in order to obtain statistically valid and meaningful results is also appreciated. It is also recognized that step 5 might alternatively be replaced by application of two or more pulses whose combined effect is the refocusing of the nuclear spins yielding a stimulated echo at step 7 and allowing more time for diffusion in between these pulses. Reference is now made to Figs. 3A and 3B which illustrate RF pulses and echoes and Magnetic Field Gradient Sequences respectively, which are employed in accordance with another embodiment of the present invention. In this embodiment of the invention, the following operational steps take place: 1. Step 1 described above. 2. Step 3 described above. 3. A time-switched magnetic field gradient pulse is applied through which the atoms and molecules of the material in the region of interest may diffuse. Typical pulse amplitude, duration and frequency are 0.1-30 G/cm for 0.1-10 ms. 4. Step 5 described above. 5. Repeat step 3. 6. Step 7 described above. 7. Derive the diffusion coefficient D, or an upper bound thereof, or the spin echo decay T2 or a lower bound thereof, from the echo amplitudes. 8. Repeat steps 1 through 6 with a different value for at least one of the following variables: magnetic field gradient strength of steps 3 and 5; magnetic field gradient duration of steps 3 and 5; timing of steps 3,4,5 and 7. 9. Derive the diffusion coefficient and/or T2 from the acquired NMR data. It is appreciated that steps 3 through 6 may be repeated multiple times successively in order to obtain a sufficiently long echo amplitude train, from which the transverse relaxation time may more meaningfully be derived. It is further appreciated that step 7 is not required if both D and T2 are unknown and neither could be considered as dominating the decay rate. Steps 8 and 9 are not required if either D or T2 is known. In that case, the unknown T2 or D can be derived from a single experiment. Likewise, no more than one experiment is required when either D or T2 is known to substantially dominate the decay of the echo amplitude. It is further appreciated that time dependency of the magnetic field gradient other than the square pulse of Fig. 3B may be used. Specifically, when the pulsed gradient is switched off, the gradient strength should not necessarily diminish and sinusoidal and other dependencies might be employed. The advantage of repeating the experiment and integrating the measurement readings in order to obtain statistically valid and meaningful results is also appreciated. It is also recognized that step 4 might alternatively be replaced by application of two or more pulses whose combined effect is the refocusing of the nuclear spins yielding a stimulated echo at step 6 and allowing more time for diffusion in between these pulses. The derivation of the diffusion coefficient D may be carried out using the following equations for the constant gradient case: an = Ae -nte(1/T2 + D(ΓGte)2/12)or for the pulsed gradient: an = A e-n(te/T2 + D (ΓGδ)2(delta - δ/2)) whereA is the magnitude of the signal at te → 0 or zero time. A might or might not be known. nis the echo number. anis its measured amplitude. teis the interecho spacing applied by the experimenter. T2is the intrinsic transverse relaxation time of the liquid at the in situ physical and chemical conditions. T2 might or might not be known prior to the measurement. D is the diffusion coefficient of the fluid at the in situ conditions. D might or might not be known prior to the measurement. Γis the gyromagnetic ratio of the isotope studied (2π x 4.26 KHz/Gauss for hydrogen). Gis the magnitude of the magnetic field gradient imposed at the volume of investigation by the experimental setup. G is known. δis the duration of the magnetic field gradient pulse, and delta is the time between the two magnetic field gradient pulses which precede each echo. Four cases are treated; 1. Two out of the three parameters of the liquid in the volume of investigation - A, T2 and D - are known. The third might then be derived from the above equations. For example, if A and T2 are known and the first echo amplitude, a₁ is measured, then for a constant gradient D = [-te/T2 - ln (a₁/A)] * 12 (ΓG)²te³ More echoes, as well as repeated measurements, may improve the statistical validity of this result. 2. The amplitude A is known, neither T2 nor D are known but only an upper bound for D and/or lower bound for T2 is sought for. An upper bound for D is obtained from the abovementioned equations by replacing the te/T2 term by zero. A lower bound for T2 is obtained by setting D = 0. Such bounds may be very useful in various cases, e.g. in discriminating hydrocarbon from water on the basis of either D or T2, or in discriminating light from heavy oil. 3. A is either known or unknown but of no interest. Several echoes are recorded and the apparent decay rate is calculated. As an example, for the constant gradient case, the apparent transverse relaxation time is: T2(app) = [1/T2 + D(ΓGte)²/12]⁻¹ It is derived from a best fit procedure of the measure of echo amplitudes, an, to their representation an = Ae-nCwhere C = te/T2(app) in which T2(app) is a fitting parameter. Alternatively, by dividing all of the amplitudes by one of the echo amplitudes, for example, a₁, the obtained ratios are to be represented by the right hand of an/a₁ = exp [-(nte-te)/T2(app)] A is factored out and D, T2 or either of their bounds can be derived from the abovementioned equation relating T2(app) T2 and D. Once again, the upper D bound is obtained by setting 1/T2 to zero and solving for D, and the lower T2 bound is obtained by setting D to zero. Alternatively, T2 or D or either of their bounds can be derived from repetition of the same experiment at least twice, varying one or more of the following parameters: te, G, delta or δ. 4. If both D and T2 are unknown and the abovementioned bounds are insufficient approximations, the apparent relaxation time should be calculated at least twice for two experiments differing in at least one of the following parameters: te, G, delta or δ. In cases such as that of a preferred embodiment of this invention, for which the gradient G is also a function of the field strength and hence a function of the resonance frequency, two or more experiments differing in the resonance frequency are sufficient. It is convenient, though not necessary, to rewrite the relation between T2(app), T2 and D in terms of R₂(app) = 1/T2(app)and R₂ = 1/T2. The equation for R₂ and D is a linear equation, e.g.: R₂(app) = R₂ + D(ΓGte²)/12 for the fixed gradient embodiment. The two or more distinct experiments yield a set of two or more linear equations for T2 and D having different values of R₂(app). Out of this set of two or more equations, T2 and D may be derived by either explicit solution of the two linear equations yielding the values of the two unknowns, or best fit (such as least squares) for a set of three or more distinct experiments. It is appreciated that several experiments of the type described above may be combined into a single experiment by acquiring all the required data from the signals of a single excitation. This can be accomplished by changing the abovementioned parameters during a single sequence. As an illustrative example: the first few echoes are spaced by one fixed time interval, the next few by another, and so on. It will be appreciated by persons skilled in the art that the present invention is not limited by what has been particularly shown and described hereinabove. Rather the scope of the present invention is defined only by the claims which follow:
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A method for conducting NMR measurement in a borehole comprising the steps of: applying a static magnetic field to polarize the nuclear spins of the borehole, thus creating bulk magnetization at the region of interest; applying a RF field to the region of interest at a preselected frequency, duration and magnitude in order to cause at least part of the magnetization to lie in a plane perpendicular to the direction of the static magnetic field, wherein the method is characterized by the steps of: 1) applying a magnetic field gradient having a predetermined adjustable set of parameters including strength, direction and duration to the region of interest thereby allowing the atoms and molecules of the material in the region of interest to diffuse in a gradient field; 2) applying a refocusing RF pulse to the region of interest; 3) acquiring an NMR spin echo having an associated amplitude; and 4) deriving the diffusion coefficient D and/or the spin echo decay T2 from the echo amplitude. A method according to claim 1 wherein step 1 of applying a magnetic field gradient is repeated between steps 2 and 3 and at least one of the parameters of the magnetic field gradient is varied. A method according to claim 1 or 2 wherein steps 1 - 3 are repeated in order to acquire a plurality of echoes and to derive one or more coefficients D and/or T2 therefrom. A method according to claim 3 wherein in the process of repeating steps 1 - 3 at least one of the following parameters is changed: 1. the time period during which the magnetic field gradient is applied, 2. the spacing between two successive applications of the magnetic field gradient, 3. the strength of the magnetic field gradient, 4. the RF pulse spacing; and 5. the applied RF frequency. A method according to any preceding claim wherein at least two NMR measurements are conducted and in the process at least one of the following parameters is changed: 1. the time period during which the magnetic field gradient is applied, 2. the spacing between two successive applications of the magnetic field gradient, 3. the strength of the magnetic field gradient, 4. the RF pulse spacing; and 5. the applied RF frequency. A method according to any preceding claim, also comprising the step of employing the diffusion coefficient D to determine at least one of the following petrophysical parameters: Water/hydrocarbon discrimination; Water and hydrocarbon saturation levels; Permeability; Pore size and pore size distribution; Oil viscosity; Formation form factor F, which is a measure of the average increase in electrical resistance due to the formation tortuosity; q-space imaging of the formation. An apparatus for conducting NMR measurement in a borehole comprising: means (108) for applying a static magnetic field to polarize the nuclear spins of the borehole, thus creating bulk magnetization at the region of interest; means (116, 120, 124) for applying a RF field to the region of interest at a preselected frequency, duration and magnitude in order to cause at least part of the magnetization to lie in a plane perpendicular to the direction of the static magnetic field, wherein the apparatus is characterized by: (1.) means (110, 129, 146) for applying a magnetic field gradient having a predetermined adjustable set of parameters including strength, direction and duration to the region of interest thereby allowing the atoms and molecules of the material in the region of interest to diffuse in a gradient field; (2.) means (116, 120, 124) for applying a refocusing RF pulse to the region of interest; (3.) means (116, 120, 126, 40) for acquiring an NMR spin echo having an associated amplitude; and (4.) means (32) for deriving the diffusion coefficient D and/or the spin echo decay T2 from the echo amplitude. An apparatus according to claim 7 further comprising means for repeated application of the NMR measurement in order to acquire a plurality of echoes and to derive one or more coefficients D and/or T2 therefrom. An apparatus according to claim 8 further comprising: means (146) for varying the time period during which the magnetic field gradient is applied, and the spacing between two successive applications of the magnetic field gradient; means (129) for varying the strength of the magnetic field gradient; means (36) for varying the RF pulse sequence and the applied frequency. An apparatus according to claims 7, 8 or 9, also comprising means for employing the diffusion coefficient D to determine at least one of the following petrophysical parameters: Water/hydrocarbon discrimination; Water and hydrocarbon saturation levels; Permeability; Pore size and pore size distribution; Oil viscosity; Formation form factor F, which is a measure of the average increase in electrical resistance due to the formation tortuosity; q-space imaging of the formation.
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NUMAR CORP; NUMAR CORPORATION
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PALTIEL ZVI; PALTIEL, ZVI
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EP-0489579-B1
| 489,579 |
EP
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B1
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EN
| 19,950,329 | 1,992 | 20,100,220 |
new
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C07C259
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A61K31
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C07C311, C07D307, C07D265, A61P43, C07C237, A61K38, C07D209, C07K5, C07C233, C07D239, A61K31, C07D295, C07D213, C07C55, A61P35, C07C259
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C07C 237/22, C07D 209/20, C07C 259/06, M07C101:14, M07D209:20, C07K 5/06A1B2, C07C 311/46, K61K38:00, C07C 55/02, C07K 5/06C1
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Peptidyl derivatives
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Compounds of formula (I): are described wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R¹ represents an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group; R² represents an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R³ represents a hydrogen atom or an alkyl group; R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents an optionally substituted alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group]; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. The compounds are metalloproteinase inhibitors and in particular have a selective gelatinase action, and may be of use in the treatment of cancer to control the development of tumour metastasises.
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Field of the InventionThis invention relates to a particular class of peptidyl derivatives, to processes for their preparation and to their use in medicine. Background to the InventionIn normal tissues, cellular connective tissue synthesis is offset by extracellular matrix degradation, the two opposing effects existing in dynamic equilibrium. Degradation of the matrix is brought about by the action of proteinases released from resident connective tissue cells and invading inflammatory cells, and is due, in part, to the activity of at least three groups of metalloproteinases. These are the collagenases, the gelatinases (or type-IV collagenases) and the stromelysins. Normally these catalbolic enzymes are tightly regulated at the level of their synthesis and secretion and also at the level of their extracellular activity, the latter through the action of specific inhibitors, such as α₂-macroglobulins and TIMP (tissue Inhibitor of metalloproteinase) which form inactive complexes with metalloproteinases. The accelerated, uncontrolled breakdown of connective tissues by metalloproteinase catalysed resorption of the extracellular matrix is a feature of many pathological conditions, such as rheumatoid arthritis, corneal, epidermal or gastric ulceration; tumour metastasis or invasion; periodontal disease and bone disease. It can be expected that the pathogenesis of such diseases is likely to be modified in a beneficial manner by the administration of metalloproteinase Inhibitors and numerous compounds have been suggested for this purpose [for a general review see Wahl, R.C. etal Ann. Rap. Med. Chem. 25, 175-184, Academic Press Inc., San Diego (1990)]. Certain hydroxamic acid peptidyl derivatives [see for example European Patent Specifications Nos. 214639, 231081, 236872 and 274453 and International Patent Specifications Nos. WO90/05716 and WO90/05719], have been described as collagenase and/or stromelysin inhibitors. We have now found a particular class of peptidyl derivatives, members of which advantageously possess a potent and selective inhibitory action against gelatinase. There is now much evidence that metalloproteinases are important in tumour invasion and metastasis. Tumour cell gelatinase, in particular, has been associated with the potential of tumour cells to invade and metastasise. Tumour invasion and metastasis is the major cause of treatment failure for cancer patients, and the use of a selective gelatinase inhibitor such as a compound of the present invention which is capable of inhibiting tumour cell invasion can be expected to improve the treatment of this disease. Thus according to one aspect of the invention we provide a compound of formula (I) wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R' represents a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group; R² represents an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R³ represents a hydrogen atom or an alkyl group; R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents an optionally substituted alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group]; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group, provided that X is not methylamino when R² is phenylethyl; and the salts, solvates and hydrates thereof. It will be appreciated that the compounds according to the invention can contain one or more asymmetrically substituted carbon atoms, for example those marked with an asterisk in formula (I). The presence of one or more of these aysmmetric centres in a compound of formula (I) can give rise to stereoisomers, and in each case the invention is to be understood to extend to all such stereoisomers, including enantiomers and diastereoisomers, and mixtures, including racemic mixtures, thereof. In the formulae herein, the ∼line is used at a potential asymmetric centre to represent the possibility of R- and S- configurations, the line and the ------- line to represent an unique configuration at an asymmetric centre. In the compounds according to the invention, when the group R represents an esterified carboxyl group, it may be for example a group of formula - CO₂R⁸ where R⁸ is a straight or branched, optionally substituted C₁₋₈alkyl group such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl group; a C₆₋₁₂arylC₁₋₈alkyl group such as an optionally substituted benzyl, phenylethyl, phenylpropyl, α-naphthylmethyl or β-naphthylmethyl group; a C₆₋₁₂aryl group such as an optionally substituted phenyl, α-naphthyl or β-naphthyl group; a C₆₋₁₂aryloxyC₁₋₈alkyl group such as an optionally substituted phenyloxymethyl, phenyloxyethyl, α-naphthyloxymethyl or β-naphthyloxymethyl group; an optionally substituted C₁₋₈alkanoyloxyC₁₋ ₈alkyl group, such as a pivaloyloxymethyl, propionyloxyethyl or propionyloxypropyl group; or a C₆₋₁₂aroyloxyC₁₋₈alkyl group such as an optionally substituted benzoyloxyethyl or benzoyloxypropyl group. Optional substituents present on the groups R⁸ include for example one or more halogen atoms such as fluorine, chlorine, bromine or iodine atoms, or C₁₋ ₄alkyl, e.g. methyl or ethyl, or C₁₋₄alkoxy, e.g. methoxy or ethoxy, groups. In general, when the group R represents an esterified carboxyl group, it may be a metabolically labile ester of a carboxylic acid. When the group R¹ in compounds of formula (I) represents an optionally substituted alkyl or alkenyl group, it may be, for example, a straight or branched C₁₋₆ alkyl or C₂₋₆alkenyl group, such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, ethenyl, 1-propenyl, 1-butenyl or 2-butenyl group optionally substituted by one or more C₁₋₆alkoxy, e.g. methoxy, ethoxy or propoxy, C₁₋₆alkylthio, e.g. methylthio, ethylthio or propylthio, C₆₋₁₂arylC₁₋₆alkoxy, e.g. phenylC₁₋₆ alkoxy such as benzyloxy, aralkylthio, e.g phenylC₁₋₆alkylthio such as benzylthio, amino (-NH₂), substituted amino, [such as -NHR⁹, where R⁹ is a C₁₋₆ alkyl e.g. methyl or ethyl], C₆₋₁₂arylC₁₋₆alkyl, e.g. phenylC₁₋₆alkyl, such as benzyl, C₆₋ ₁₂aryl, e.g. phenyl, C₃₋₈cycloalkyl, e.g. cyclohexyl, or C₃₋₈cycloalkylC₁₋ ₆alkyl, e.g. cyclohexylmethyl group], carboxyl (-CO₂H) or -CO₂R⁸ [where R⁸ is as defined above] groups. Aryl groups represented by R¹ in compounds of formula (I) include C₆₋₁₂ aryl groups such as phenyl or α- or β-naphthyl groups. Aralkyl groups represented by R¹ include C₆₋₁₂arylC₁₋₆alkyl groups such as phenylC₁₋₆alkyl, or α- or β-naphthylC₁₋₆alkyl, for example benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, α- or β-naphthylmethyl, naphthylethyl, naphthylpropyl, naphthylbutyl or naphthylpentyl groups. When the group R¹ in compounds of formula (I) is a heteroaralkyl group, it may be for example a C₃₋₆heteroarylC₁₋₆alkyl group, such as an optionally substituted pyrrolylmethyl, furanylmethyl, thienylmethyl, imidazolylmethyl, oxazolylmethyl, thiazolylmethyl, pyrazolylmethyl, pyrrolidinylmethyl, pyridinylmethyl, pyrimidinylmethyl, morpholinylmethyl, or piperazinylmethyl group. Heteroarylthioalkyl groups represented by R¹ include C₃₋₆heteroarylthioC₁₋ ₆alkyl groups such as optionally substituted pyrrolylthiomethyl, furanylthiomethyl, oxazolylthiomethyl, thiazolylthiomethyl, pyrazolylthiomethyl, pyrrolidinylthiomethyl, pyridinylthiomethyl, pyrimidinylthiomethyl, morpholinylthiomethyl, or piperazinylthiomethyl groups. The aryl, aralkyl, heteroaralkyl, or heterarythioalkyl groups represented by R¹, and the groups represented by R² in compounds of formula (I) may each optionally be substituted in the cyclic part of the group by one, two or more substituents [R¹⁰] selected from halogen atoms, e.g. fluorine, chlorine, bromine or iodine atoms, or C₁₋₆alkyl, e.g. methyl or ethyl, C₁₋₆alkoxy e.g. methoxy or ethoxy, C₂₋₆alkylenedioxy, e.g. ethylenedioxy, haloC₁₋₆alkyl, e.g. tri-fluoromethyl, C₁₋₆alkylamino, e.g. methylamino or ethylamino, C₁₋ ₆dialkylamino, e.g. dimethylamino or diethylamino, amino (-NH₂ ), nitro, cyano, hydroxyl (-OH), carboxyl (-CO₂H), -CO₂R⁸, where R⁸ is as defined above, C₁₋₆alkylcarbonyl, e.g. acetyl, sulphonyl (-SO₂H), C₁₋ ₆alkylsulphonyl, e.g. methylsulphonyl, aminosulphonyl (-SO₂NH₂), C₁₋₆ alkylaminosulphonyl, e.g. methylaminosulphonyl of ethylaminosulphonyl, C₁₋₆dialkylaminosulphonyl e.g. dimethylaminosulphonyl or diethylaminosulphonyl, carboxamido (-CONH₂), C₁₋₆alkylaminocarbonyl, e.g. methylaminocarbonyl or ethylaminocarbonyl, C₁₋₆dialkylaminocarbonyl, e.g. dimethylaminocarbonyl or diethylaminocarbonyl, sulphonylamino (-NHSO₂H), C₁₋ ₆alkylsulphonylamino, e.g. methylsulphonylamino or ethylsulphonylamino, or C₁₋₆dialkylsulphonylamino, e.g. dimethylsulphonylamino or diethylsulphonylamino groups. It will be appreciated that where two or more R¹⁰ substituents are present, these need not necessarily be the same atoms and/or groups. The R¹⁰ substituents may be present at any ring carbon atom away from that attached to the rest of the molecule of formula (I). Thus, for example, in phenyl groups any substituents may be present at the 2-, 3-or 4- 5- or 6- positions relative to the ring carbon atom attached to the remainder of the molecule. When the groups R³ and R⁴ in compounds of formula (I) are alkyl groups, they may be for example C₁₋₆alkyl groups such as methyl or ethyl groups. The group R⁵ in compounds of formula (I) may be an optionally substituted straight or branched C₁₋₆alkyl, e.g. methyl, ethyl, n-propyl i-propyl, n-butyl, i-butyl, n-pentyl or n-hexyl or C₂₋₆alkenyl e.g. ethenyl or 1-propenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups where R⁷ is a hydrogen atom or a C₁₋₆alkyl group such as a methyl group. Optional substituents which may be present on alkyl or alkenyl groups R⁵ include C₆₋₁₂arylC₁₋₆alkyl groups such as optionally substituted phenylC₁₋₆ e.g. benzyl groups, C₆₋₁₂arylC₁₋₆alkoxy groups such as optionally substituted phenylC₁₋₆alkoxy e.g. benzyloxy groups, C₆₋₁₂aryl e.g. optionally substituted phenyl groups, C₃₋₈heteroaryl e.g. optionally substituted indole, imidazole or quinoline groups, C₆₋₁₂arylC₁₋₆alkoxyC₆₋ ₁₂aryl, e.g. benzyloxyphenyl groups, -OH, -SH, C₁₋₆alkylthio e.g. methylthio or ethylthio, carboxyl (-CO₂H), amino (-NH₂), carboxamido (-CONH₂) or guanido -NHC(NH₂)=NH, groups. The optional substituents present on these groups may be R¹⁰ substituents as discussed above. When X in the compounds of formula (I) represents a substituted amino group it may be for example a group of formula -NR¹¹R¹², where R¹¹ and R¹², which may be the same or different, is each a hydrogen atom (with the proviso that when one of R¹¹ or R¹² is a hydrogen atom, the other is not) or an optionally substituted straight ot branched alkyl group, optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- or aminocarbonyloxy [-NHC(O)O-] groups or R¹¹ and R¹², together with the nitrogen atom to which they are attached, may form an optionally substituted C₃₋₆cyclic amino group optionally possessing one or more other heteroatoms selected from -O- or - S-, or -N(R⁷)- groups. When R¹¹ and/or R¹² is an alkyl group it may be for example a C₁₋₆alkyl group such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, or t-butyl group, optionally interrupted by one or more -O- or -S- atoms, or - N(R⁷)- or aminocarbonyloxy groups and may be for example a methoxymethyl ethoxymethyl, ethoxymethyl, ethoxyethyl or ethylaminocarbonyloxymethyl group. The optional substituents which may be present on such groups include hydroxyl (-OH), carboxyl (-CO₂H), esterified carboxyl (-CO₂R⁸), carboxamido (-CONH₂), substituted carboxamido, e.g. a group -CONR¹¹R¹² where NR¹¹R¹² is as defined herein, amino (-NH₂), substituted amino, for example a group of formula -NR¹¹R¹², or aryl, e.g. C₆₋₁₂ aryl such a phenyl, optionally substituted by one, two or more R¹⁰ substituents selected from those listed above in relation to the group R². Particular examples of cyclic amino groups represented by -NR¹¹R¹² include morpholinyl, imidazolyl, piperazinyl, pyrrolyl, oxazolyl, thiazolyl, pyrazolyl, pyrrolidinyl, pyridinyl and pyrimidinyl groups. When the group X is a substituted hydroxyl group it may be for example a group -OR¹¹ where R¹¹ is as defined above, other than a hydrogen atom. Salts of compounds of formula (1) include pharmaceutically acceptable salts, for example acid addition salts derived from inorganic or organic acids, such as hydrochlorides, hydrobromides, hydroiodides, p-toluene sulphonates, phosphates, sulphates, perchlorates, acetates, trifluoroacetates, propionates, citrates, malonates, succinates, lactates, oxalates, tartrates and benzoates. Salts may also be formed with bases. Such salts include salts derived from inorganic or organic bases,. for example alkali metal salts such as sodium or potassium salts, alkaline earth metal salts such as magnesium or calcium salts, and organic amine salts such as morpholine, piperidine, dimethylamine or diethylamine salts. When the group R in compounds of the invention is an esterified carboxyl group, it may be a metabolically labile ester of formula -CO₂R⁸ where R⁸ may be an ethyl, benzyl, phenylethyl, phenylpropyl, α- or β-naphthyl, 2,4-dimethylyphenyl, 4-t-butylphenyl, 2,2,2-trifluoroethyl, 1-(benzyloxy)benzyl, 1-(benzyloxy)ethyl, 2-methyl-1-propionyloxypropyl, 2,4,6-trimethylbenzoyloxymethyl or pivaloyloxymethyl group. In the compounds of formula (I) the group R¹ may in particular be a C₁₋₆alkyl group such as a methyl group, an aralkyl group such as benzyl group, an arylthioalkyl group such as a phenythiomethyl group or a heteroarylthioalkyl group such as thienylthiomethyl, pyridinylthiomethyl or pyrimidinylthiomethyl group or is especially a hydrogen atom. The groups R³ and R⁴ in compounds of formula (I) may each in particular be a methyl group, or, especially, a hydrogen atom. The group R⁵ in compounds of formula (I) may in particular be a C₁₋₆alkyl group. e.g. an i-propyl or i-butyl group, or an optionally substituted benzyl, benzyloxybenzyl or indolymethyl group. The group X in compounds of formula (I) may be in particular an amino (-NH₂) or -NR¹¹R¹² group. Particular -NR¹¹R¹² groups are -NHR¹² groups. Groups of this type include those where R¹² is a C₁₋₆alkyl group, for example a methyl, ethyl, or n-propyl group, optionally interrupted by one or more -O- or -S- atoms or -N(R⁷) [e.g. NH- or -N(CH₃)-] or aminocarbonyloxy groups and optionally substituted by a hydroxyl, carboxyl, carboxyalkyl, e.g. carboxymethyl, carboxamido, amino, -NR¹¹R¹², [for example di-C₁₋ ₆alkylamino such as dimethylamino, C₁₋₆alkylamino such as methylamino, or C₃₋₆ cyclic amino such as morpholinyl, pyrrolidinyl or pyridinyl] or phenyl optionally substituted by one, two or more R¹⁰ substituents. A particularly useful group of compounds according to the invention is that of formula (I) where R² is an optionally substituted phenylpropyl group. A further particularly useful group of compounds of formula (I) are those wherein X is an amino or substituted amino group. In general, in compounds of formula (I) the groups R¹, R³ and R⁴ is each preferably a hydrogen atom. In a further preference, the group R in compounds according to the invention is a -CONHOH or a-CO₂H group or a metabolically labile ester thereof. In a particular preference, however, R is a -CONHOH or a -CO₂H group An especially useful group of compounds according to the invention has the formula (Ia) wherein R, R², R⁵ and X are as defined for formula (I); and the salts, solvates and hydrates thereof. A particularly useful group of compounds of formula (Ia) are those wherein R represents a -CONHOH or -CO₂H group; R² represents an optionally substituted phenylpropyl group; X is an amino (-NH₂) or substituted amino group; and the salts, solvates and hydrates thereof. In the compounds of formula (Ia) X may be a -NH₂ group or a group - NR¹¹R¹² as defined for compounds of formula (I). The group R⁵ may in particular be a C₁₋₆alkyl group such as an i-propyl or i-butyl group, or an optionally substituted benzyl, benzyloxybenzyl or indolymethyl group. The compounds according to the invention may be prepared by the following processes. In the description and formulae below the groups R, R¹, R², R³, R⁴, R⁵ and X are as defined above, except where otherwise indicated. It will be appreciated that functional groups, such as amino, hydroxyl or carboxyl groups, present in the various compounds described below, and which it is desired to retain, may need to be in protected form before any reaction is initiated. In such instances, removal of the protecting group may be the final step in a particular reaction. Suitable amino or hydroxyl protecting groups include benzyl, benzyloxycarbonyl or t-butyloxycarbonyl groups. These may be removed from a protected derivative by catalytic hydrogenation using for example hydrogen in the presence of a metal catalyst, for example palladium on a support such as carbon in a solvent such as an alcohol e.g. methanol, or by treatment with trimethylsilyl iodide or trifluoroacetic acid in an aqueous solvent. Suitable carboxyl protecting groups include benzyl groups, which may be removed from a protected derivative by the methods just discussed, or alkyl groups, such as a t-butyl group which may be removed from a protected derivative by treatment with trifluoroacetic acid in an aqueous solvent. Other suitable protecting groups and methods for their use will be readily apparent. The formation of the protected amino, hydroxyl or carboxyl group may be achieved using standard alkylation or esterification procedures, for example as described below. Thus according to a further aspect of the invention a compound of formula (I) may be prepared by coupling an acid of formula (II) or an active derivative thereof, with an amine of formula (III) followed by removal of any protecting groups. Active derivatives of acids for formula (II) include for example acid anhydrides, or acid halides, such as acid chlorides. The coupling reaction may be performed using standard conditions for amination reactions of this type. Thus, for example the reaction may be achieved in a solvent, for example an inert organic solvent such as an ether, e.g. a cyclic ether such a tetrahydrofuran, an amide e.g. a substituted amide such as dimethylformamide, or a halogenated hydrocarbon such as dichloromethane at a low temperature, e.g. -30°C to amibient temperature, such as -20°C to 0°C, optionally in the presence of a base, e.g. an organic base such as an amine, e.g. triethylamine or a cyclic amine such as N-methylmorpholine. Where an acid of formula (II) is used, the reaction may additionally be performed in the presence of a condensing agent, for example a diimide such as N,N'-dicyclohexylcarbodiimide, advantageously in the presence of a triazole such as I-hydroxybenzotriazole. Alternatively, the acid may be reacted with a chloroformate for example ethylchloroformate, prior to reaction with the amine of formula (III). Free hydroxyl or carboxyl groups in the starting materials of formulae (II) [where R is -CONHOH or CO₂H] and (III) may need to be protected during the coupling reaction. Suitable protecting groups and methods for their removal may be those mentioned above. It will be appreciated that where a particular steroisomer of formula (I) is required, this may be obtained by resolution of a mixture of isomers following the coupling reaction of an acid of formula (II) and an amine of formula (III). Conventional resolution techniques may be used, for example separation of isomers by Chromatography e.g. by use of high performance liquid chrormatography. Where desired, however, appropriate homochiral starting materials may be used in the coupling reaction to yield a particular stereo isomer of formula (I). Thus, in particular process a compound of formula (Ia) may be prepared by reaction of a compound of formula (IIa) with an amine of formula (IIIa) as described above Intermediate acids of formula (II) wherein R is a carboxyl or esterified carboxyl group may be prepared by hydrolysing a corresponding ester of formula (IV) where R¹³ is an alkyl group, for example a methyl or t-butyl group, using for example trifluoroacetic acid, or, when R¹³ is a methyl group using enzymatic hydrolysis, such as for example with α-chymotrypsin, in an aqueous solvent. In this reaction, enzymatic hydrolysis (for example as more particularly described in the Examples herein) usefully provides a method of isomer selection. The ester of formula (IV) may be prepared by esterification of the corresponding acid of formula (V) using an appropriate acyl halide, for example an acyl chloride in a solvent such as an alcohol, e.g. methanol at a low temperature, e.g. around O°C. Acids of formula (V) may be prepared by alkylation of a compound of formula (VI) with an appropriate halide, e.g. a compound R²Hal, where Hal is a halogen atom such as a chlorine or bromine atom in the presence of a base, for example an alkoxide such as sodium ethoxide in a solvent such as an alcohol, e.g. ethanol at ambient temperature, followed by decarboxylation using for example concentrated hydrochloric acid at an elevated temperature, e.g. the reflux temperature. Intermediates of formula (VI) are either known compounds or may be prepared by methods analogous to those used for the preparation of the known compounds. Intermediate acids of formula (IV) wherein R is a -CONHOH group or a protected derivative thereof may be prepared by reaction of an anhydride of formula (VII) with a hydroxylamine such as O-benzylhydroxylamine in a solvent such as tetrahydrofuran at a low temperature, e.g. around -20°C, followed where desired by removal of the protecting group as described above. The intermediate anhydrides of formula (VII) may be prepared for example by heating for example at the reflux temperature, a diacid of formula (V) where R is -CO₂H with an acyl chloride such as acetyl chloride. The homochiral acids of formula (IIa) may be prepared according to another feature of the invention by oxidation of an oxazolidinone of formula (VIII) (where Ph is a phenyl group) using an oxidising agent such as peroxide, e.g. hydrogen peroxide in a solvent such as an ether e.g. a cyclic ether such as tetrahydrofuran, at a low temperature, e.g. around 0°C followed by treatment with a base, such as lithium hydroxide, at an elevated temperature. The compounds of formula (VIII) are novel, particularly useful, intermediates for the preparation of stereoisomers of formula (Ia). The compounds of formula (VIII) may be prepared by reaction of an acyl halide RCH₂CH(R²)COHal (where Hal is a halogen atom such as chloride, bromine or iodine atom) with a solution of (S)-4-(phenylmethyl)-2-oxazolidinone in the presence of a base such as n-butyl lithium in a solvent such as tetrahydrofuran at a low temperature, e.g. around -78°C. Acyl halides RCH₂ CH)(R²)COHal may be prepared by treatment of the corresponding known acids RCH₂CH(R²)CO₂H with conventional halogenating agents for example thionyl halides under standard reaction conditions. In another process according to the invention, a compound of formula (I) where R is a carboxyl group may be prepared by decarboxylation of a corresponding compound of formula (IX). The reaction may be achieved using standard conditions, for example by heating a compound of formula (IX) in an inert solvent, such as an aromatic hydrocarbon, e.g. xylene, at the reflux temperature. The intermediate acids of formula (IX) may be prepared by reaction of a protected acid of formula (X) where R is a protected carboxyl group such as a benzyloxycarbonyl group and Z¹ is a protecting group such as a benzyl group with an amine of formula (III) using reagents and conditions as described above for coupling compounds of formula (II) and (III), followed by removal of the protecting groups. The intermediates of formula (X) may be prepared by treatment of an appropriate malonic ester RCH₂CO₂Z¹ with a halide of formula (XI) (where Hal is a halogen atom, e.g. a chlorine or bromine atom) in the presence of a base such as potassium t-butoxide in a solvent such as dimethylformamide at ambient temperature. Halides of formula (XI) may be prepared by halogenation and subsequent decarboxylation of a di-acid of formula (XII). using for example a halogenating agent such as bromine in a solvent such as diethyl ether at ambient temperature, followed by heating of the resulting halogenated intermediate in a solvent such as an aromatic hydrocarbon e.g. xylene, at the reflux temperature. Intermediates of formula (XII) may be prepared by hydrolysis of the corresponding di-alkylester (e.g. the dimethyl or diethyl ester) using a base such as sodium or potassium hydroxide in a solvent such as an alcohol e.g. methanol at the reflux temperature. The di-alkyl ester starting materials are either known compounds or may be prepared by methods analogous to those used for the preparation of the known compounds, for example as described in the Examples herein. Compounds of formula (I) may also be prepared by interconversion of other compounds of formula (I). Thus, for example, a compound of formula (I) wherein R is a -CONHOH group may be prepared by reaction of a corresponding acid of formula (I) wherein R is a -CO₂H group or an active derivate thereof (for example an acid chloride or an acid anhydride) with hydroxylamine or an O-protected derivative or a salt thereof. The reaction may be performed using the reagents and conditions described above in the preparation of compounds of formula (I) from the starting materials of formulae (II) and (III). In another interconversion process, compounds of formula (I) wherein R is - CO₂H and/or X contains a -CO₂H group may be prepared by hydrolysis of the corresponding esterified compounds (for example where R is a -CO₂R⁸ group and/or X contains a similar group) using conventional procedures, for example by treatment with a base, e.g. an alkali metal hydroxide such as lithium hydroxide in a solvent such as an aqueous alcohol, e.g. aqueous methanol, or by treatment with an acid such as a mineral acid, e.g. hydrochloric acid in the presence of a solvent, e.g. dioxan. Similarly esters of formula (I), for example where R is a CO₂R⁸ group and/or X contains a -CO₂R⁸ group may be prepared by reaction of the corresponding acids, where R is a -CO₂H group and/or X contains a -CO₂H group or an active derivative thereof, with an alcohol R⁸OH using standard conditions. The compounds according to the invention are potent and selective inhibitors of gelatinase. The activity and selectivity of the compounds may be determined by the use of appropriate enzyme inhibition test for example as described in Example A hereinafter. In our tests using this approach, compounds according to the invention have been shown to inhibit gelatinase with Ki values in the picomolar-nanomolar range and to have around a 40 fold or greater selectivity for gelatinase over stromelysin, and around a 20-fold or greater selectivity for gelatinase over collagenase. The ability of compounds of the invention to prevent tumour cell invasion may be demonstrated in a standard mouse model. Thus, briefly, nude mice may be inoculated with a tumour cell line showing gelatinase - dependent invasion and the ability of compounds according to the invention to reduce subsequent lung tumour colonisation may be evaluated in accordance with standard procedures. In out tests, compounds according to the invention, when administered intravenously at 1mg/kg to mice in the above model have reduced lung tumour colonisation to negligable levels. The compounds according to the invention can be expected to be of use to prevent tumour cell metastasis and invasion. The compounds may therefore be of use in the treatment of cancer, particularly in conjunction with radiotherapy, chemotherapy or surgery, or in patients presenting with primary tumours, to control the development of tumour metastasises. Particular cancers may include breast, melanoma, lung, head, neck or bladder cancers. For use according to this aspect of the invention, the compounds of formula (I) may be formulated in a conventional manner, optionally with one or more physiologically acceptable carriers, diluents or excipients. Thus according to a further aspect of the invention we provide a pharmaceutical composition comprising a compound of formula (I) and a pharmaceutically acceptable diluent, carrier or excipient. In a still further aspect the invention provides a process for the production of a pharmaceutical composition comprising bringing a compound of formula (I) into association with a pharmaceutically acceptable diluent, carrier or excipient. Compounds for use according to the present invention may be formulated for oral, buccal, parental or rectal administration or in a form suitable for nasal administration or administration by inhalation or insufflation. For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g. pregelatinised maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g. lactose, microcrystalline cellulose or calcium hydrogen phosphate); lubricants (e.g. magnesium stearate, talc or silica); disintegrants (e.g. potato starch or sodium glycollate); or wetting agents (e.g. sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents, emulsifying agents, non-aqueous vehicles; and preservatives. The preparations may also contain buffer salts, flavouring, colouring and sweetening agents as appropriate. Preparations for oral administration may be suitably formulated to give controlled release of the active compound. For buccal administration the compositions may take the form of tablets or lozenges formulated in conventional manner. The compounds of formula (I) may be formulated for parental administration by injection e.g. by bolus injection or continuous infusion. Formulations for injection may be presented in unit dosage form. The compositions for injection may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilising and/or dispersing agents. Alternatively, the active ingredient may be in powder form for constitution with a suitable vehicle, e.g. sterile pyrogen-free water, before use. The compounds of formula (I) may also be formulated in rectal compositions such as suppositories or retention enemas, e.g. containing conventional suppository bases such as cocoa butter or other glycerides. In addition to the formulations described above the compounds of formula (I) may also be formulated as a depot preparation. Such long acting formulations may be administered by implantation or by intramuscular injection. For nasal administration or administration by inhalation the compounds for use according to the present invention are conventiently delivered in the form of an aerosol spray presentation for pressurised packs or a nebuliser, with the use of suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. The compositions may, if desired, be presented in a pack or dispenser device which may contain one or more unit dosage forms containing the active ingredient. The pack or dispenser device may be accompanied by instructions for admininstration. The doses of compounds of formula (I) used to control the development of tumour metastasises will vary depending on the condition of the patient to be treated but in general may be in the range around 0-5mg to 50mg/kg body weight, particularly from about 1mg to 40mg/kg body weight. Dosage units may be varied according to the route of administration of the compound in accordance with conventional practice. Description of Specific EmbodimentsThe invention is further illustrated in the following non-limiting Examples. In the Examples, the following abbreviations are used: RT- room temperature DCCI- N,N'-dicyclohexylcarbodiimide DMF- dimethylformamide THF- tetrahydrofuran TFA- trifluoroacetic acid RPHPLCreverse phase high performance liquid chromatography HOBT- N-hydroxybenzotriazole Reference Example[4-N-(Hydroxyamino)-2R-isobutylsuccinyl]-L-valyl-L-alanine amideR,S - Isobutylsuccinic acid KSodium ethoxide was prepared by adding sodium metal (2.5g, 108mmoL) to anhydrous ethanol (150ml) under nitrogen. Triethyl 1,1,2-ethanetricarboxylate (26.6g, 25ml, 108mmoL) was added and the mixture stirred at room temperature (RT) for 20 minutes. Isobutyl bromide (19.12g, 15ml, 108mmoL) was added dropwise over 1 hour and the solution raised to reflux overnight. The precipitated sodium bromide was filtered off and the filtrate concentrated in vacuo. The residue was treated with cold H₂O (200ml) and extracted with diethyl ether (3 x 100ml). The organic layer was dried (Na₂SO₄) and concentrated to give a clear oil (32.2g) which was refluxed with concentrated hydrochloric acid for 96 hours. On cooling, a white crystalline solid precipitated which was filtered, washed with ice cold water and dried in vacuo to give the titlecompound K (11.0g) ¹HNMR (CDCL₃) δ 0.85 (3H, d, J = 6Hz), 0.90 (3H, d, J=6Hz), 1.3-1.45 (1H, m), 1.55-1.75 (2H, m), 2.50 (1H, dd, J=6 and 18 Hz), 2.70 (1H, dd, J=9 and 18 Hz), 2.85-2.95 (1H, m). 3-(R,S)-Isobutylsuccinic anhydrideLThe diacid K (10.21g, 59mmoL) was treated with acetyl chloride (27ml, 376mmoL) under reflux for 2.1/2 hours. Volatiles were removed under reduced pressure to give the anhydride L (9.37g, 100%) as a brownish oil. ¹HNMR (CDCL₃) 0.95 (3H, d, J = 6Hz), 1.05 (3H, d, J=6Hz), 1.48-1.90 (3H, m), 2.65 (1H, dd, J=7 and 18Hz), 3.10 (1H, dd, J= 9 and 18 Hz), 3.15-3.25 (1H, m). [4-(N-Benzyloxyamino)-2 R,S-Isobutyl) succinic acidMO-Benzyl hydroxylamine (7.8g, 63.4mmoL) in dry THF (50ml) was added dropwise (over 1 hour) to a solution of the anhydride L (9.37g, 60.0mmoL) in dry THF (100ml) at -20°C. After stirring a further 1 hour, volatiles were removed in vacuo and the residue taken up in ethyl acetate. After washing with 1.0MHCL (x3), the organic phase was dried (MgSO₄) and evaporated to give a white solid. The crude solid was dissolved in hot diethyl ether and filtered. Colourless crystals of the acid M deposited on standing (6.7g, 41%). ¹HNMR (CDCL₃) δ 0.8-1.0 (6H, m), 1.2-1.4 (3H, m), 2.1-2.4 (2H, m), 2.8-3.0 (1H, m), 4.85 (2H, s), 7.3 (5H,bs), 8.6 (1H, bs). [4-N-(Hydroxyamino)-2R-isobutylsuccinyl]-L-valyl-L-alanine amideThe acid M (502mg, 1.8mmoL) was dissolved in dry THF (20ml) and cooled to -20°C. Ethylchloroformate (245mg, 233µl, 1.8mmoL) and N-methyl morpholine was added and the suspension left for 1 hour at -20°C. A DMF solution (10ml) of L-valine-L-alanine amide (500mg) was added dropwise. Once the addition was completed the cooling bath was removed and the reaction allowed to warm up to room temperature overnight. The organic solution was poured into 10% HCl and extracted with ethyl acetate (x3). The organic layer was dried (MgSO₄) and concentrated in vacuo to give a solid. The solid was dissolved in degassed MeOH (20ml) and hydrogenolysed using 5% Pd-C and hydrogen gas. After 1 hour at RT the catalyst was filtered off and the product purified on RPHPLC using 0.1%TFA/H₂O→ 0.1%TFA/CH₃CN (43:57) isocratically to yield the title compound. ¹HNMR (CD₃OD) δ 0.95 (12H, m), 1.35 (3H, d, J=6Hz), 1.95 (3H, m), 2.20 (1H, m), 2.35 (1H, m) 2.85 (2H, m), 4.35 (2H, m) The following compounds of Examples 1 - 4 were prepared in a similar manner to the Reference Compound using the appropriate analogous starting materials Example 1[4-N-(Hydroxyamino)-2R-(2-phenylethyl)succinyl]-L-leucine-N-(2-phenylethyl) amide¹HNMR (CD₃OD) 7.15-7.30 (10H, mult, Ar); 4.40 (1H, mult, NCHCO); 3.35-3.55 (2H, mult, CH₂N); 2.20-2.85 (7H, mult, CHCO + CH₂Ar); 1.50-1.95 (5H, mult. CHC) 0.95 (6H, dd, CH3) Example 2[4-(N-Hydroxyamino)-2R-phenylpropylsuccinyl]-L-leucine-N-(2-phenylethyl) amide¹HNMR (CD₃OD) 7.1-7.3 (10H, mult, Ar); 4.30 (1H, dd, NCHCO) 3.35 (2H, mult, CH₂N); 2.15-2.80 (7H, mult, CHCO+CH₂Ar); 1.5-1.75 (7H, mult, CHC); 0.95 (6H, dd, CH₃) Example 3[4-(N-Hydroxyamino)-2(R)-isobutylsuccinyl]-L-tryptophan amide¹HNMR (CD₃OD) δ 7.65 (1H, d), 7.35 (1H, d), 6.95-7.15 (3H, m), 4.65 (1H, dd), 3.05-3.2 (1H, m), 2.7-2.85 (2H, m), 2.0-2.2 (2H, m), 1.3-1.5 (2H, m) 1.05-1.15 (1H, m) 0.7 (3H, d), 0.65 (3H, d) Example 4[4-(N-Hydroxyamino) 2(R)-isobutylsuccinyl]-L-valine amide¹HNMR (CD₃OD) δ 4.15 (1H, d) 2.8-2.9 (1H, m) 2.2-2.35 (1H, m) 1.95-2.15 (2H, m), 1.45-1.55 (2H, m) 1.1-1.2 (1H, m) 0.8-1.05 (12H, m) EXAMPLE AThe activity and selectivity of the compounds of the invention may be determined as described below. All enzyme assays to determine Ki values were performed using the peptide substrate Dnp-Pro-Leu-Gly-Leu-Trp-Ala-D-Arg-NH₂. [M. Sharon Stock and Robert D. Gray. JBC 264, 4277-81, 1989). The enzymes cleave at the Gly-Leu bond which can be followed fluorimetrically by measuring the increase in Trp fluorescence emission associated with the removal of the quenching dinitrophenol (Dnp) group. Essentially, enzyme (e.g. gelatinase, stromelysin, collagenase) at 0.08-2nM; a range of inhibitor concentrations (0.1-50 x Ki) and substrate (approx. 20µm) are incubated overnight in 0.1M Tris/HCl buffer, pH 7.5, containing 0.1M NaCl, 10mM CaCl₂ and 0.05%. Brij 35 at either room temperature or 37°C depending on the enzyme. The reaction is stopped by adjusting the pH to 4 using 0.1M sodium acetate buffer and the fluorescence read at an excitation wavelength of 280nm and emission wavelength of 346nm. Ki values can be established using the equation for tight-being inhibition:- where Vo is the initial rate of reaction in the absence of inhibitor, Vi is the initial rate in the presence of inhibitor, [E] is the total enzyme concentration and [I] the total inhibitor concentration in the reaction mixture. For stromelysin and collagenase, Ki (app) was assumed to approximate to the true Ki as [S] « Km for the substrate hydrolysis. For gelatinase the Ki was determined by performing the analyses at several substrate concentrations. A plot of Ki(app) vs. [S] then gave the true Ki as the value of the y-axis intercept. The following results were obtained with compounds according to the invention. Ki (nM)Collagenase Stromelysin-1 Gelatinase -72KD Reference Compound30312933 Compound of Example 279160.17
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A compound of formula (1): wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R¹ represents a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl, aralkyl, heteroaralkyl or heteroarylthioalkyl group; R² represents an optionally substituted phenylethyl, phenylpropyl or phenylbutyl group; R³ represents a hydrogen atom or an alkyl group; R⁴ represents a hydrogen atom or an alkyl group; R⁵ represents an optionally substituted alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group]; X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group, provided that X is not methylamino when R² is phenylethyl; and the salts, solvates and hydrates thereof. A compound according to claim 1 wherein R represents a -CONHOH or carboxyl (-CO₂H) group. A compound according to claims 1 or 2 wherein R¹, R³ and R⁴ is each a hydrogen atom. A compound according to any of claims 1-3 wherein R⁵ is a straight or branched C₁₋₆alkyl or C₂₋₆alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- [where R⁷ is a hydrogen atom or a C₁₋₆ alkyl group] and optionally substituted by a C₆₋₁₂arylC₁₋₆alkyl, C₆₋₁₂arylC₁₋ ₆alkoxy, C₆₋₁₂ aryl, C₃₋₈heteroaryl, C₆₋₁₂arylC₁₋₆alkoxyC₆₋₁₂aryl, -OH, -SH, C₁₋₆alkylthio, carboxyl (-CO₂H), amino (-NH₂) carboxamide (-CONH₂) or guanido -NHC(NH₂)=NH group. A compound according to any of claims 1-4 wherein R² is an optionally substituted phenylpropyl group. A compound according to any of the preceding claims wherein X is an amino or substituted amino group. A compound of formula (1a) wherein R represents a -CONHOH, carboxyl (-CO₂H) or esterified carboxyl group; R² represents an optionally substituted phenylpropyl group; R⁵ represents an optionally substituted alkyl or alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆alkyl group]; and X represents an amino (-NH₂), or substituted amino, hydroxyl or substituted hydroxyl group; and the salts, solvates and hydrates thereof. A compound according to claim 7 wherein R represents a carboxyl (-CO₂H) group. A compound according to claim 7 wherein R represents a -CONHOH group. A compound according to claims 7-9 wherein R⁵ represents a straight or branched C₁₋₆ alkyl or C₂₋₆ alkenyl group. A compound according to claims 7-9 wherein R⁵ represents a straight or branched C₁₋₆ alkyl or C₂₋₆ alkenyl group interrupted by one or more -O- or -S- atoms or -N(R⁷)-, where R⁷ is a hydrogen atom or a C₁₋₆ alkyl group. A compound according to claims 7-9 wherein R⁵ represents a straight or branched C₁₋₆alkyl or C₂₋₆alkenyl group optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- [where R⁷ is a hydrogen atom or a C₁₋₆ alkyl group] and substituted by a C₆₋₁₂aryl C₁₋₆alkyl, C₆₋₁₂aryl C₁₋₆alkoxy, C₆₋₁₂aryl, C₃₋₈heteroaryl, C₆₋₁₂aryl C₁₋₆alkoxy, C₁₋₆alkoxy, C₆₋ ₁₂aryl, -OH, -SH, C₁₋₆alkylthio, carboxyl (-CO₂H), amino (-NH₂) carboxamide (-CONH₂) or guanido -NHC(NH₂)=NH group. A compound according to claims 7-12, wherein X is - NH₂. A compound according to claims 7-12, wherein X is a -NHR¹² group where R¹² is a C₁₋₆ alkyl group optionally interrupted by one or more -O- or -S- atoms or aminocarbonyloxy groups and optionally substituted by a hydroxyl, carboxyl, carboxyalkyl, carboxamido, amino, di-C₁₋₆alkylamino, C₁₋₆alkylamino, C₃₋₆cyclic amino or optionally substituted phenyl groups. A compound according to claims 7-12, wherein X is a -NR¹¹ R¹² group where R¹¹ and R¹² are the same or different and is each a hydrogen atom (with the proviso that when one of R¹¹ or R¹² is a hydrogen atom, the other is not) or an optionally substituted straight or branched alkyl group, optionally interrupted by one or more -O- or -S- atoms or -N(R⁷)- [where R⁷ is a hydrogen atom or a C₁₋₆ alkyl group] or aminocarbonyloxy [-NHC(O)O-] groups or R¹¹ and R¹², together with the nitrogen atom to which they are attached, form an optionally substituted C₃₋₆ cyclic amino group optionally possessing one or more other heteroatoms selected from -O-or -S-, or -N(R⁷)- groups [where R⁷ is a hydrogen atom or a C₁₋₆ alkyl group]. A compound according to any of claims 7 to 15 wherein R² is a phenylpropyl group. A compound according to any of claims 7 to 16 wherein R² is a phenylpropyl group substituted in the cyclic part of the group by one, two or more halogen atoms or C₁₋₆alkyl, C₁₋₆alkoxy, C₂₋₆alkylenedioxy, halo C₁₋₆alkyl, C₁₋₆alkylamino, C₁₋₆dialkylamino, amino (-NH₂), nitro, cyano, hydroxyl (-OH), carboxyl (-CO₂H), esterified carboxyl, C₁₋ ₆alkylcarbonyl, sulphonyl (-SO₂H), C₁₋₆alkylsulphonyl, aminosulphonyl (-SO₂NH₂), C₁₋₆alkylaminosulphonyl, C₁₋ ₆dialkylaminosulphonyl, carboxamido (-CONH₂), C₁₋ ₆alkylaminocarbonyl, C₁₋₆dialkylaminocarbonyl, sulphonylamino (-NHSO₂H), C₁₋₆alkylsulphonylamino, or C₁₋ ₆dialkylsulphonylamino groups. A pharmaceutical composition comprising a compound according to any one of Claims 1-17 and a pharmaceutically acceptable diluent, carrier or excipient. A process for preparing a compound of formula (I) as defined in Claim 1, the process comprising: (a) coupling an acid of formula (II) or an active and/or protected derivative thereof, with an amine of formula (III) or a protected derivative thereof followed by removal of any protecting groups; or (b) decarboxylating a compound of formula (IX) to produce a compound of formula (I) wherein R is a -CO₂H group; and/or (c) interconverting a compound of formula (I).
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CELLTECH LTD; CELLTECH LIMITED
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BEELEY NIGEL ROBERT ARNOLD; MILLICAN THOMAS ANDREW; MORPHY JOHN RICHARD; PORTER JOHN ROBERT; BEELEY, NIGEL ROBERT ARNOLD; MILLICAN, THOMAS ANDREW; MORPHY, JOHN RICHARD; PORTER, JOHN ROBERT
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EP-0489580-B1
| 489,580 |
EP
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B1
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EN
| 19,960,228 | 1,992 | 20,100,220 |
new
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G02B21
| null |
G02B21
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G02B 21/00M4A9, G02B 21/00M4A7C, Y01N8:00
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Confocal laser scanning differential interference contrast microscope
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A confocal laser scanning differential interference contrast microscope comprises a laser source (1), an illuminating optical system (9) for condensing a light beam from the laser source (1) and forming a light spot on an object to be examined (5), a condensing optical system (4) for condensing the light beam from the object to be examined on a detecting surface, a detecting device for detecting the light beam condensed on the detecting surface, the detecting device having a substrate (6) formed with a channel waveguide and two light detecting elements (11),(12), the channel waveguide having a double mode channel waveguide (7) having an entrance end surface on the detecting surface and a waveguide fork which forks the double mode channel waveguide into two channel waveguides (9,10), the two detecting elements detecting lights propagated through the forked two channel waveguides, a scanning device (3) for moving the object to be examined and the light spot relative to each other, and a signal processing device (13) for producing the differential information of the object to be examined by the detection signals of the detecting elements.
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BACKGROUND OF THE INVENTIONField of the InventionThis invention relates to a confocal laser scanning differential interference contrast microscope. Related Background ArtA confocal laser scanning microscope has the advantage that its depth of focus is very shallow and has various applications. Specifically, it has a laser source, an illuminating optical system for condensing a light beam from the laser source on an object to be examined and forming a light spot, a condensing optical system for condensing a light beam from the object to be examined on a detecting surface, detecting means for detecting the light beam condensed on the detecting surface, and scanning means for moving the light spot relative to the object to be examined, and condenses the laser beam on the object to be examined and detects the light on the detecting surface as well through a pin-hole opening. To obtain a differential interference contrast image by the use of such a confocal laser scanning microscope, use can be made of the construction of a differential interference device in a conventional popular optical microscope. However, this is a complicated construction and moreover, requires a special objective lens of little distortion, a Nomarski prism, a wavelength plate, etc. and therefore, the manufacture of various optical elements at high accuracy is difficult, and this has led to the expensiveness of the apparatus. The document JP-A-02 267 513 discloses a confocal laser scanning microscope using waveguides on a substrate. SUMMARY OF THE INVENTIONAccording to one aspect of the present invention, there is provided a confocal laser scanning differential interference contrast microscope comprising a laser source; optical illuminating means for condensing a light beam from said laser source and forming a light spot on an object to be examined; optical condensing means for condensing the light beam from said object to be examined on a detecting surface; a detecting device for detecting the light beam condensed on said detecting surface, the detecting device comprising light detecting means and a substrate having channel waveguide means; scanning means for moving said object to be examined and said light spot relative to each other; and signal processing means for producing information on said object to be examined by the detection signals of said detecting means; characterised in that said channel waveguide means of said detecting device has a double mode channel waveguide which has an entrance end on said detecting surface in which an even mode and an odd mode can be excited at the wavelength of the light incident on the entrance end surface and in which the excited modes are propagable, and a waveguide fork at which said double mode channel waveguide forks into first and second waveguide fork branches ; and in that said detecting device includes two detecting elements for detecting light propagated through said first and second waveguides fork branches respectively, and said signal processing means includes differential means for producing differential information on the object to be examined by outputting the difference between the signals from said detecting elements. Embodiments of the present invention may provide a confocal laser scanning differential interference contrast microscope which is compact and easy to manufacture. For the above, the present invention uses a waveguide device and obtains a differential interference contrast image by a principle entirely differing from the conventional construction. That is, in a confocal laser scanning microscope, a substrate formed with a channel waveguide is provided on light detecting means, and said channel waveguide has a double mode waveguide region having an entrance end surface on said detecting surface and a waveguide fork which forks said double mode waveguide into two single mode waveguides, and is further provided with detecting elements for detecting light propagated through the two single mode waveguides. According to another aspect of the present invention, there is provided a confocal laser scanning differential interference contrast microscope comprising: a substrate formed with channel waveguide means; a laser source for supplying a laser beam through said channel waveguide; optical illuminating means for condensing the laser beam passed through said channel waveguide to form a light spot on an object to be examined, and condensing light reflected from said object to be examined on an end surface of said channel waveguide; light detecting means for detecting light from said object to be examined passing through said channel waveguide; scanning means for moving said object to be examined and said light spot relative to each other; and signal processing means for producing information on said object to be examined by the detection signals of said detecting means; characterised in that said channel waveguide means comprises a double mode channel waveguide which has an entrance end at said end surface and in which an even mode and an odd mode can be excited at the wavelength of the light incident on the end surface and the excited modes are propagable, and a waveguide fork at which said double mode waveguide forks into first, second and third waveguide fork branches ; in that said light detecting means includes first and second light detecting elements corresponding to the outer two of said waveguide fork branches ; and in that said signal processing means is arranged to produce differential information of said object from the detection signals of said detecting elements. In a confocal laser scanning microscope of the so-called fall illumination type using a common objective lens for an illuminating optical system and a condensing optical system, it is possible to provide a waveguide for illumination on the waveguide substrate of detecting means to thereby make them integral with each other. In this case, it is preferable that the channel waveguide on the substrate be made into a construction having a double mode waveguide region having an end surface on said detecting surface and a waveguide fork which forks said double mode waveguide into three single mode waveguides, and an illuminating light beam from a laser source be directed to the middle one of the three single mode waveguides to thereby form a light spot on an object to be examined through an objective lens and provision be made of detecting elements for detecting lights propagating through the two outer ones of the three single mode waveguides. In embodiments of the present invention, a laser spot reflected by the object to be examined becomes a spot image again on the detecting surface by a condensing optical system comprising an objective lens, an imaging lens, etc. When at a position whereat this spot image is formed, the double mode channel waveguide is disposed so that the center of the spot image and the center of the double mode channel waveguide may coincide with each other, if the amplitude distribution of the spot image in the widthwise direction of the waveguide is an even function when the center of the spot is the origin, only an even mode is excited in the double mode waveguide. In the other cases, both of even and odd modes are excited. If a waveguide fork region forking into single mode channel waveguides is provided subsequently to the double mode region, when only the even mode is excited, equal quantities of light are distributed in the two forks, and in the other cases, the interference between the even mode and the odd mode occurs and therefore, the quantities of light distributed in the two forks are generally not equal. Generally, if in the object to be examined, there are inclinations, i.e., a physical inclination as well as all inclinations such as refractive index inclinations which vary the length of the optical path and the inclination of light transmittance distribution or light reflectance distribution, the amplitude distribution of the spot image will have an odd function component and at this time, both of even and odd modes will be excited in the double mode waveguide and as a result, the quantities of light distributed into the two forks will become equal. Accordingly, by detecting the difference between the quantities of light propagating through the two forks, the microscopic inclination of the object to be examined can be detected. Let it be assumed that the angle of inclination of the object to be examined is and sin = α. If the amplitude distribution of the laser spot when the inclination is 0 is u(x) and the field distribution of each eigen mode of the double mode waveguide is fe(x) and fo(x) with respect to the even and odd modes, respectively, u(x) and fe(x) are even functions and fo(x) is an odd function. With k = 2π/λ (λ: wavelength), the amplitude distribution of the laser spot uα(x) when there is an inclination is expressed as uα(x) ≃ u(x)exp(ikαx) = u(x)[cos(kα x) + isin(kαx)]. Here, the coupling efficiency ηe of the even mode is ηe= ∫u(x)cos(kαx)fe*(x)dx∫|u(x)|2dx∫|fe(x)|2dx, while the coupling efficiency ηo of the odd mode is ηo= i∫u(x)sin(kαx)fo*(x)dx∫|u(x)|2dx∫|fo(x)|2dx. If the integration range is suitably chosen and |kαx| << 2π within this range, cos(kαx) ≃ 1, sin(kαx) ≃ kαx and hence, from the fact that u(x), fo(x) and fe(x) are predetermined functions, it can be seen that ηe ≃ constant, ηo ∝iα. If C₁ and C₂ are real constants and is the phase difference between the even and odd modes at the point of branch-off, the variation in the intensity of light by the interference between the even mode and the odd mode is I∝|ηe±iηoexp{i}|2 = |C1±iαC2exp{i}|2. Consequently, if exp{i} is selected to exp{i} = ±i, equation (5) substantially becomes I = C1 2 ∓ 2αC1C2 and a variation in the intensity proportional to α is obtained, and a so-called differential image can be obtained. Accordingly, to obtain such a differential image, it is necessary that at the point of branch-off between the double mode and the single mode, a phase difference an odd number times as great as 90° be brought about between the two modes. For this reason, the well-known fully coupled length of the two modes (the length for which the phase difference between the even and odd modes is 180°) is Lc, it is preferable that the length L of the double mode region be L = Lc(2m+1)/2. (m = 0, 1, 2, ...) Note that expression (1) takes the inclination of the object into consideration and thus, supposes a phase object. The present invention is applicable not only to a phase object, but also an intensity modulation object (an object of which the light transmittance or reflectance varies). Such an object, for example, with α as a real number, can be expressed as uα (x) = u(x)(1 + αx). At this time, obviously, ηe ≃ constant, ηo ∝ α and hence, it is when there is brought about a phase difference integer times as great as 180° between the two modes, that is, when exp{i} = ±1 is placed in equation (5), that the ratio of quantity of light distributed in the two forks becomes greatest by the interference between the even and odd modes. Consequently, to see the differential image of an intensity modulation object, it is preferable that the length L of the double mode region be integer times as great as the coupled length Lc, i.e., L = mLc. (m = 1, 2, ...) That is, depending on how the length L of the double mode region is assumed, the differential image of only the phase modulating portion or the intensity modulating portion of the object can be seen. Where the substrate has an electro-optical effect, a voltage can be applied to the double mode region through an electrode disposed on this region, thereby varying the fully coupled length Lc. Accordingly, even if the length of the double mode region is a predetermined value L, it is possible to satisfy both of equation (7) and equation (10) above by the adjustment of the voltage, and it is possible to make the mechanical length of the double mode region constant and yet obtain the phase information and amplitude information of the object independently of each other by the electro-optical effect. That is, by applying a voltage to the electrode disposed on the double mode region of the channel waveguide, the fully coupled length Lc in the double mode region can be varied into Lc₁ and Lc₂, and by adopting a construction in which for the predetermined length L of the double mode region, is established, in the case of Lc₁, the amplitude information of the object can be obtained as shown in equation (10) above, and in the case of Lc₂, the phase information of the object can be obtained as shown in equation (7) above. By the principle of the differential interference contrast microscope using the channel waveguide as described above, it is possible to obtain the differential information in the widthwise direction of the double mode channel waveguide, but the direction of the differential information is restricted to this direction. So, by combining two detecting means so that the widthwise directions of the double mode waveguides thereof may be orthogonal to each other, it becomes possible to obtain differential information in a desired direction without rotating the object to be examined and the microscope relative to each other. That is, the differential information in the directions orthogonal to each other can be obtained from each detecting means, and by combining the signals from the two detecting means, it becomes possible to observe the differential image as a contrast difference in any direction. Specifically, when the signals obtained in the first and second detecting means are I₁ and I₂, respectively, and if the combined signal of the two is I, signal processing is effected such that I = I1sin + I2cos. Here, by varying within the range of 0-π, the direction in which the contrast of the differential image is created can be changed, and a differential image having a contrast in a desired direction can be obtained without the sample and the microscope being rotated relative to each other. In practical use, it is preferable to suitably vary the value of said and choose such a value of that the differential image of the object to be examined can be expressed most accurately while observing the monitor image as the confocal laser scanning microscope. BRIEF DESCRIPTION OF THE DRAWINGSFigure 1 schematically shows the construction of a first embodiment of the present invention. Figure 2 schematically shows the construction of a second embodiment of the present invention. Figure 3 schematically shows the construction of a third embodiment of the present invention. Figure 4 schematically shows the construction of a fourth embodiment using a substrate on which electrodes are provided. Figure 5 schematically shows the construction of a fifth embodiment using a substrate on which electrodes are provided. Figure 6 schematically shows the construction of a sixth embodiment in which two detecting means are combined. Figure 7 schematically shows the construction of a seventh embodiment in which two detecting means are combined. DESCRIPTION OF THE PREFERRED EMBODIMENTSFigure 1 schematically shows the construction of a first embodiment of the present invention. Light emitted from a semiconductor laser source 1 is reflected by a half mirror 2, enters an objective lens 4 via well-known X-Y two-dimensional scanning means 3 and is condensed on an object surface 5. The light reflected by the object surface 5 and transmitted through the half mirror 2 again via the objective lens 4 and the X-Y two-dimensional scanning means 3 is condensed on a detecting surface on which is disposed the entrance end surface of a channel waveguide 7 formed on a substrate 6. The channel waveguide 7 is a double mode waveguide, and the light propagated through the double mode waveguide 7 soon reaches a branch-off region 8 and has its power distributed into two single mode waveguides 9 and 10, and arrives at two photodetectors 11 and 12 joined to the substrate 6. The entrance end of the channel waveguide 7 performs a function similar to that of a pin-hole and therefore, this construction constitutes a confocal laser scanning microscope. The half mirror 2 and the objective lens 4 together form an illuminating optical system, and the objective lens 4 forms a condensing optical system. When as previously described, there is an inclination at a point on the object 5 illuminated by the laser spot, there is created an inclination in the phase distribution of the laser spot imaged on the entrance end of the channel waveguide 7. By this inclination, even and odd modes are excited in the double mode waveguide 7, and the ratio of light powers arriving at the two photodetectors 11 and 12 is varied by the interference between the two modes. Consequently, the differential signal 14 of the outputs of the two detectors 11 and 12 is taken by differential detecting means 13, whereby minute unevenness of the object surface can be detected. At this time, the length L of the double mode region, with the fully coupled length as Lc, can be L = Lc(2m+1)/2 (m = 0, 1, 2, ...) and this construction provides a differential interference system as already described. Specifically, by control means 15 for memorizing the differential signal 14 from the X-Y two-dimensional scanning means 3 correspondingly to the position of the light beam on the object to be examined and making it into an image, a differential interference image can be displayed on a monitor 16. Figure 2 schematically shows the construction of a second embodiment of the present invention. In this construction, an objective lens 28 is used in common for an illuminating optical system and a condensing optical system, and a portion of a waveguide for detection has also the function of an illuminating system for directing a laser beam. A laser source 21 is a semiconductor laser, and is fixed to a substrate 22 so that the light coupling efficiently may be greatest relative to a single mode channel waveguide 23 formed on the substrate 22. The laser beam which has entered the waveguide 23 is propagated through a double mode waveguide 25 via a fork 24. In the fork 24 of the waveguide, three single mode waveguides are coupled to the double mode waveguide 25, and the middle single mode waveguide 23 is used for illumination and the outer two single mode waveguides are used for detection which will be described later. At this time, by providing such a positional relation that the center line of the middle single mode channel waveguide 23 and the center line of the double mode waveguide 25 coincide with each other, the light entering the double mode waveguide 25 from the middle single mode channel waveguide 23 excites only the even mode in the double mode waveguide 25. Accordingly, the laser beam virtually emerges from an end surface 26 in a single mode state. The illuminating light beam emerging from the end surface of the double mode waveguide 25 enters an objective lens 28 via X-Y two-dimensional scanning means 27 and is condensed on an object surface 29. The light beam reflected by the object surface 29 and thereafter passed again through the objective lens 28 and the X-Y two-dimensional scanning means 27 is condensed on a detecting surface 26 on which is disposed the end surface of the channel waveguide 25 formed on the substrate 22, and a laser spot is formed thereon. Therefore, as in the first embodiment, the power ratio distributed into two single mode channel waveguides 30 and 31 changes with the inclination of the object surface, and if the light from the waveguides 30 and 31 is detected by photodetectors 32 and 33 fixed to the substrate 22 and the differential signal 34 thereof is taken, there will be obtained a differential interference signal. In Figure 2, control means for making the differential signal 34 into an image by a signal from the X-Y two-dimensional scanning means 27 and a monitor are the same as those in the first embodiment shown in Figure 1 and therefore are not shown. Figure 3 schematically shows the construction of a third embodiment of the present invention. A light beam from a laser source 41 is converted into a parallel light beam by a collimator lens 42 and is reflected by a half mirror 43, whereafter it is condensed on an object 46 to be examined by an objective lens 45 via X-Y two-dimensional scanning means 44. The reflected light from the object 46 to be examined is subjected to the condensing action of the objective lens 45, and is transmitted through the X-Y two-dimensional scanning means 44 and the half mirror 43 and directed to detecting means. In the construction of this third embodiment, two waveguide devices 50 and 60 are used as detecting means, and a half mirror 70 for supplying the reflected light from the object to each waveguide device is disposed. Of course, the half mirror 70 may be a pivotable mirror or a removably mounted reflecting mirror. On the respective waveguide devices, as on the waveguide device formed on the substrate 6 in the first embodiment shown in Figure 1, there are provided double mode waveguides 51, 61 and two single mode waveguides 52, 53 and 62, 63 branching off subsequently thereto, and photodetectors 54, 55 and 64, 65 are joined to the exit ends of the respective single mode waveguides. As in the construction of Figure 1, there are provided differential detecting means 56 and 66 for obtaining the differential signal of the signals from the respective photodetectors. What is important here is the lengths L₁ and L₂ of the double mode waveguide regions 51 and 61, respectively, in the first waveguide device 50 and the second waveguide device, 60, respectively. If with the fully coupled length of the even mode and the odd mode as Lc, L₁ and L₂ are chosen to be L1 = mLc (m = 1, 2, ...) L2 = Lc(2m+1)/2, (m = 0, 1, 2, ...) A phase difference integer times as great as 180° is brought between the double mode and the single mode from the output of the first waveguide device 50 and therefore, the differential image of the intensity distribution of the object can be taken out, and since a phase difference odd number times as great as 90° is brought between the two modes from the output of the second waveguide device 60, the differential image of the phase distribution of the object can be taken out. Again in the construction of Figure 3, the control means and the monitor are the same as those in the first embodiment shown in Figure 1 and therefore are not shown. A fourth embodiment shown in Figure 4 is such that in the construction of the first embodiment shown in Figure 1, the substrate has an electro-optical effect and electrodes 17 are provided in the double mode channel waveguide region. By changing the voltage applied to this electrodes 17, it becomes possible to arbitrarily change the fully coupled length in the double mode channel waveguide, and by satisfying any one relation shown in expression (11) above, it becomes possible to obtain the amplitude information and phase information of the object independently of each other. The construction of a fifth embodiment shown in Figure 5 is such that in the construction of the second embodiment shown in Figure 2, the substrate likewise has an electro-optical effect and electrodes 35 are provided in the double mode channel waveguide region. Again in this construction, by changing the voltage applied to the electrodes 35, it becomes possible to obtain the amplitude information and phase information of the object independently of each other. In the fourth and fifth embodiments described above, each two electrodes 17 and 35 for applying a voltage to the double mode waveguides 7 and 25, respectively, are arranged symmetrically with respect to the waveguides 7 and 25, respectively, but depending on the state of the substrate used (in the case of a crystal substrate, the direction or the like of the crystal axis), the electrode arrangement as shown in Figures 4 and 5 is not always optimal. Figure 6 schematically shows the construction of a sixth embodiment of the present invention. In this embodiment, by combining two detecting means, it is made possible to detect the differential information of the object to be examined in any direction. As shown in Figure 6, light emitted from a semiconductor laser source 101 is reflected by a half mirror 102, enters an objective lens 104 via well-known X-Y two-dimensional scanning means 103 and is condensed on an object surface 105. The light reflected by the object surface 105 and thereafter again passed through the objective lens 104 and the X-Y two-dimensional scanning means 103 and transmitted through the half mirror 102 is caused to branch off to two optical paths by a second half mirror 128. The light transmitted through the second half mirror 128 is condensed on the entrance end surface of a channel waveguide 107 formed on a first substrate 106 which constitutes first detecting means. Also, the light reflected by the second half mirror 128 is condensed on the entrance end surface of a channel waveguide 117 formed on a second substrate 116 which constitutes second detecting means. The first substrate 106 and the second substrate 116 are equivalent substrates both having an electro-optical effect. The channel waveguide 107 formed on the first substrate 106 is a double mode waveguide comprising electrodes 115 disposed on a substrate, and the light propagated through the double mode waveguide 107 soon arrives at a branch-off region 108 and its power is distributed into two single mode waveguides 109 and 110, and the light passes to two photodetectors 111 and 112 joined to the substrate 106. Likewise, the channel waveguide 117 formed on the second substrate 116 is a double mode waveguide comprising electrodes 125 disposed on a substrate, and the light propagated through the double mode waveguide 117 arrives at a branch-off region 118 and its power distributed into two single mode waveguides 119 and 120, and the light arrives at two photodetectors 121 and 122 joined to the substrate 116. Since the entrance ends of the channel waveguides 107 and 117 perform a function similar to that of a pin-hole, this construction constitutes a confocal laser scanning microscope. The half mirror 102 for illumination and the objective lens 104 together form an illuminating optical system, and the objective lens 104 forms a condensing optical system. When as previously described, there is an inclination or a gradient of reflectance at a point on the object 105 illuminated by the laser spot, an inclination is created in the phase distribution or intensity distribution of the laser spot imaged on the entrance ends of the channel waveguides 107 and 117, and the direction thereof corresponds to the widthwise direction of each double mode region. By the inclination in the widthwise direction of each double mode region, even and odd modes are excited in the double mode waveguides 107 and 117, respectively, and the ratio of the light powers arriving at the two pairs of photodetectors 111, 112 and 121, 122 is varied by the interference between the two modes. Consequently, by taking the differential signals 114 and 124 of the outputs of the pairs of detectors 111, 112 and 121, 122 by differential detecting means 113 and 123, a minute level difference or a variation in reflectance on the object surface can be detected with respect to each direction. At this time, the length L of the double mode region, with the fully coupled length as Lc, when the phase distribution of the object is observed, can be L = Lc(2m+1)/2, (m = 0, 1, 2, ...) and when the intensity distribution of the object is observed, can be L = mLc, (m = 1, 2, ...) and this construction provides a differential interference system, as described above. The substrates 106 and 116 each has an electro-optical effect and therefore, if the voltage applied to the electrodes 115 and 125 is varied, the fully coupled length Lc can be varied. Consequently, the above two conditions are established relative to the length L of the same double mode region by adjusting the voltage applied to the electrodes 115 in the first substrate 106. That is, the phase distribution and the intensity distribution of the object can be detected indepedently of each other by one waveguide device. A similar action becomes possible by adjusting the voltage applied to the electrodes 125 in the second substrate 116, but since the widthwise direction of the double mode region 117 is perpendicular to that of the first substrate 106, the direction in which there is created the contrast of the obtained signals of the phase distribution and intensity distribution is orthogonal to the direction in which a contrast is created by the signals obtained in the substrate 106. As described above, by signal-processing the differential signals 114 and 124 obtained by the two substrates 106 and 116, there can be obtained a differential interference image having a contrast in a desired direction. Specifically, when the differential signals 114 and 124 are said I₁ and I₂, respectively, signal processing means 129 processes so that the combined signal I of the two may be given by equation (12) above. Control means 126 can memorize the output from the signal processing means 129 correspondingly to the position of the light beam on the object to be examined from the X-Y two-dimensional scanning means 103 and convert this output into image information, and display a desired differential interference image on a monitor 127. Here, for the signal processing means 129, can be arbitrarily varied within the range of 0 - π, and by suitably varying this , the direction in which the contrast of the differential image is created can be arbitrarily changed. Figure 7 schematically shows the construction of a seventh embodiment of the present invention. This construction, like that shown in Figure 6, is a construction of the coaxial fall type in which an objective lens 138 is used in common for an illuminating optical system and a condensing optical system, but a portion of a waveguide in two detecting means has also the function of an illuminating system for directing a laser beam. With regard to a first substrate 132 which constitutes first detecting means, a laser source 131 is a semiconductor laser and is fixed to the substrate 132 so that the light coupling efficiency may be greatest for a single mode channel waveguide 133 formed on the substrate 112 having an electro-optical effect. The laser beam which has entered the waveguide 133 is propagated via a fork 134 through a double mode waveguide 135 comprising electrodes 145 disposed on the surface of substrate. In the fork 134 of the waveguide, three single mode waveguides are coupled to a double mode waveguide 135, and the middle single mode waveguide 133 is used for illumination and the outer two single mode waveguides 140 and 141 are used for detection which will be described later. By providing such a positional relation that the center line of the middle single mode channel waveguide 133 and the center line of the double mode waveguide 135 coincide with each other, the light entering the double mode waveguide 135 from the single mode channel waveguide 133 excites only the even mode in the double mode waveguide 135. Accordingly, the laser beam virtually emerges from an end surface 136 in a single mode state. A second substrate 148 which constitutes second detecting means is constructed similarly to the substrate 132, and a laser beam from a semiconductor laser 147 is propagated through a single mode waveguide 149 via a fork 150 and through a double mode waveguide 151, and emerges from an end surface 152 in a single mode state. The illuminating light beam emerging from the end surfaces of the double mode waveguides 135 to 151 passes through a half mirror 146 to an objective lens 138 via X-Y two-dimensional scanning means 137, and is condensed on an object surface 139. The light beam reflected by the object surface 139 and thereafter again passed through the objective lens 138 and the X-Y two-dimensional scanning means 137 passes through a half mirror 146 and a part of this light beam arrives at the first substrate 132 of the first detecting means and the remainder arrives at the second substrate 148 of the second detecting means. The light beam is condensed on the end surfaces (detecting surfaces) of the double mode waveguides 135 and 151 formed on the respective substrates, and laser spots are formed thereon. Thereafter, as in the first embodiment, the ratio of powers distributed into the outer two single mode channel waveguides 140, 141 and 153, 154 of the three single mode waveguides in the respective substrates changes with the inclination of the object surface, and if the lights from the waveguides 140, 141 and 153, 154 are detected by photodetectors 142, 143 and 155, 156 fixed to the substrates 132 and 148, respectively and differential signals 144 and 157 are taken, there are obtained differential interference signals by the respective detecting means. Again in this construction, the substrates 132 and 148 each have an electro-optical effect and therefore, if the voltage applied to the electrodes 145 and 158 is varied, the fully coupled length Lc can be varied and the phase distribution and intensity distribution of the object can be detected independently of each other by one waveguide device. Likewise, the widthwise direction of the double mode waveguide 135 in the first substrate 132 is perpendicular to the widthwise direction of the double mode waveguide 151 in the second substrate 148 and therefore, the directions in which there are created the contrasts of the obtained signals of the phase distribution and intensity distribution are also orthogonal to each other, and by signal-processing differential signals 144 and 157, there is obtained a differential interference image having a contrast in a desired direction. In Figure 7, signal processing means for the differential signals 144 and 157, control means for making the differential signals into an image by a signal from the X-Y two-dimensional scanning means and a monitor are the same as those in the sixth embodiment shown in Figure 6 and therefore are not shown. In the construction shown in Figure 7, illuminating lights are supplied from the laser sources 131 and 147 in both of the two substrates 132 and 148, but since an illuminating light can be supplied from only one of the two laser sources, the other laser source is not always necessary. In such case, it will become possible to replace one of the substrates 132 and 148 of the two detecting means shown in Figure 7 with the substrate 106 or 116 shown in Figure 6. Where laser sources are provided on both substrates, if a laser beam is supplied from only one of the laser sources and switching is made to the other laser source when one laser source goes wrong, it will become possible to continue the operation of the microscope without interchanging the laser sources. Also, in the sixth and seventh embodiments described above, there is adopted a construction in which the differential signals from the two detecting means are combined and image-processed, but it is also possible to design such that by displaying the differential signals from the two detecting means on discrete monitors, the differential images of the object in a certain direction and a direction orthogonal thereto are observed discretely from each other. Description will now be made of suitable materials for forming the channel waveguides in the construction of each of the above-described embodiments. Soda glass, Pyrex and molten quartz are known as waveguide substrate, but these have no electro-optical effect, and it is difficult to construct a laser diode as a light source and a light receiving element integrally and monolithically. Where use is made of LiNbO₃, LiTaO₃, GaAs or InP as a substrate, it is possible to form an electrode on the basis of the electro-optical effect of these materials to thereby change the fully coupled length Lc of the double mode waveguide region, and by GaAs and InP, a laser diode LD and a detecting element can be made monolithically integral with each other. When Si is used for a substrate, it is possible to make light receiving elements integral with each other. Including these, the materials of substrates and waveguide layers for forming channel waveguides usable in the present invention can be pigeonholed as follows, and it is preferable to use suitable materials on the basis of the characteristics of the materials. Waveguide Structure Substrate Waveguide layer Materials capable of forming electrodesLiNbO₃Ti-diffused LiNbO₃ Proton exchange LiNbO₃ (HxLi1-xNbO₃) LiTaO₃Nb-diffused LiTaO₃ Cu-diffused LiTaO₃ LiNbO₃ Al₂O₃PLTZ Materials capable of making light receiving elements integralSiO₂/Sibariumborosilicate glass Si₃N₄ ZnO Nb₂O₅ Ta₂O₅ (SiO₂)x-TaO2yMaterials capable of forming electrodes and making LD and light receiving elements integralGaAsGa1-xAlxAs InPInxGa1-xAsPy Materials incapable of forming electrodes and making LD and light receiving elements integralSoda glassion exchange glass polyurethane epoxy photoresist Pyrexbariumborosilicate glass Molten quartzPMMA photopolymer Now, each of the above-described embodiments uses an objective lens in common for the illuminating optical system and the condensing optical system, and constitutes a microscope of the so-called fall illumination type, but of course, the present invention may also be constructed as a so-called transmission type microscope in which an illuminating optical system is disposed on one side of an object to be examined and a condensing optical system is disposed on the other side. Further, in each of the above-described embodiments, the laser source and photodetectors are exteriorly disposed relative to the waveguide device, but if a silicon substrate is used, the photodetectors can be constructed on the same substrate as the waveguide device, and if a compound semiconductor substrate such as gallium arsenide, both of the laser source and the photodetectors can be monolithically integrated on the same substrate as the waveguide, whereby the compactness, light weight and energy saving for adjustment of the apparatus can be further put forward. However, where it is difficult to construct the laser source and photodetectors integrally with the waveguide device, these may be separately disposed and design may be made such that light is directed by optical fiber or a lens system. The double mode waveguide may be replaced by two single mode waveguides disposed proximately to each other. Further, of course, by applying suitable processing to the differential signal from the light detecting element which detects the intensity of light passing through the two single mode waveguides, there can be obtained images having various contrasts. In each of the above-described embodiments, a construction in which a light spot is scanned on the object to be examined by an X-Y two-dimensional scanner such as a vibratory mirror or a rotatable mirror is adopted as means for moving the object to be examined and the light spot relative to each other, but alternatively, it is possible to adopt a construction in which the light spot is fixed and a stage on which the object to be examined is placed is scanned. Where the light beam in the optical system is vibrated by a vibratory mirror, a rotatable mirror or the like and the light spot is scanned, it may be impossible due to the influence of the residual aberrations of the optical system to strictly maintain the conjugate relation between the light spot on the object to be examined and the light spot condensed on the light receiving surface of the detecting means (the end surface of the double mode waveguide region), and in such a case, it is preferable to resort to the scanning of the stage. As described above, according to the present invention, neither any special objective lens nor any special optical element such as a Nomarski prism or a wavelength plate is necessary, and on the basis of a new principle using waveguides, there can be provided a confocal laser scanning differential interference contrast microscope having a compact and simple construction. Also, the construction of the second embodiment shown in Figure 2 has the advantage that the alignment of the laser source and the light reception side pin-hole which has heretofore been difficult becomes unnecessary. As described in connection with the third embodiment shown in Figure 3, the phase modulation portion and intensity modulation portion of the object can be taken out independently of each other by changing the length L of the double mode region and the differential images thereof can also be seen. This separation of the phase information and intensity information shows the essential characteristic and usefulness of the microscope according to this embodiment of the present invention. Also, by changing the fully coupled length of the double mode channel waveguides by the utilization of the electro-optical effect of the substrate, it becomes possible to detect the phase modulation portion and intensity modulation portion of the object independently of each other. Moreover, by combining two detecting means, it becomes possible to obtain a differential image in any direction. Although embodiments have been described of a construction in which the double mode waveguide region is forked into a plurality of channel waveguides, the forked channel waveguides are not limited to single mode channel waveguides, but can be constructed of any channel waveguides which can direct light. In the construction of the present invention, it is possible to detect the differential information of the object to be examined by the difference signal of the quantities of light passing through the forked two channel waveguides, but of course, where a signal of the sum instead of the difference is taken, the microscope of the present invention functions as an ordinary confocal laser scanning microscope.
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A confocal laser scanning differential interference contrast microscope comprising: a laser source (1; 21; 41; 101; 131; 147); optical illuminating means (2, 4; 28, 42, 43, 45; 102, 104) for condensing a light beam from said laser source and forming a light spot on an object (5; 29; 46; 105; 139) to be examined; optical condensing means (4; 28; 45, 47; 28; 104; 138) for condensing the light beam from said object to be examined on a detecting surface; a detecting device for detecting the light beam condensed on said detecting surface, the detecting device comprising light detecting means and a substrate (6; 22; 50, 60; 106, 116; 132, 148) having channel waveguide means ; scanning means (3; 27; 44; 103; 137) for moving said object to be examined and said light spot relative to each other; signal processing means for producing information on said object to be examined by the detection signals of said detecting means; characterised in that said channel waveguide means of said detecting device has a double mode channel waveguide (7; 25; 51, 61; 107, 117; 135, 151) which has an entrance end on said detecting surface in which an even mode and an odd mode can be excited at the wavelength of the light incident on the entrance end surface and in which the excited modes are propagable, and a waveguide fork (8; 24; 108, 118; 134, 150) at which said double mode channel waveguide forks into first and second waveguide fork branches (9, 10; 30, 31; 52, 53, 62, 63; 109, 110, 119, 120; 140, 141, 153, 154); and in that said detecting device includes two detecting elements (11, 12; 32, 33; 54, 55, 64, 65; 111, 112, 121, 122; 142, 143, 155, 156) for detecting light propagated through said first and second waveguide fork branches respectively, and said signal processing means includes differential means (13; 56, 66; 113, 123) for producing differential information on the object to be examined by outputting the difference between the signals from said detecting elements. A confocal laser scanning differential interference contrast microscope comprising: a substrate (22; 132) formed with channel waveguide means thereon ; a laser source (21; 131) for supplying a laser beam through said channel waveguide; optical illuminating means (28; 146, 138) for condensing the laser beam passed through said channel waveguide to form a light spot on an object (29; 139) to be examined, and condensing light reflected from said object to be examined on an end surface (26; 136) of said channel waveguide; light detecting means for detecting light from said object to be examined passing through said channel waveguide; scanning means (27; 137) for moving said object to be examined and said light spot relative to each other; and signal processing means for producing information on said object to be examined by the detection signals of said detecting means; characterised in that said channel waveguide means comprises a double mode channel waveguide (25; 135, 151) which has an entrance end at said end surface and in which an even mode and an odd mode can be excited at the wavelength of the light incident on the end surface and the excited modes are propagable, and a waveguide fork (24; 134, 150) at which said double mode waveguide forks into first, second and third waveguide fork branches (23, 31, 32; 133, 140, 141, 149, 153, 154); in that said light detecting means includes first and second light detecting elements (32, 33; 142, 143, 155, 156) corresponding to the outer two (30, 31; 140, 141, 153, 154) of said waveguide fork branches ; and in that said signal processing means is arranged to produce differential information (34; 144, 157) of said object from the detection signals of said detecting elements. A confocal laser scanning differential interference contrast microscope according to claim 1 or claim 2, wherein the double mode channel waveguide (7; 25; 51, 61; 107, 117; 135, 151) of said channel waveguide satisfies one of the following relations: L ≃ mLc (m = 1, 2, ...) L ≃ Lc (2m + 1)/2, (m = 0, 1, 2, ...) where L is the length of the double mode channel, and Lc is the fully coupled length, for which the phase difference between the even and the odd mode is 180°, of even and odd modes in said double mode channel. A confocal laser scanning differential interference contrast microscope according to any preceding claim, wherein said substrate (6; 22; 106, 116; 132, 148) has an electro-optical effect and has an electrode (17; 35; 115, 125; 145, 158) provided on said double mode channel waveguide (7; 25; 107, 117; 135, 151). A confocal laser scanning differential interference contrast microscope according to claim 4, wherein the electrode (17; 35; 115, 125; 145, 158) is connected to a voltage source whereby the fully coupled length Lc in said double mode channel waveguide (7; 25; 107, 117; 135, 151) may be varied to Lc₁ and Lc₂, the following relations being established relative to the predetermined length L of said double mode channel waveguide : L ≃ mLc1 (m = 1, 2, ...) L ≃ Lc2 (2m + 1)/2 (m = 0, 1, 2, ...). A confocal laser scanning differential interference contrast microscope according to any preceding claim, wherein said substrate (6; 22; 50, 60; 106, 116; 132, 148) is a semiconductor substrate, and said light detecting elements (11, 12; 32, 33; 54, 55, 64, 65; 111, 112, 121, 122; 142, 143, 155, 156) are monolithically formed with said waveguide means on said semiconductor substrate.
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NIPPON KOGAKU KK; NIKON CORPORATION
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IWASAKI JUN; OKI HIROSHI; IWASAKI, JUN; OKI, HIROSHI
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EP-0489582-B1
| 489,582 |
EP
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B1
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EN
| 19,960,522 | 1,992 | 20,100,220 |
new
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H04N1
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B41C1
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G03F3, H04N1, G03F1, B41M3, B41C1
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B41M 3/06, H04N 1/387E2
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Platemaking process and system for printing of abstract patterns
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This invention seeks to render baby-plate making, confirmation of whether or not there is a glitch and glitch removal easy in printing abstract patterns on architectural materials. A unit material is separated by an input scanner 1 into pixels of given density for reading. Image data on the unit material read are dissolve-composited given times vertically and horizontally in an endless processor 9 to construct pattern data of given size. Some pixels are extracted from the pattern data in a glitch-checking processor 10 for display on the screen of a monitor 14. It is thus possible to confirm if there is an undesired pattern, i.e., a glitch,by viewing the screen of monitor 14. If there is a glitch, then it can be removed by a glitch removal processor 11. The glitch removal process 11 includes glitch removal means working on three, i.e., scramble, pixel copy and Fourier transform schemes, thereby achieving glitch removal effectively depending on what state the glitch is occurring in.
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This invention relates to a platemaking process and system for printing abstract patterns onto architectural materials, as well as the printed materials obtained using a plate made by such a process or system. As an alternative to wood or other natural materials now in short supply, various forms of architectural materials such as plywood and gypsum boards have recently been developed. For decorating and protecting the surfaces of such materials, printing techniques are now playing an important rôle. Known types of patterns printed on architectural materials include grained patterns following such natural patterns as the grain of wood or a stone, and man-made abstract patterns such as geometrical patterns, sand patterns, ground tints and flower patterns. This invention relates to the making of plates bearing such abstract patterns. A typical conventional platemaking process for printing architectural materials with an abstract pattern is diagramatically illustrated in Fig. 18. A sample of material bearing an abstract pattern defined e.g. by a design, picture or photograph is first fed to the platemaking process to take a photograph of the material sample with a process camera, thereby making a process film. This is successively composed by step-and-repeat printing down (or film composition) with the application of a suitable mask to eliminate any out-of-register between this and material samples adjacent thereto, thereby making a precursor plate for a proof sheet (hereinafter called the baby plate ). The film, on which the material sample has been photographed, is usually about 3 to 5 cm² in size. As shown in Fig. 18B, however, a baby plate (102) of about 1 m² in size may be made by subjecting a film 101 to a step-and-repeat process nine times, both horizontally and vertically. Then, gravure engraving is carried out using the baby plate to make a press plate for gravure printing, followed by printing of a proof. If the desired abstract pattern is obtained, the baby plate is then subjected to the step-and-repeat process to make a form plate, on the basis of which a press plate is in turn made from which to re-print a proof. If the desired abstract plate pattern is again obtained, then printing is carried out with a printing machine. The foregoing are the steps for making the baby plate by film composition, which are all manually carried out by an operator. In recent years, however, there has been an attempt to perform some of the above steps under electronic control by using a layout scanner. For instance, the layout scanner is used to perform the steps from reading a film on which a material sample has been photographed to repeating the resulting image data to produce outputs from the film to making a baby plate. However, the step of subjecting the baby plate to the step-and-repeat process to make a form plate still relies on manual work including photographic composition of the baby plate. As mentioned above, however, the conventional platemaking processes for printing architectural materials, for the most part, are manually carried out, not only posing the problem of incurring much cost but also giving rise to a serious disadvantage as referred to below. Some material samples vary in density or have distorted patterns. These variations in density or pattern distortions are not a problem to the material samples themselves, but they are accentuated on baby plates made by the step-and-repeat process, and show up in the form of a pattern repetition as unintended by creators or designers. This pattern repetition attracts much more attention than do the original abstract patterns, thus causing a grave problem. In the present disclosure, such pattern repetition as is not intended by creators or designers will hereinafter be called a glitch . Now, if a material sample 103 with a fine pattern (not shown) varying in density, as shown at 104 in Fig. 19A, is subjected to the step-and-repeat process seven times horizontally and four times vertically, as shown in Fig. 19B, to make a baby plate (105), then the recurring patterns of the density variation are accentuated on a press plate made by means of the baby plate (105), as shown in Fig. 19C, when it is used for gravure printing, giving rise to a glitch. When jointing is applied to the press plate, however, the grating pattern of the joint attracts relatively more attention then does the glitch. Hence, even though there is a glitch, it is not a problem. Thus, since the occurrence of glitches is a fatal defect in architectural materials with abstract patterns, whether or not there is a glitch should be ascertained somewhere in the process leading to printing with a form plate. Hitherto, this has been achieved with a proof sheet. Confirmation of whether or not there is a glitch may possibly be achieved with the process film, but much difficulty would be involved in making sure of detecting the presence or absence of a glitch with a process film which is monochromic, because the state in which the glitch occurs depends upon a color. Therefore it is necessary to detect the presence or absence of the glitch on the baby plate, although this is costly. Glitch removal work is called retouching , where the remade mask is used to rearrange or rotate the pattern for film composition and the film is subjected to the step-and-repeat process to remake the baby plate. However, retouching requires not only a great amount of skill and labour, but is time-consuming as well, because all this is done manually. As a result, it can be costly to keep a specified appointed time limit for delivery. In addition, a proportion of glitches can never be eliminated by manual retouching. In this case, the plan itself becomes unfeasible, ending up with a waste of the plate made. The foregoing applies to the use of a layout scanner; that is, it is sure that the layout scanner enables the process leading to making the pattern on the baby plate to be automated, but it leaves the above problem totally unsolved, because retouching still relies on manual work. It goes without saying that the pattern of the material sample read by an input scanner may be displayed on a monitor screen to rotate it or subject it to the step-and-repeat process through a suitable mask, but this is essentially tantamount to manual retouching work in terms of work-load. In other words, this is nothing but an alternative to optical work using a film, wherein a pointing device, such as a mouse or stylus pen, is manipulated on the monitor screen. In addition, since the entire pattern of the baby plate of about 1 m² in size cannot be displayed on the monitor screen, it is impossible to confirm whether or not the pattern has been glitch-free, even though retouching work could be performed on the monitor screen. To put it another way, it is impossible to see if glitches will have occurred on the basis of the pattern alone of the material sample. It is after the material sample has been subjected to the step-and-repeat process to make a baby plate that the occurrence of glitches can be confirmed Therefore, in order to confirm if there is a glitch, it is necessary that the whole pattern of the baby plate be displayed on the monitor screen, but this is unachievable with the monitor of a conventional layout scanner. Furthermore, even if the whole pattern of the baby plate could be displayed on the monitor screen, thereby confirming that the baby plate is glitch-free, it is likely that the glitch may occur on a form plate which will be made by subjecting the baby plate to the step-and-repeat process. However, this cannot be solved by the conventional platemaking systems for printing abstract patterns on architectural materials using layout scanners. In order to provide a solution to the above problems, it is an object of this invention to provide a platemaking process and system for printing abstract patterns on architectural materials, which renders it easy to make baby- and form-plates and achieve glitch-checking and removal; and whereby it is easy to make the baby plates. A further object of this invention is to provide a platemaking system for printing abstract patterns for such process which can clear fine abstract patterns of glitches automatically, and/or can clear abstract patterns of a relatively large area of glitches easily, and/or can automatically eliminate density variations of the abstract patterns. The invention is as set out in the claims. By means of this invention,which makes any film unnecessary until baby-plate data are to be output, platemaking work can be carried out in clean office environments, contributing to improving on working conditions and heightening the will of workers to work. According to this invention wherein the endless pattern is constructed by dissolve-compositing unit materials, not only is that composition performed automatically, but whether or not there is a glitch can also be confirmed on the screen of the display means; even when a glitch is found in the endle-ss pattern, some effective means can be taken to meet the situation in early stages, not only thereby avoiding incurring some extra expense and reducing work load considerably but also thereby improving on the accuracy of platemaking, thus leading to reductions in the platemaking cost and the appointed time limit of delivery. In addition, since whether or not there is a glitch can be confirmed at the endless pattern step, a glitch, if found, can be removed in the early stages. This invention also makes it possible to automate retouching, which has so far been performed manually so that much skill and manual dexterity are needed; a glitch, if found, can be removed within a short time, leading to not only cost reductions but also shortening the production time. Furthermore, this invention can easily cope with glitches which could not be removed manually, enabling productivity to be increased greatly. In the accompanying drawings: FIGURE 1 is a block diagram showing the construction of one specific embodiment of the platemaking system of the invention for printing abstract patterns on architectural materials, FIGURE 2 is a block diagram showing one example of a platemaking process utilizing the present platemaking system for printing abstract patterns on architectural materials, FIGURE 3 is a diagram for showing the dissolve composition for making an endless pattern, FIGURE 4 is a view illustrating how the glitch-checking processor operates, FIGURE 5 is a block diagram showing one example of the construction of glitch removal according to a scramble scheme, FIGURE 6 is a view illustrating the substitution of pixels in the block on the scramble scheme, FIGURE 7 is a view showing examples of the geometry of the mask used for the substitution of pixels in the block, FIGURE 8 is a view showing the effectiveness of a pixel copy scheme, FIGURE 9 is a block diagram showing one example of the construction for glitch removal on the pixel copy scheme, FIGURE 10 is a view showing one example of the display screen in selecting source patterns, FIGURE 11 is a view showing how to find the threshold value for constructing mask data on the pixel copy scheme, FIGURE 12 is a view illustrating the binary processing for constructing mask data, FIGURE 13 is a view illustrating the operation of the pixel copy scheme, FIGURE 14 is a block diagram showing one example of the construction for glitch removal on a Fourier transform scheme, FIGURE 15 is a view illustrating the operation of a normalization processor, FIGURE 16 is a view illustrating the operation of a low-frequency component eraser, FIGURE 17 is a view illustrating how to make a baby plate, FIGURE 18 is a block diagram showing an example of one conventional platemaking system for printing abstract patterns on architectural materials, and FIGURE 19 is a view illustrating glitches. One specific embodiment of this invention will now be explained with reference to the drawings. The construction of this embodiment of the platemaking system for printing abstract patterns on architectural materials is shown in Fig. 1, in which reference numeral stands for an input scanner, 2 an output scanner, 3 control means, 4 input means, 5 memory means, 6 a gravure engraving machine, 7 color hard copy, 8 means for processing a plate with an abstract pattern, 9 an endless processor, 10 a glitchchecking processor, 12 a step-and-repeat processor, 13 display processing means, and 14 a monitor. Referring to Fig. 1, the input scanner 1 scans a color film, on which a material sample has been photographed, to separate each pixel into four colors, i.e., cyan (C), magenta (M), yellow (Y) and black (K), and then outputs digital image data with a given bit number, e.g., 1 byte. This is similar in construction to that used with a conventional layout scanner. The output scanner 2 outputs the colors C, M, Y and K from the film, and is similar in construction to that used with a conventional layout scanner. The control means 3, as a whole, places the operation of the platemaking system for printing abstract patterns on architectural materials under control, and is made up of a microcomputer, ROM, RAM, etc. The input means 4 is made up of such input devices as a keyboard and a pointing device. The memory means 5 is constructed from memory devices such as a RAM and/or a hard disk, etc. The gravure engraving machine 6 is provided to engrave both a baby plate and a form plate. The color hard copy 7 is made through a thermal sublimation transfer printer, an ink-jet printer or other printer. The printer used should have the capability to produce color hard copy at least equal in size to the baby plate. More preferably, it should have the capability to produce color hard copy having the size of the form plate. The means 8 for processing a plate with an abstract pattern includes the endless processor 9, the glitch-checking processor 10, the glitch-removal processor 11 and the step-and-repeat processor 12, the operations of which will be referred to later. The display processing means 13 is provided to control a display on the monitor 14, and includes a video RAM of given capacity corresponding to the number of pixels in the monitor 14. The monitor 14 may be built up of such a display device as a color CRT, but should preferably be a device capable of providing high-precision displays. How the embodiment of Fig. 1 operates will now be explained with reference to Fig. 2. Fig. 2 is a block diagram showing an example of the platemaking process utilizing the platemaking system for printing abstract patterns on architectural materials, shown in Fig. 1. Upon receipt of a unit material that is the minimum recurring unit of an abstract pattern, it is set on the input scanner for reading (Step S1). Reading this unit material may be achieved, as with a conventional layout scanner. Bear in mind that when the unit material is a film, it can be set directly on the input scanner; however, in order to read a design or picture, it may be taken on a color film for reading or, if required, it may be photographed with a process camera to form a process film for reading. The image data on the unit material read at Step S1 are stored in the memory means 5. Upon receipt of an instruction for endless processing from the input means 4, the control means 3 operates to drive the endless processor 9 of the processor means 8 to execute endless processing. The term endless processing used herein refers to a process in which while the unit material is being masked, unit materials vertically adjacent thereto are dissolve-composited to form pattern data 4 or 9 times larger in area than the unit material. In the present disclosure, the pattern obtained by endless processing will hereinafter be called the endless pattern. The image data on the baby plate is obtained by simply repeating the endless pattern a desired plurality of times. That is, the endless pattern lies intermediate between the unit material and the baby plate, thereby reducing work load on the operator to a considerable degree. In other words, a conventional baby plate has so far been directly made by subjecting the unit material to the step-and-repeat process through a mask but, as already described, it takes much labor and time to make the baby plate, because the unit material is 3 to 5 cm² in size whereas the baby plate is about 1 m² in size. According to this invention, however, the endless pattern can be obtained by compositing the unit material approximately 9 times at most, although masking is still applied. Since the baby plate can be automatically made by simply repeating the thus obtained endless pattern without recourse to any mask, the work load can be much reduced as compared with the prior art. In what follows, endless processing will be explained in detail with reference to Fig. 3. Now suppose that an instruction is given to composite the unit material three times horizontally and vertically each to form the endless pattern. Then, the unit material will be composited three times horizontally and vertically each in the endless processor 9. According to this invention, however, the composition is carried out horizontally with an operlapping width of WY and vertically with an overlapping width of WT, and the second row is displaced horizontally by an amount WO, as depicted in Fig. 3A. Then, dissolve composition in the horizontally and vertically overlapping regions takes place at the proportion defined by R₂ in Fig. 3B. Referring here to the composition of unit materials 15₁ and 15₂ as an example, the proportion of the pattern on the unit material 15₁ is 100 % in a region R₁ in Fig. 3B, but it decreases linearly to 0 % in a region R₂, while the proportion of the pattern on the unit material 15₂ increases linearly from 0 % to 100 % in that region R₂ and is kept at 100 % in a region R₃. This is also true of vertical composition. In this manner, automatic composition of the unit material is achieved. However, this is not suitable for when it is expected that there might be a step between the overlapping regions of unit materials or a pattern of a relatively large area present in the overlapping regions might be destructed by composition. For this reason, the endless processor 9 is designed to be operable in another mode in which a compositing mask can be located arbitarily. In this mode, for instance, two masks M₁ and M₂ are located on horizontally overlapping regions, as depicted in Fig. 3C, and in the region sandwiched between them, dissolve composition may be performed at the proportion shown by a region R₂ in Fig. 3B. This is also true of vertical composition. Notice that for vertical composition, masks are separately located. Note that the horizontally overlapping width WY, the vertically operlapping width WT, and the displacement WO on the second row may all be preprogrammed as fixed values in the endless processor 9. Alternatively, they may be input by the operator through the input means 4, whenever necessary. In order to locate the two masks, the patterns on the horizontally and vertically overlapping regions may be displayed on the monitor 14, on the screen of which the masks outlines may be traced through a mouse or stylus pen to construct the thus traced pattern data as mask pattern data. Note also that the masks located for horizontal composition are commonly usable for all horizontal composition and those located for vertical composition are commonly usable for all vertical composition. Following completion of the composition of unit materials in the above manner, the endless processor 9 operates to display the composition results on the screen of the monitor 14. Now let us assume that any one point P₁ (Fig. 3A) the unit material 15₁ positioned on an upper-left corner, for instance, is instructed. Then, the endless processor 9 finds coordinate values of points P₂, P₃ and P₄ on the composited pattern with respect to unit materials 15₃, 15₇ and 15₉ positioned on the upper-right, lower-left and lower-right corners of the composited pattern, respectively, said points P₂, P₃ and P₄ having the same address as that of point P₁ and then delimit a rectangle by these four points P₁, P₂, P₃ and P₄ to register it as the endless pattern. Why such delimitation must be performed is,to prevent any step from being generated in making the baby plate. As described later, the baby plate is made by simple repetition of the endless pattern. If the delimitation is performed as mentioned above, then no step is generated even when the endless pattern is repeated vertically, because the pattern on both sides of a line connecting two points P₁ and P₂ in Fig. 3A is quite the same as that on both sides of a line connecting two points P₃ and P₄. This is the reason why the pattern obtained by endless processing is called the endless pattern. The same also holds for horizontal composition. The foregoing is the explanation of Step S2 shown in Fig. 2, and by making the endless pattern lying intermediate between the unit material and the baby plate in this manner, it is possible to much reduce the work load as compared with the prior art. Following completion of endless processing, whether or not there is a glitch in the endless pattern is judged (Step S3). According to the prior art, whether or not there is a glitch has been detected so far with a proof. However, the platemaking system for printing abstract patterns on architectural materials shown in Fig. 1 includes the glitch-checking processor 10, whereby whether there is a glitch can be confirmed early and easily enough. The glitch-checking processor 10 is driven by the control means 3 when a predetermined menu is selected by the input means 4, and gives access to the endless pattern made and registered in Step S2 to cull out (or extract some pixels from) the image data on the endless pattern to scale it down to a given magnification, e.g. quarter the original size. For instance, let us consider that the endless pattern is that shown in Fig. 4A. Then, the glitch-checking processor 10 operates to cull out the pixels in the endless pattern 16 at given intervals, thereby scaling it down to a quarter, as depicted at 16′ in Fig. 4B. Subsequently, this processor 10 operates to repeat the thus scaled-down endless pattern both vertically and horizontally to form a pattern array with no space among the patterns, whereby a pattern array containing endless-pattern repetition is obtained, as shown in Fig. 4C. The processor 10 delivers this array to the display processor means 13 for display on the screen of the monitor 14. We now explain why the endless pattern is scaled down and repeated for display. Since a glitch may be found, in some case at the stage of the baby plate, as already mentioned, and in another case at the original plate, although it has not been detected at the stage of the baby plate, whether or not there is a glitch should preferably be confirmed with a pattern as close to the original pattern as possible. Therefore, whether or not there is a glitch can easily enough be confirmed by scaling down and repeating the endless pattern for display, rather than by displaying the endless pattern alone on the screen of the monitor, as mentioned above. To what degree the endless pattern is scaled down or how many times it is repeated vertically and horizontally may be a matter of option. The more the amount of the image data to be culled out, the more the number of repetitions. However, culling out the image data would give rise to a change in the state of a glitch. Thus, it is desired that the scaled-down endless pattern be repeated twice or thrice vertically and horizontally each, as depicted in Fig. 4C. Indeed, it has been found that this suffices in confirmation of the glitch. If no glitch is detected on the screen of the monitor, as shown in Fig. 4C, then data on the baby plate are constructed (Step S5), and if a glitch is detected, then it is removed. To this end, the platemaking system for printing abstract patterns on architectural materials according to this invention is preferably provided with the glitch removal processor 11 working on the following three schemes: First or scramble scheme in which a pattern located at a given address of the endless pattern is replaced with a pattern located at another address, thereby removing the glitch; Second or pixel copy scheme in which a given pattern is shifted or rotated to other desired position, thereby removing the glitch; and Third or Fourier transform scheme in which the unit material is cleared of a density variation, thereby removing the glitch. Glitch removal on the scramble scheme will first be explained. The scramble scheme is suitable for removing glitches from such fine abstract patterns as sand patterns or ground tints. As can be best seen from Fig. 5, it includes two modes, one being a display mode for simulating glitch removal and the other a batch mode for performing glitch removal actually. The glitch removal processor 11 is driven by the control means 3, when glitch removal is indicated by the input means 4. However, when glitch removal on the scramble scheme is indicated, the display mode of the scramble scheme is driven first. In the interactive mode, the image data on the endless pattern are first culled out until pixels of about 2K bits x 2K bits or less are obtained, and they are read in an image memory 20, whence they are transferred to display processor means 13 for display on the screen of the monitor 14. Then, the pixels in the endless pattern obtained by culling out the image data are divided to blocks of given size, each having about 200 pixels x 200 pixels, for instance. The number of execution of pixel replacement indicated by the operator is given to a random address generator 21 to generate random digits, thereby generating address pairs to indicate two different pixel blocks in only the number corresponding to the number of execution and transferring them to pixel block transfer means 22. Also, such various mask patterns as shown in Figs. 7A to 7E have been registered in mask data storage means 23, and one mask pattern is called out of them by the input means 4 and transferred to the pixel transfer means 22, which in turn extracts the pixel data of the blocks positioned on an address pair AD₁ and AD₂ of the pixel block generated by the random address generator 21, replaces the pixels in these blocks with the mask geometry generated in the mask data storage means 23, and writes them in the original address position. In consequence, the pixels in the mask pattern of the block at the address AD₂ are written in the mask pattern of the block at the address AD₁, and the pixels in the mask pattern of the block at the address AD₁ are written in the mask pattern of the block at the address AD₂. The foregoing operations are repeated by the number of execution indicated. Now let us assume that the culled-out endless pattern 24 is divided into 9 (columns) × 8 (rows) blocks, as depicted in Fig. 6, a mask pattern taking such a shape as shown in Fig. 7A is selected, and the random address generator 21 generates an address pair BL₁ and BL₂ in the first replacement processing. Then, the pixel block transfer processor 22 replaces the pixels in the addresses BL₁ and BL₂ with those contained in the circular mask. Next, suppose that the address generator 22 generates an address pair BL₃ and BL₄. Then, the pixel block transfer processor 22 replaces the pixels in the blocks on the addresses BL₃ and BL₄ with those contained in the circular mask. This operation is subsequently repeated by the number of execution indicated. After the replacement of the pixels in the blocks has been carried out by the number of execution indicated, the image data on the image memory 20 is sent to the display processing means 13 for display on the monitor 14, whereby the operator can confirm on the monitor 14 whether or not there is a glitch. If there is no glitch, then the interactive mode is followed by execution of the batch mode. If there is a glitch, then the number of execution is input to repeat the foregoing operations. The foregoing are the operations of the interactive mode, and the data on the number of execution and the mask shape at the time of completion of the display scheme are stored in a given file. Hereinafter, how the batch mode operates will be explained. Upon confirmation of the fact that any glitch has been removed, the batch mode is indicated. At the time of the batch mode, the image date on the original endless pattern are written in the image memory 20, and the number of execution and the mask shape at the time of the interactive mode are loaded in the random address generator 21 and mask data storage means 23, respectively, thereby performing the above replacement of the pixels in the blocks. The image data on the endless pattern, which has been cleared of a glitch, if any, in this manner, are registered in a given file of the storage means 5. Note that when the image data on the endless pattern are separated into four colors, Y, M, C and K, the image memory 20 must have a capacity of about 8K x 8K x 8 x 4 (bits) in order to perform the above scramble processing for all the colors. This is because one pixel in the data on one color is 8 bits. While the use of only one mask pattern has been described, the mask pattern may be replaced, e.g. by generating random digits for each replacement. Alternatively, it may be possible to generate addresses for two mask patterns to be replaced without recourse to blocking. In the above embodiment, pixel replacement has been described as being displayed on the monitor 14 after carried out by the number of execution indicated. However, if the image is displayed every time 100 pixel replacements without indicating the number of execution, thereby allowing the operator to make sure of glitch removal, then such replacements are stopped forcedly. In the way as mentioned above, it is possible to perform glitch removal work automatically, which has so far been carried out manually. The foregoing is the explanation of how glitches are removed on the scramble scheme. In what follows, how glitches are removed on the pixel copy scheme will be explained. The pixel copy scheme is applied to retouching a distinctive abstract pattern of relatively large size, such as a grained pattern, of glitches. In other words, when a unit material 25 has an archipelagic arrangement of patterns 26₁ to 26₄ of relatively large size, as depicted in Fig. 8, it is likely to give rise to a glitch. If it is intended to remove such a glitch on the scramble scheme, these distinctive patterns may then possibly be destructed, because the image of the endless pattern is divided into blocks on this scheme. To this end, the pixel copy scheme is provided, thereby retouching such a distinctive abstract pattern of the glitch. As diagrammatically shown in Fig. 9, the pixel copy scheme is carried out in two modes, one being an interactive type mode for simulating pixel copy on the screen of the monitor 14 in an interactive mode and the other a batch mode in which the same processing as carried out in the interactive mode is performed automatically. Upon receipt of an instruction to remove a glitch on the pixel copy scheme, the interactive mode is driven, whereby the image data on the endless pattern is culled out until the number of pixels is reduced to about 2K bits x 2K bits, and read in the image memory 30. The image data on the image memory 30 is also sent to the display processing means 13 for display on the screen of the monitor 14. While viewing the screen on the monitor 14, the operator selects a pattern to be moved (which will hereinafter be referred to as the source pattern). Selection of the source pattern is performed by indicating the apexes of the opposite angles of a region surrounding the source pattern by mouse dragging. At this time, the movement of the mouse is sent to a command controller 35 to generate a cursor pattern by a cursor generator 36, which is then written in the location of the mouse on the image memory 30. In consequence, cursors 38₁-38₄ such as those shown in Fig. 10 are displayed on the screen of the monitor 14, and their addresses are recorded in a command recorder 37. It is noted that in Fig. 10 the source pattern is shown at 39. When a rectangular region is thus indicated, a pixel block transfer processor 31 operates to transfer the pixel data in said rectangular region to a source buffer 32, the content of which is then transferred to an automatic mask generator 34, where a source pattern mask is generated as follows. That is, the automatic mask generator 34 applies an operation of 0.3R + 0.59G + 0.11B to the image data of the three primary colors, R, G and B being transferred from the source buffer 32, thereby making the image monochromatic. Then, this monochromic image is smoothed a selected number of times, e.g., 20 times through a filter, whereby fine patterns are erased, leaving only a pattern having a large area. Note that smooth filtering may be achieved in known manner, as by taking the average of 9 nearby pixels. Following smooth filtering, the automatic mask generator 34 operates to calculate a histogram for a pixel density value and find as a threshold value a density value at which frequency is minimized in the density range of 0 to up to about the total frequency of about 50%, and then determines a binary direction from the representative values of the peripheral and central portions of the rectangular region to perform binary processing and generate a mask for the source pattern. Explaining this illustratively with reference to Fig. 11, for instance, now let 40 and 41 denote the frequency and total frequency of the level value of each pixel. Then, the density value at which frequency is minimized at the total frequency of about 50% is calculated to be ND₀, which is determined as the threshold value. Now suppose that such a profile as shown at 42 in Fig. 12 is obtained by this threshold value. Then, the mask for the source pattern is generated using binary numbers [1, 0] denoting the interior and periphery of the profile 42, respectively. This enables the periphery of the profile 42 to be constantly masked. Note that the threshold value may be arbitarily determined by the input means 4. With the mask generated in the above manner, glitch removal is fundamentally performed by moving the source pattern to another position for copying; provided to this end are at least the following commands: (1) Dragging Command According to the pixel copy scheme wherein the source pattern is moved to other position for copying, it is a dragging command which is operable to drag that source pattern to a desired position. With the dragging command indicated and the destination of the source pattern indicated by a cursor, the pixel block transfer means 31 uses the indicated position as a target to transfer a pixel block on that target location to a target transfer buffer 33, thereby copying the content of the source buffer 32 to the target location with reference to the mask pattern generated in the automatic mask generator 34. As will be appreciated by those skilled in the art, the pixel block transferred to the target buffer 33 is used to return the old target location to the original one, when the target location is altered by the next cursor addressing. Referring illustratively to Fig. 13, for instance, in order to move a source pattern S to a target postion T₁, the operator picks up the source pattern S using a mouse, and then moves it to the position T₁. This allows the pixel block transfer means 31 to extract at the target location T₁ the pixels from a rectangular region of the same size as that when the source pattern S has been indicated, and writes them in the target buffer 33. Subsequently, the pixel block transfer means 31 writes the pixels in a region defined by the mask pattern [1] of the content of the source buffer 32 in the target location T₁ with reference to the mask patterns generated in the automatic mask generator 34. By doing so, the source pattern located at S in Fig. 13 has been copied to the target location T₁. The result is sent to the display processing means 13 for display on the monitor 14. Next, when the target location is changed from T₁ to T₂, the content of the target buffer 33 is returned to T₁, followed by the same operation as mentioned above, using T₂ as a new target location. (2) Rotating CommandAccording to the pixel copy scheme, copying is achievable while not only is the source pattern moved at a fixed angle, but also it is rotated through a given angular increment from, e.g., 90° to 360° either clockwise or counterclockwise. It is a rotating command which does this. With the rotating angle indicated by the rotating command, the pixel block transfer means 31 operates to copy the content of the target buffer 33 to the original location of the target pattern with reference to the mask data. Then, the content of the source buffer 32 and the mask data constructed in the automatic mask generator 34 are rotated by the angle indicated, so that while they are being rotated, the content of the target location is copied to the target buffer 33 and the content of the source buffer 32 is copied to the target location with reference to the mask data. Explaining this with reference to Fig. 13, for instance, in order that a pattern located at the target position T₂ and shown by a dotted line is rotated through 90° in the clockwise direction, the pixel block transfer means 31 operates first to write at the target location T₂ the pixels in a rectangular region of the same size as that when the source pattern S has been indicated in the target buffer 33. Then, the content of the source buffer 32 and the mask data in the automatic mask generator 34 are rotated through 90° in the clockwise direction, so that while they are being rotated, the content of the target location T₂ is taken in the target buffer 33 and of the content of the source buffer 32, the pixels in a region having mask data [1] are written in the target location T₂. This enables the pattern lying at the position T₂ and shown by a dotted line in Fig. 13 to have been rotated into the location lying at the same position and shown by a solid line. This result is sent to the display processing means 13 for display on the monitor 14. (3) Source Pattern Erasing CommandIn glitch removal on the pixel copy scheme, it is required to erase the pattern at the original location in order to move the source pattern to another position. It is a source pattern erasing command which does this. With that command and the target location indicated, the pixel block transfer means 31 operates to copy the content of the target buffer 32 to the source pattern location with reference to the mask pattern. Explaining now this with reference to Fig. 13, for instance, in order to erase the source pattern shown therein and copy the pattern lying at a target location T₃ to that position, the pixel block transfer means 31 operates to extract at the target location T₃ the pixels from a rectangular region of the same size as that of the rectangular region when the source pattern S has been indicated by the dragging operation to T₃ and write in the location of the source pattern S the pixels in a region having mask data [1] of the content written in the target buffer 33. This enables the source pattern S to have been erased and the pattern lying at the target location T₃ has been copied to that position in Fig. 3. This result is displayed on the monitor 14. (4) Pattern Replacement CommandThis command is used to copy the pixels lying at a first target location to another second target location, using the mask data for the source pattern. With the first target and that command indicated, the pixel block transfer means 31 operates to return the content of the target buffer 33 to the first target location and copy the pixel block lying at the first target location to be copied to the source buffer 32. With the second target indicated, the pixel block to be copied, lying at the second target, is then transferred to the target buffer 33 to copy the content of the source buffer 32 to the second target location with reference to the mask data. For instance, now let assume that, in Fig. 13, an instruction is given to pick up the pixels lying at the target T₁ and copy them to the target location T₃. The pixel block transfer means 31 operates to return the content of the target buffer 33 to the target location T₁ and write the pixel block lying at the target location T₁ in the source buffer 32 and the pixel block lying at the target location T₃ in the target buffer 33, respectively. Next, of the content of the source buffer 32, the pixels in a region having mask data [1] are written in the target location T₃. This enables the pixels in the target T₁ to have been copied to the target location T₃ in Fig. 13. This result is displayed on the monitor 14. As will be understood by those skilled in the art, the reason why the pixel block lying at the target location to be copied is once transferred to the target buffer 33 is to return it to the original state immediately, if the result of copying is found to be undesired. In addition to the above four commands which have been explained at great length, there are some commands, for instance, a command for clearing the old target location data and the content of the target buffer 33 and returning them to the initial states to execute pixel copy, and an exit command which is operable to copy the content of the target buffer 33 to the original target location with reference to the mask data to return the image to the original state and escape from pixel copy. These commands may be used in various combinations to remove glitches. The foregoing are the interactive mode operations, and the commands, cursor coordinates, etc. indicated in the interactive mode are recorded in command recorder means 37 in the order manipulated by the input means 4. Following completion of the interactive mode, the batch mode is started up. During the batch mode, the image data on the original endless pattern are written in the image memory 30, and the commands, cursor coordinates, etc. recorded in the command recorder means 37 are read out in order and input to command control means 35 for execution. As a result, the same processings as performed by the operator in the interactive mode are applied to the endless pattern data to remove glitches. According to the pixel copy scheme as explained above, even glitches found in an abstract pattern of relatively large size can be removed simply and easily. In what follows, the third or Fourier transform scheme for glitch removal will be explained. As already stated, some glitches may ensue from the density variations of a unit material. The Fourier transform scheme for glitch removal is designed to eliminate the density variations of the unit material - which will end up with glitches - at the endless pattern step. Usually, this scheme is carried out prior to glitch removal on the above scramble and pixel copy schemes. A glitch removal processor 11 for performing glitch removal according to the Fourier transform scheme is constructed, as shown in Fig. 14. With glitch removal according to the Fourier transform indicated, image data on the endless pattern are transferred to normalization means 44 where using as the number of source pixels a value exceeding the number of pixels in the rows and columns of the endless pattern but nearest to a continued product of 2, the surplus is filled in by repeating, as shown in Fig. 15. This is because the so-called fast Fourier transform (FFT) algorithm is applicable to an image having a pixel number that is a continued product of 2. The source image, which has been converted into the image data having a pixel number that is a continued product of 2 in the normalization means 44, is written as such in a source image memory 45, while a given number of pixels are culled out of the source image for writing in a frame memory 46. This is because testing must be performed with a limited number of pixels due to the fact that the time needed for Fourier transform processing increases in proportion to the number of pixels. Then, the content of the frame memory 46 is sent to the display processing means 13 for display on the monitor 14. Bear in mind that the memory capacity of the source image memory 45 must be about 8K x 8K x 4 (bytes), because it must be 1 byte per pixel for each of the Y, M, C and K colors. Note also that the capacity of the frame memory 46 may be about 1K x 1K (bytes) for each color of the R, G and B colors. The respective contents of the source image memory 45 and frame memory 46 are Fourier transformed through a Walsh transform processor 47 for writing in a Fourier transform memory 48. Then, the content written in the Fourier transform memory 48 is cleared of components having a given frequency W or less, say, 10 or less, of horizontal and vertical frequencies Fh and Fv with the exception of a d.c. component DC in a low-frequency component eraser 49, as shown in Fig. 16, and two-dimensional Fourier transform is performed in a Walsh reverse transform processor 50, so that image data on the source image memory 45 and image data on the frame memory, from which some pixels have been extracted, are written in a reverse transform source image memory 51 and a frame memory 52, respectively. The image data written in the frame memory 52 are displayed on the monitor 14 through the display processing means 13, allowing the operator to confirm if the density variations have been removed by viewing the screen of the monitor 14. Usually, outputting from the frame memory 46 to the frame memory 52 is the first to be performed, and after confirmation on the monitor 14, the image in the source image memory 45 is manipulated. Applicant's experimentation indicates that the density variations could be almost completely removed by erasing frequencies of 10 or less, both vertical and horizontal. For this reason, the low-frequency component eraser 49 is designed to erase such frequency components as mentioned above. As will be apparent to those skilled in the art, the frequency components to be erased may be indicated by the input means 4. When a unit material or baby plate varies in density, the unit material must be once again photographed to remove such density variations according to the conventional processes. According to this invention, however, they can be easily removed on the image data, contributing to considerable cost and work-load reductions. While the three glitch removal schemes have been described, it is understood that almost every glitch can be removed by a suitable combination of these schemes. The foregoing are the process of Step S4 shown in Fig. 2, and if glitches are removed at the endless pattern step, then data on the baby plate are constructed (Step S5). As shown in Fig. 17, the baby plate is made by simply repeating the endless pattern vertically and horizontally, and provided to this end is a step-and-repeat processor 12. That is, with baby-plate making indicated by the input means 4, the step-and-repeat processor 12 is started up to arrange image data on the endless pattern given times vertically and horizontally. The thus constructed baby-plate data are registered in the storage means 5. Following completion of the baby-plate making, whether or not there is a glitch on the baby plate is again determined (Step S6). In this case, confirmation of whether or not there is a glitch may be done by viewing the baby-plate data displayed on the monitor 14, from which some pixels have been extracted. It is preferable, however, that this be done by supplying the baby-plate data from the storage means 5 to the color hard copy 7 for hard-copying, because the baby plate is of large size and used for representation to the user. If a glitch is detected at Step S6, then the above glitch removal is again done at Step S4, but if no glitch is found, then the baby-plate data are output (Step S7). For outputting the baby-plate data, there are two approaches according to one of which the baby-plate data are supplied directly to the gravure engraving machine 6 to make a press plate directly and according to the other the baby-plate data are output to a film by the output scanner 2 to make a press plate using that film. Using either of the two may be a matter of decision by the operator. Following making the press plate of the baby-plate in the above manner, it is used to print a proof, with which whether or not there is a glitch is again checked out (Step S8). If there is a glitch, then the operator goes back to either Step S1 to reread the unit material or Step S4 to remove the glitch at the endless pattern stage. If the operator goes back to Step S1, it would be a waste of all the steps done so far. However, this waste is limited to a minimum, because the present process is more reduced in cost and work load than the conventional processes, owing to being automated. If no glitch is detected with the proof using the baby-plate, then data on a form plate are output (Step S9). This is done by arraying the baby-plate data by the desired number of times vertically and horizontally with the step-and-repeat processor 12, and the thus constructed form-plate data are registered in the storage means 5, whence they are output. As in the case of outputting the baby-plate data, the form-plate data may be supplied to the gravure engraving machine 9 to make a form plate directly, or alternatively may be output to a film by the output scanner 2 to make a press plate using that film. Following outputting the form-plate data in the above manner, a proof is again printed for the last checking (Step S10). If a good result is produced, then the form plate is used for printing with an actual printing machine (Step S11). With this step, the entire process is completed. Note that if there is a glitch on the proof of the form plate, then the operator goes back to either Step S1 or S4.
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A process for dissolve-compositing an abstract pattern for use in producing architectural materials with said abstract pattern thereon, comprising the steps of: (a) copying image data of a unit material (15), read only once by an input scanner (1), M times vertically (where M is a positive integer) and N times horizontally (where N is a positive integer), for providing a pattern (16) of a predetermined size; and (b) trimming said pattern (16) at upper, lower, left and right edges, wherein the upper and lower edges are equivalently positioned relative to the image data and the left and right edges are equivalently positioned relative to the image data. A process according to Claim 1, further comprising the step of: (c) forming a press plate with the trimmed pattern (16'). A process according to Claim 2, wherein step (c) comprises: (i) replicating said trimmed pattern (16') a plurality of times to form a pattern array composed of a plurality of contiguous replicas of said trimmed pattern (16'); and (ii) forming a press plate with the pattern array (Fig. 4C). A process according to Claim 2, wherein the image data comprises pixel data and said step (c) comprises: (i) culling a plurality of pixels (39) from said trimmed pattern to form a reduced pattern (16'); (ii) replicating said reduced pattern (16') a plurality of times to form a pattern array composed of a plurality of contiguous replicas of said reduced pattern (16'); (iii) determining whether an undesired pattern is present in the pattern array ; and (iv) if no undesired pattern is determined in step (c) (iii), forming a press plate with the trimmed pattern, and otherwise modifying the trimmed pattern by repeating steps (i), (ii) and (iii) and forming a press plate with the modified trimmed pattern. A method for making a printed material having an abstract pattern, obtained from a process as claimed in any preceding Claim, wherein the press plate is used for printing an image on a print receiving material. A method as claimed in Claim 5 as appendant to any one of Claims 1 to 3, comprising the further steps of: (a) determining whether an undesired pattern is present in the pattern; (b) if no undesired pattern is determined in step (a), forming a press plate with the pattern, and otherwise modifying the pattern and forming a press plate with the modified pattern. A method as claimed in Claim 6, wherein step (b) comprises: (i) providing mask data representative of a given shape; (ii) applying the mask data to the pattern at a first location and removing data of the pattern corresponding to the given shape defined by the mask date; (iii) applying the mask data to the pattern at a second location for defining replacement data of the pattern corresponding to the given shape defined by the mask data; (iv) replacing the removed data of step (b) (ii) with the replacement data of step (b) (iii) thereby replacing data of the first location with that of the second location in accordance with the mask data; and (v) repeating steps (i)-(iv) a plurality of times for new first and second locations. A method according to Claim 7, wherein the mask data is generated according to data of the pattern at one of said first and second locations. A method according to Claim 6 wherein the modification of step (b) comprises: (i) subjecting said pattern to a two-dimensional Fourier transform; (ii) cancelling given frequencies from the Fourier transformed pattern for providing a transformed pattern; and (iii) reverse Fourier transforming said transformed pattern for providing a filtered pattern. A system for dissolve-compositing an abstract pattern for printing on architectural materials, comprising: input scanner (1) means for scanning a unit material and producing first image data; first means (9) for copying the first image data M times vertically and N times horizontally, wherein M and N are positive integers, for generating second image data of an abstract pattern and trimming said pattern; second means (10) for determining if an undesired pattern is present in the second image data; and third means (11) for modifying said second image data for removing the undesired pattern if determined by said second means. A system according to Claim 10, wherein the third means (11) comprises means (23) for providing mask data representative of a given shape, means (22) for applying the mask data to the second image data at a first location to define a first portion of the second mask data, and at a second location to define a second portion of the second image data, and means for replacing said first portion of the second image data with said second portion of the second image data, thereby replacing data of the first location with data of the second location with the replacement data being defined in accordance with the mask data, and means for operating said providing means, said applying means and said replacing means a plurality of times using new first and second locations for eliminating said undesired pattern. A system according to Claim 11 further comprising means (21) for randomly determining the first and second locations for each operation of the applying means. A system according to Claim 11 of Claim 12, wherein said means (23) for providing mask data comprises means (34) for generating mask data from a portion of the second image data, and said means (31) for replacing comprises means for copying data of the second location to the first location on the basis of said mask data for eliminating said undesired pattern. A system according to Claim 10, wherein said third means comprises means (47,49,50) for subjecting the second pattern data to a two-dimensional Fourier transform for producing transformed pattern data, deleting given frequency components from the transformed pattern data for producing filtered pattern data, and reverse Fourier transforming the filtered pattern data, thereby removing the undesired pattern from the second image data. A plate making system for printing on architectural materials an abstract pattern obtained from a system as claimed in any one of Claims 10 to 14, further comprising fourth means for forming a press plate according to said second image data if no undesired pattern is determined, otherwise according to said modified second image data.
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DAINIPPON PRINTING CO LTD; DAI NIPPON PRINTING CO., LTD.
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ARAI EISUKE; KURATA MICHIO; MODEGI TOSHIO; MUROTA HIDEKI; ARAI, EISUKE; KURATA, MICHIO; MODEGI, TOSHIO; MUROTA, HIDEKI; Arai, Eisuke, c/o Dai Nippon Printing Co., Ltd.; Kurata, Michio, c/o Dai Nippon Printing Co., Ltd.; Modegi, Toshio, c/o Dai Nippon Printing Co., Ltd.; Murota, Hideki, c/o Dai Nippon Printing Co., Ltd.
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EP-0489585-B1
| 489,585 |
EP
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B1
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EN
| 19,951,122 | 1,992 | 20,100,220 |
new
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C07C6
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B01J23
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C07C11, C07C6, B01J23, C07B61
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M07C521:06, M07C521:14, M07C527:224, M07C523:30, C07C 6/04+11/02, B01J 23/30, M07C521:10, M07C521:08
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A metathesis process for olefines and a catalyst to be applied therein
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A metathesis process for the conversion of olefines, in which an olefine is brought into contact with a solid catalyst system comprising, on a solid silica carrier, 0.1 - 40% by weight of a wolfram compound, under reaction conditions in which the catalyst system converts the olefine into olefines having a different molecular weight; the silica carrier being a magnesium oxide or titanium oxide-containing co-gel prepared by means of a co-gelling system.
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The invention relates to a metathesis process for the conversion of olefins as well to a catalyst to be applied therein. The metathesis or disproportionation of olefins refers to a reaction, in which one or more olefins are converted into olefins having a different molecular weight. The olefin may be disproportionated with itself into olefins having a higher molecular weight and into olefins having a lower molecular weight. In this case, the reaction may be called a self-disproportionation . Two different olefins can also be converted into other olefins by means of the metathesis reaction. In order to function, the metathesis reactions of olefins require a catalyst system, which includes a transition metal compound, often a cocatalyst, and sometimes also a compound acting as a promoter. Catalyst systems based on tungsten and molybdenum are especially efficient. Such catalysts generally comprise a tungsten or molybdenum oxide on an inorganic carrier, such as silica or alumina. It is known to add to such catalysts different substances acting as a promoter. Thus, for example according to the EP publication 152,112, a titanium oxide or titanium-containing substances are added to the surface of the catalyst as a promoter. The US patent 4559320 describes the use of tungsten catalyst on a silica-carrier, to which catalyst is also added a magnesium oxide. According to Catalysis Reviews, 3(1), pages 37-60 (1969) it is stated that the best olefin disproportionation catalysts are oxides and sulfides of molybdenum and tungsten and oxides of rhenium, niobium, tantalum and tellurium. Magnesium silicate, magnesia-titania, alumina-titania, alumina and silica have been used as supports. Silica, alumina and aluminum phosphate are reported as the best supports according to this publication. In accordance with the present invention, it has surprisingly been observed that the activity of said tungsten catalysts can be that contain magnesium oxide or titanium oxide considerably improved in the metathesis process of olefins, if a silica co-gel is used as a carrier, in which the silica is gelled together with a magnesium oxide or titanium oxide before the addition of tungsten. Thus, the inventive metathesis process is characterized by the characteristic features presented in Claim 1. In accordance to a certain additional feature of the invention, improvements are also achieved in the activity, if the catalyst in the metathesis process of olefins is fitted into a reactor in a certain manner. In the catalyst to be used in the inventive process, the co-gel to be used as a carrier may be prepared from solutions of silicate and magnesium or titanium compounds. The sodium silicate solution is thus reacted with a suitable magnesium salt, e.g. with a magnesium oxide, magnesium hydroxide, magnesium nitrate, magnesium sulphate, magnesium acetate) the pH-value being over 8, whereby co-gels are obtained, whose general properties depend on the SiO₂/Mg stoichiometry and the processing conditions. The magnesium salts may alternatively be mixed with hydrosols, which have been obtained by acidifying sodium silicate solutions when the pH-value is less than 4, whereby silica/magnesia co-gels are obtained, whose general properties depend on the stoichiometric conditions used, the pH-value, the reaction time and the temperature. The testing and adjustment of these parameters is apparent to those skilled in the art. The hydrogel obtained in this way is washed and dried. Silica-titanium oxide co-gels are prepared in a similar manner. The co-gels obtained are advantageously ion exchanged by means of any acid or ammonium salt for removing the alkali metal cations suitable for the ion exchange. In addition, the co-gels obtained can be activated before use by heating them to a temperature of over 200°C into a water content of about 10%, whereby at least the surface layer of the co-gel changes into an acid form. In the inventive process, such co-gels can be preferably used as a carrier of the catalyst, in which the Si/Mg ratio is in the range 10/1 - 10000/1 or the Si/Ti ratio is in the range 10/1 - 10000/1. The tungsten catalyst to be used in the inventive process is prepared from co-gels prepared in the manner described above by adding thereto a tungsten oxide in any manner desired. The tungsten may be added either directly as an oxide or as precursor. In the last-mentioned case, the oxide precursor is changed into an oxide form by calcination. Suitable oxides or precursors are tungsten compounds, which can be changed into an oxide form in the calcination conditions. Examples of suitable tungsten compounds include oxides, halides, sulphides, sulphates, nitrates, acetates and their mixtures. Examples of suitable tungsten compounds thus include tungsten pentachloride, tungsten dichloride, tungsten tetrachloride, tungsten hexafluoride, tungsten trioxide, tungsten dioxychloride, tungsten trisulphide, metatungsten acid, orthotungsten acid, ammonium phosphotungstenite and ammonium metatungstenite. The quantity of the tungsten oxide or tungsten precursor in the co-gel carrier may vary from 0.1% by weight of tungsten oxide to 40% by weight. A suitable quantity is generally within the range 2-20% by weight. The tungsten oxide or precursor may be added to the co-gel carrier either by dry mixing or by absorbing from a solution. In the latter case, the co-gel carrier is treated with a tungsten-compound solution, and the extra solution is then removed. Alternatively, the solution can be used only to such an extent, which the co-gel carrier is capable of absorbing. If the tungsten compound is in the precursor form, a calcination is performed for the catalyst, in which it is heated in the presence of an oxygen-containing gas, e.g. air. The temperature required is generally 300-800°C and the reaction time from 15 minutes to 20 hours. The calcination can also occur in the presence of an olefine containing 2-20 carbon atoms. A solid tungsten catalyst can be in the desired form, such as in the form of balls, granules or agglomerates, when a solid-bed catalyst is used in the metathesis of olefines. If slurry catalyst systems are used, the catalyst is preferably in the form of a fine powder. The inventive WO₃/SiO₂ metathesis catalysts can be applied to the metathesis reactions of olefins in a known manner. The metathesis reaction of olefins is typically performed within a temperature range of 250-500°C, preferably within the range of 380-430°C. The metathesis reaction is specific for the catalyst system used. A suitable temperature range for the WO₃/SiO₂ system is thus within the range of 300-450°C. The metathesis is performed by bringing the feeding olefin in either a liquid or gas phase into contact with the inventive catalyst. If the reaction is performed in a liquid phase, suitable solvents or diluents may be used, such as saturated aliphatic hydrocarbons, e.g. pentane, hexane, cyclohexane, etc., or aromatic hydrocarbons, such as benzene or toluene. If the reaction is performed in a gas phase, suitable diluents may be used, such as aliphatic hydrocarbons, e.g. methane, ethane, propane, butane or inert gases, such as nitrogen. The reaction time is not critical, and it may vary within a wide range. A reaction time from 0.1 seconds to 24 hours is generally sufficient. The metathesis reaction is typically performed by passing the olefin through a reaction vessel, which is partially or totally packed full with the catalyst. It has been observed according to the invention that the activity and conversion of the catalysts can be essentially improved by diluting the tungsten-containing catalyst with such a carrier, which contains no tungsten. This may result from the fact that the reaction balance is reached very rapidly in the metathesis reaction. The reaction balance is reached in the catalyst already on its surface layers, whereby the remaining portion of the catalyst can no longer affect the balance position, but is in a way unnecessary. A considerably diluted catalyst can thus be used in the catalyst bed. Thus, in the inventive process, a catalyst bed can be used, which includes a catalyst containing ca. 6% of tungsten, the remaining portion being formed of the inventive carrier prepared by gelling. The dilution in the catalyst bed can also be achieved so that the tungsten containing catalyst is placed under the carrier layers containing no tungsten or between such layers. The inert layer then acts as a heat compensator and a mixing intensifier. In the inventive metathesis process there may be converted e.g. acyclic mono-olefins, e.g. 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexane, 1,4-hexadiene, 2-heptane, 1-octane, 2-nonene, 1-dodecene, etc. Propene is especially suitable. In addition thereto, a raffinate to be derived from an MTBE unit may be used as a feed, which raffinate contains various quantities of suitable butenes as well as paraffins acting as diluents. The oxygen containing components have to be removed before the metathesis reaction, since they impede the reaction. For example an activated alumina, a copper catalyst and molecular sieves can be used for purifying the raffinate feed. Example 1A metathesis catalyst was prepared by impregnating 1.34 g of a carrier (manufacturer Grace Co) twice with a 4% NH₄WO₃ water solution and by drying the water periodically by heating in an oven at 115°C. This silica titania co-gel is a silica titania carried prepared by gelling, in which the titane is homogenously distributed into the whole gel quantity. The gel's titane content was 4.3%, particle size 0.05 mm, surface area 467 m²/g and pore volume 1.07 ml/g. The catalyst thus obtained was dried at 120°C overnight. The catalyst was examined in the propene metathesis reaction by loading into a tube reactor a mixture, which contained 0.102 g of the catalyst prepared in the manner described above and 0.718 g of the same carrier without tungsten. The catalyst was activated by passing through the catalyst bed first air at 600°C at a flow rate of 10 l/h for 1.5 hours and then nitrogen at the same temperature at a flow rate of 10 l/h for 30 minutes. Thereafter, propene was passed into the reactor at 400°C first at a flow rate of 1.07 l/h and after 3 hours at a flow rate of 3.5 l/h. The propene then converted into ethene and butenes. The results are shown in Table 1, in which the activities of the catalyst are given as units g of the converted propene / g of Wo x h. The percentages of the product distributions are percents by weight. Time (h) Ethene (%) Propene (%) Butenes (%) Others (%) Conversion (%) Activity (g/gh) 010.07765.02122.0592,8434.98300.80 511.19561.66025.5981.5538.341078.80 1011.10461.87125.6491.4738.131072.54 2010.52963.55024.7261.2036.451025.32 309.95765.44523.5841.0034.56972.01 409.72966.16523.1980.9133.83951.76 The metal content of the catalyst was 5.25%. The reaction was an extremely pure metathesis reaction without acid catalytic side reactions. Example 2A metathesis catalyst was prepared, as described in Example 1, but as a carrier was used a silica-magnesia co-gel (manufacturer W.R. Grace), which is a silica-magnesia prepared by gelling, in which the magnesium occurs only as surface ions. The gel's magnesium content was 1.0%, particle size 0.05 mm, surface area 334 m²/g and pore volume 1.07 ml/g. The catalyst obtained was examined in the propene metathesis reaction by loading into a tube reactor uppermost 0,0945 g of a pure catalyst and under this layer a mixture, which contained 0.0268 g of the catalyst prepared in the manner described above as well as 0.0707 g of a pure carrier. The tungsten content of the catalyst was 5.8% of the catalyst. The activation of the catalyst was performed as in Example 1. Thereafter, propene was passed into the reactor at 400°C first at a flow rate of 3.0 l/h and after 2 hours at a flow rate of 5.0 l/h. The results are shown in Table 2. Time (h) Ethene (%) Propene (%) Butenes (%) Others (%) Conversion (%) Activity (g/gh)2 09.92148.98534.5976,5051.021357.01 28.69948.85735.4996.9551.142267.36 59.46851.39337.2941.8548.612154.93 108.86852.60037.4601.0747.402101.42 207.79758.85633.0530.2941.141824.07 As in Example 1, the reaction was an extremely pure metathesis reaction without acid catalytic side reactions. Comparison example 1 A catalyst was prepared in the same way as described in Example 1, but a pure silica was used as a carrier. The tungsten content of the catalyst was 5.8% and 0.3782 g of this catalyst was used in the catalyst bed. The activation was performed by passing through the bed air at 600°C for 90 minutes. The metathesis reaction of propene was examined in the presence of this catalyst according to Example 1. The results are shown in Table 3. Time (h) Ethene (%) Propene (%) Butenes (%) Others (%) Conversion (%) Activity (g/gh) 17.87746.43534.53311,15553.56533.71207.86050.78239.9821.37649.21893.85258.10151.41839.3661.11548.582123.52297.40754.80336.8630.92745.197173.50Comparison example 2A metathesis catalyst was prepared, as described in Example 1, but PQ's silica CS-1231 was used as a carrier. Particle size of the silica was 0.6-1.6 mm and the surface area 330 m²/g. The carrier was impregnated twice with a 4% NH₄WO₃ water solution. After the drying, the catalyst was still sieved with an 0.5 mm sieve and the fine portion was rejected. The W content of the coarse portion used as catalyst was 5.8%. MgO sieved with an 0.5 mm sieve and comprising 1.5% of the weight was mixed mechanically into the catalyst described above and packed by layers into the reactor such that 0.1064 g of the carrier and 0.1025 g of the catalyst were placed first and finally 0.1026 g of the carrier. The activation of the catalyst was performed as in Example 1. The results are shown in Table 4. Time (h) Ethene (%) Propene (%) Butenes (%) Others (%) Conversion (%) Activity (g/gh) 110.0644.8131.3913.1955.19135.9839.3548.1934.527.8651.81370.78108.4451.3537.063.0648.65348.17 235.6368.2025.920.2431.80378.29Comparison Example 3In the same way as described in Example 1, a wolfram catalyst was prepared for an SiO₂-MgO carrier, the metal content of which catalyst was 6.03%. In the Example, a larger reactor was used, into which a larger quantity of the catalyst could be loaded, and ethene and t-and c-butenes were now used as feeds. The feeding ratios could be adjusted within a relatively large range for examining the properties of the catalyst. When loading the catalyst, an inert silicon carbide was now used as a diluent instead of a pure carrier. Starting from the top portion of the reactor, 1.0 g of SiC, 0.5 g of the catalyst and 5.06 g of SiC were packed into the reactor. The catalyst was calcinated, as in Example 1. Table 5 shows the results of the run. The temperature of the reactor was maintained at 400°C during the entire run. Time (h) Ethene (%) Propene (%) t-butene (%) c-butene (%) Others (%) Met.act. (g/gmet*h) Conversion (g/gh) 516.0630.0032.798.599.55278.035.506013.1051.3121.1012.740.61475.549.1712514.7448.1223.3312.290.51445.946.7819011.7950.8518.4117.360.59471.246.4637012.8946.5417.3422.350.22418.340.1940613.0944.8316.7524.510.82403.038.96Note! The Table uses standard-run values, whereto it has been returned after each change. Comparison Example 4The Example was performed according to Comparison Example 3, and also the catalyst load was similar. As a feed was now used Neste's own raffinate (OLEFJK), which according to the product specification contains ca 50% of butenes and 8% of 1-butene, which are metathesis active. For removing the impurities, MeOH, MTBE, dimethyl ether and isobutene, in the olefine fraction, the feed was provided with an efficient purification system. In this connection, also the reactor temperature was varied. Time (h) Ethene (%) Propene (%) t-butene (%) c-butene (%) Others (%) Met.act. (g/gmet*h) Conversion (g/gh) 4.5*51.4113.438.403.350.00151.126.30 65.546.7428.542.401.260.40320.964.51 223.546.4330.922.301.370.44347.763.83 Note! The Table shows only a standard-level stability after the changes. The catalyst is extremely stable and requires no regeneration. Feeds: ethene 17.66 l/h and raff II 7.24 l/h.
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A metathesis process for the conversion of olefins, in which an olefin is brought into contact with a solid catalyst system comprising, on a solid silica carrier, 0.1-40% by weight of a tungsten compound, under reaction conditions in which said catalyst system converts the olefin into olefins having a different molecular weight, characterized in that the silica carrier is a magnesium oxide or titanium oxide-containing co-gel prepared by means of a co-gelling system. A process according to claim 1, characterized in that the carrier contains at least 80% of silica and not more than 20% of magnesium oxide. A process according to claim 1, characterized in that the carrier contains at least 80% of silica and not more than 20% of titanium oxide. A process according to any of the preceding claims, characterized in that the catalyst system comprises a catalyst bed, which contains a mixture of the silica carrier, which does not contain tungsten or, optionally, another inert medium, such as silicon carbide, together with the tungsten-containing carrier. A process according to any of the preceding claims, characterized in that the catalyst system comprises a catalyst bed, in which, in the direction of the feed flow, the first layer comprises the silica carrier, which does not contain tungsten, or, optionally, another inert medium, and the second layer comprises the tungsten-containing carrier. A process according to any of the preceding claims, characterized in that the olefin comprises one or more olefins containing 2-20 carbon atoms. A process according to claim 6, characterized in that the olefin mixture can contain 0-80% of i- or n-paraffins. A process according to any of the preceding claims, characterized in that the metathesis reaction is performed at a temperature of 250-500°C. A metathesis catalyst to be used in the process according to any one of claims 1-8, characterized in that it comprises 0.1-40% of weight of a tungsten compound on a silica carrier, which is a magnesium- or titanium-containing co-gel prepared by means of a co-gelling system, which co-gel is optionally calcinated by heating at 300-800°C for 15 minutes - 20 hours. A catalyst according to claim 9, characterized in that the calcination is performed in the presence of air or of an olefin containing 2-20 carbon atoms at a temperature of 300-800°C.
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NESTE OY
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HIETALA JUKKA; KNUUTTILA PEKKA; LINNA ANJA; HIETALA, JUKKA; KNUUTTILA, PEKKA; LINNA, ANJA
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EP-0489586-B1
| 489,586 |
EP
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B1
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EN
| 19,950,426 | 1,992 | 20,100,220 |
new
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B41N7
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B41N7, B41N10
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B41N10, B41N7
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B41N 10/04, B41N 7/06
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Printing offset blanket and rubber roll
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A printing offset blanket in accordance with the present invention has a surface printing layer (3) made of a mixture of silicone rubber and oil-resisting rubber rupported on a supporting layer (1). Similarly a printing rubber roll in accordance with the present invention has a printing surface made of a mixture of silicone rubber and oil-resisting rubber and supported on a supporting layer.
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The present invention relates to an offset blanket and rubber rolls used for offset printing. In printed matter such as filter or display prints or the like in which ink layers printed on the surface of a transparent member are seen through transmitted light, thickness variations in the ink layers, if any, are represented in terms of difference in color shade. It is therefore required that the ink layers have a substantially even thickness. In offset printing using an offset blanket, however, a major portion of the ink transferred from the printing block to the blanket surface is not transferred to the surface of a member to be printed thereon, but remains on the blanket surface. Accordingly, the ink layers on the surface of the member to be printed thereon disadvantageously present concavo-convex portions due to cohesive failure, causing the layer thicknesses to become considerably uneven. Further, the print edges cannot be clearly reproduced. A normal printing offset blanket has a supporting layer which incorporates or does not incorporate a porous compressive layer, and a surface printing layer on the supporting layer. The surface printing layer is made of a highly oil-resisting rubber material, mainly an acrylonitrile-butadiene copolymer (hereinafter referred to as NBR). However, when printing is conducted at a high speed with the use of such a normal offset blanket, an adhering force is produced between paper and the blanket. This may cause the paper to be curled or broken. Similar problems are produced at the time of printing on a smooth member such as coated paper or the like. These problems are generally produced when so-called paper discharging properties (paper releasing properties) are low. Since such troubles greatly lower the productivity, the blanket is required to present good paper discharging properties. To improve the paper discharging properties in a conventional offset blanket, there have been proposed a variety of methods such as a method in which polishing the surface of the surface printing layer is so conducted as to make the polished surface coarse, a method in which starch incorporated in the surface printing layer is first vulcanized and then extracted as dissolved in a solvent (Japanese Patent Publication No. 238/1991), a method in which ultraviolet rays are irradiated onto the surface of the surface printing layer (Japanese Patent Unexamined Application No. 37706/1976), a method of surface chlorination (Japanese Patent Publication No. 51729/1972) and the like. However, according to the method of making the surface roughness coarse or forming small holes in the surface, the contact area of the printing layer with paper is reduced to deteriorate the net-point shape, thus reducing the reproducibility of the net points. According to the method of surface chlorination, micro-cracks are produced in the surface of the surface printing layer, resulting in deterioration of net-point reproducibility, washing quality and the like. The method of surface treatment with ultraviolet rays is effective in improvements in paper discharging properties and is excellent in net-point reproducibility. However, this method requires not only an ultraviolet irradiation installation but also strict control of irradiation dose. In addition to paper discharging properties, attention should be placed on the problem of paper powder accumulated on the offset blanket due to long-term printing. More specifically, regenerated paper is increasingly used with the trend of resource conservation and recycling. However, the regenerated paper which is deteriorated in quality, is liable to produce paper powder. Accumulation of paper powder on the offset blanket provokes problems of decrease in printing quality, increase in the number of washing steps and the like. To lessen the generation of paper powder, it is effective to make the surface roughness of the surface printing layer coarse as done for improvement in paper discharging properties. It is however difficult to reduce the retention of paper powder without injuring the net-point reproducibility. On the other hand, recent offset printing is liable to use ultraviolet-curing ink (UV ink) in order to prevent the working environment from being polluted by solvent components evaporated from ink, as well as for more efficient printing at a higher speed. With the diversification of a member to be printed thereon (particularly, plastics), the demand for the ultraviolet-curing ink is increased, particularly in the field of food packing which should be kept free from printing smell. In a commercially available offset printing machine, ink transfer rolls 5a, ink kneading rolls 5b and ink applying rolls 5c are disposed from an ink reservoir 6 to a printing cylinder 7 for kneadingly supplying ink 8 to the printing cylinder 7, as shown in Fig. 13. In view of the strength and affinity with oil ink, such rubber rolls 5a, 5b, 5c are generally made of a material mainly made of oil-resisting rubber such as NBR, urethane rubber or the like, or plastic such as polyvinyl chloride or the like. However, when the ultraviolet-curing ink is used in the offset printing machine using such oil-resisting rubber, the rolls are disadvantageously swollen or decreased in outer diameter due to elution of additives such as a plasticizer or the like contained in the rubber rolls. As a result, the rubber rolls cannot be used for a long period of time, requiring frequent replacement. Summary of the InventionIt is a main object of the present invention to provide an offset blanket suitable for printing printed matter such as filter or display prints, which is capable of forming, on the surface of a member to be printed thereon, ink layers which have a substantially even thickness and of which edges are clear. It is another object of the present invention to provide a printing offset blanket which is improved in paper discharging properties and retention of paper powder without the net-point reproducibility injured. It is a further object of the present invention to provide a printing rubber roll which is excellent in stability with respect to ultraviolet-curing ink and which can be used for a long period of time. To achieve the objects above-mentioned, the inventors studied hard the rubber material forming the surface printing layer of an offset blanket. The inventors presumed that the use of silicone rubber which was hardly wetted with ink, reduced the amount of ink remaining on the blanket surface at the time of printing, thus solving the problems above-mentioned. However, when the surface printing layer was made of the silicone rubber alone, the transferability of ink (ink applicability) from the printing block to the blanket is extremely deteriorated. This rather provoked the problems of concavo-convex portions, unclear edges and the like mentioned earlier. In the worst case, the prints became blurred. Further, since the silicone rubber is poor in oil resistance, the silicone rubber is liable to be deteriorated and swollen by ink or a solvent used for washingly removing the ink, causing the resulting prints to be distorted. In view of the foregoing, the inventors have further studied and found that, by the combination of the silicone rubber and rubber excellent in oil resistance, there could be obtained a surface printing layer excellent in the transferability of ink from the blanket to the surface of a member to be printed thereon, in transferability of ink from the printing block to the blanket and in oil resistance. Further, the inventors have also found a novel fact that, by mixing silicone rubber and oil-resisting rubber as a material of a surface printing layer, the surface printing layer has been remarkably improved in paper discharging properties and retention of paper powder without deterioration of oil resistance of the surface printing layer, deterioration of printing quality such as net-point shape, ink applicability and the like, increase in the number of printing steps or the like. Based on the findings above-mentioned, the present invention has been now accomplished. More specifically, the offset blanket according to the present invention comprises a supporting layer and a surface printing layer disposed thereon and made of a mixture of silicone rubber and oil-resisting rubber. On the other hand, the inventors have also studied hard a rubber material excellent in stability with respect to ultraviolet-curing ink, and found that silicone rubber has been excellent in durability with respect to ultraviolet-curing ink. However, the silicone rubber presents a low strength and a small affinity with ink. Accordingly, rubber rolls made of silicone rubber cannot sufficiently achieve their objects such as ink kneading, ink transfer and the like. More specifically, in an offset printing machine, a number of rubber rolls are disposed from an ink reservoir to a printing cylinder and ink is passed through gaps among the rolls so that the ink is kneaded to form an even ink film. When there is used a rubber material poor in rubber strength such as tensile strength or the like, the between-roll gaps cannot be sufficiently reduced, causing the ink not to be sufficiently kneaded. The poor ink transferability causes trouble in the transfer of ink from rubber rolls to the surface of the printing cylinder. In any case, the silicone rubber is disadvantageous in view of lowered printing quality such as printing blur or the like. Further, the silicone rubber is poor in oil resistance and is therefore liable to be readily deteriorated and swollen by normal oil ink or a solvent used for washingly removing the ink. Accordingly, when rolls made of silicone rubber are used with normal oil ink, printed characters or images may be distorted. On the other hand, normal oil-resisting rubber such as NBR is poor in durability with respect to ultraviolet-curing ink, but is excellent in strength and presents good ink kneading and ink transfer which are objects to be achieved by rubber rolls. The inventors have further studied and found that rubber rolls made of a mixture of silicone rubber and oil-resisting rubber have been excellent in durability with respect to ultraviolet-curing ink, as well as in rubber strength and ink transferability. Further, even though used with normal oil ink, rubber rolls made of a mixture of oil-resisting rubber and silicone rubber are prevented from being deteriorated or swollen by oil ink or a solvent used for washingly removing the ink. According to the present invention, the rubber rolls refer to ink rolls such as ink transfer rolls 5a, ink kneading rolls 5b, ink applying rolls 5c or the like as shown in Fig. 13, except for the offset blanket. Brief Description of the DrawingsFigures 1 to 3 are schematic section views of examples of the lamination structure of an offset blanket in accordance with the present invention; Figure 4 is a graph illustrating the relationship between blending proportion of silicone rubber/NBR and oil resistance in an offset blanket; Figure 5 is a graph illustrating the relationship between blending proportion of silicone rubber/NBR and printing characteristics in an offset blanket; Figure 6 is a graph illustrating the relationship between blending proportion of silicone rubber/NBR and printing characteristics in an offset blanket; Figure 7 (a), (b) and (c) are graphs respectively illustrating the sections of ink layers obtained in Printing Test 1 using offset blankets of Example 1 and Comparative Examples 1 and 2; Figure 8 (a), (b) and (c) are graphs respectively illustrating the sections of ink layers obtained in Printing Test 2 using offset blankets of Example 1 and Comparative Examples 1 and 2; Figure 9 (a), (b) and (c) are graphs respectively illustrating the sections of ink layers obtained in Printing Test 2 using offset blankets of Example 1 and Comparative Examples 1 and 2; Figure 10 is a graph illustrating the relationship between the blending proportion of silicone rubber/NBR and volume increase rate due to swelling in a printing rubber roll; Figure 11 is a graph illustrating the relationship between the blending proportion of silicone rubber/NBR and tensile strength in a printing rubber roll; and Figure 12 is a graph illustrating changes, with the passage of time, in outer diameter of rubber rolls of Example 11 and Comparative Example 5; and Figure 13 is a schematic view illustrating the arrangement of rubber rolls disposed in a commercially available offset printing machine. Detailed Description of the InventionAs silicone rubber to be used for the offset blanket and rubber rolls of the present invention, there may be suitably used, out of a variety of conventional silicone rubbers, millable-type silicone rubber which can be handled in the same manner as for normal rubber. The millable-type silicone rubber is supplied as a rubber compound mainly made of straight-chain polyorganosiloxane (silicone rubber) having a high polymerization degree (6,000 to 10,000) to which there are blended a silica-type reinforcing filler, an extender filler, a dispersion accelerator and the like. As the silicone rubber, the most prevailing one is methylvinyl silicone [(CH₂ = CH)(CH₃ SiO], but there may also be used polyorganosiloxane in which a polymeric unit such as (CH₃)₂ SiO, (CF₃ CH₂ CH₂)SiO, (C₆ H₅)₂ SiO or the like is being introduced in the straight chain. Examples of the oil-resisting rubber include acryl rubber and NBR. There are commercially available a variety of NBRs having different grades dependent on the molecular weight and proportion of acrylonitrile. For an offset blanket, it is preferable to use NBR in which the amount of acrylonitrile is in a range from about 30 to about 40 % in view of compatibility of oil resistance and ink transferability. For rubber rolls, it is preferable to use NBR in which the amount of acrylonitrile is not less than 30%, preferably from about 40 to about 50 %, in view of compatibility of oil resistance and ink transferability. In the offset blanket, the blending proportion by weight of silicone rubber/oil-resisting rubber is preferably in a range from 2/98 to 80/20. In such a range, the offset blanket is excellent not only in paper discharging properties, but also in retention of paper powder and ink transferability. More specifically, if the proportion of silicone rubber exceeds 80 % by weight, the transfer of ink from the printing block is not good, causing the ink amount to be insufficient. This involves the likelihood of the generation of concavo-convex portions and unclear edges mentioned earlier, blurred prints and the like. Further, such an offset blanket is lowered in oil resistance so that the surface printing layer is liable to be deteriorated and swollen by ink during printing operation, or by a solvent. On the other hand, if the proportion of silicone rubber is below 2 % by weight, such addition of silicone rubber is meaningless to deteriorate the paper discharging properties. If the proportion of silicone rubber is extremely high, the paper discharging properties and retention of paper powder are improved, but the ink applicability and the oil resistance are apt to be lowered. Accordingly, when particularly desired to improve the paper discharging properties and the retention of paper powder, it is preferred to increase the proportion of silicone rubber (generally, not less than 10 % by weight for the total amount of rubber raw materials). On the other hand, if the proportion of silicone rubber is extremely small, the paper discharging properties and the retention of paper powder are apt to be lowered. Accordingly, when particularly desired to improve the ink transferability and the oil resistance in the application where great importance is not placed on the paper discharging properties and the like, it is preferred to lessen the proportion of silicone rubber (generally, not more than 60 % by weight for the total amount of rubber raw materials). Accordingly, in view of balanced relationship among the ink transferability from the block to the blanket, the paper discharging properties and the retention of paper powder, the blending proportion of silicone rubber/oil-resisting rubber is preferably in a range from 10/90 to 60/40. On the other hand, the blending proportion by weight of silicone rubber/oil-resisting rubber in a printing rubber roll is preferably in a range from 20/80 to 60/40. In such a range, the resulting rubber roll is excellent in durability with respect to ultraviolet-curing ink and improved in rubber strength and ink transferability. If the proportion of silicone rubber exceeds 60 % by weight, the durability with respect to ultraviolet-curing ink is improved, but the rubber strength is lowered to lower ink kneading and ink transferability, and the oil resistance is also lowered, causing the resulting rubber roll to be readily swollen by oil ink. If the proportion of silicone rubber is below 20 % by weight, the durability with respect to ultraviolet-curing ink is lowered. Thus, the use of ultraviolet-curing ink provokes swelling of the rubber roll, elution of additives or the like. According to the present invention, the surface printing layer of the offset blanket may be manufactured by forming, in the form of a surface printing layer, a rubber compound prepared by mixing silicone rubber and oil-resisting rubber with a variety of additives such as a vulcanizer, vulcanizing accelerator, vulcanizing supplement accelerator, filler, plasticizer and the like, and by vulcanizing the resulting mixture in a conventional manner. The rubber roll of the present invention may be manufactured in a manner similar to that above-mentioned. Examples of the vulcanizer contained in the rubber compound include sulfur, organic sulfur-containing compounds such as tetramethyl thiuram disulfide (TMTD), N,N′-dithiobis morpholine. As the vulcanizer, there may also be used a crosslinking agent of the organic peroxide type. Examples of the crosslinking agent of the organic peroxide type include tert-butylhydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-bis (tert-butyl peroxy) cyclododecane, 2,2-bis(tert-butyl peroxy) octane, 2,5-dimethyl-2,5 di(tert-butyl peroxy) hexane, 1,3-bis(tert-butyl peroxy isopropyl) benzene, n-butyl-4,4-bis(tert-butyl peroxy) vallerite, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxy benzoate and the like. Examples of the vulcanizing accelerator include, as a main accelerator, thiazoles such as dibenzothiazyl disulfide(MBTS), N-oxydiethylene-2-benzothiazyl sulfenic amide (OBS), N-cyclohexyl-2-benzothiazyl sulfenic amide (CBS), N-tert-butyl-2-benzothiazyl sulfenic amide (TBBS) and the like. As necessary, there may be suitably used, as a secondary accelerator, 1,3-diphenyl guanidine (DPG), tetramethyl thiuram monosulfide (TMTM), zinc dimethyldithiocarbamate (ZnMDC), zinc ethylphenyldithio carbamate (ZnEPDC), tetramethyl thiuram disulfide (TMTD) which has been mentioned as the examples of the vulcanizer, and the like. Examples of the filler include inorganic fillers such as calcium carbonate, hard clay, soft clay, water-containing silicic acid, silicic acid anhydride, barium sulfade, diatomaceous earch, talc, mica, asbestos, graphite, pumice and the like; and organic fillers such as regerated rubber, powdery rubber, asphalts, styrene resin, glue and the like. Fig. 1 shows the arrangement of a compressive offset blanket having a supporting layer 1 containing a compressive layer 2 made of a synthetic resin foamed body or the like, and a surface printing layer 3 formed on the surface of the supporting layer 1. Fig. 2 shows the arrangement of a normal offset blanket having a supporting layer 1 and a surface printing layer 3 laminated directly on the supporting layer 1. In each of the offset blankets in Figs. 1 and 2, the supporting layer 1 is formed by laminating a plurality of layers of supporting bases 11 (three layers in Figs. 1 and 2) through primer layers (adhesive layers) 4, and the surface printing layer 3 is formed on the supporting layer 1 through a primer layer 4. The thickness of the surface printing layer 3 is not limited to a specific value, but is preferably not greater than 350 µm. In the offset blanket in Fig. 1, primer layers 4 are also disposed between the surface printing layer 3 and the compressive layer 2 in order to prevent the surface printing layer 3 from being positionally shifted by the application of pressure at the time of printing, provoking defective prints such as positional shift in net point, misregister and the like. As the supporting base 11, a woven fabric of cotton, Rayon or the like is normally used but, as shown in Fig. 3, a sheet body 10 of a plastic film such as a polyester film, polypropylene film or the like, an aluminium foil or sheet, or the like, may be used instead of a plurality of supporting bases 11. Fig. 3 shows the arrangement of offset blanket in which, in the layer arrangement in Fig. 1, three supporting bases 11 below the compressive layer 2 are replaced with one sheet body 10. However, it is also possible that, in the layer arrangement in Fig. 2, three supporting bases 11 are replaced with one sheet body 10. In this case, it is preferable to form a surface printing layer 3 on the sheet body 10 through a primer layer 4, likewise in the arrangement in Fig. 2. According to the present invention, the offset blanket is not limited to any of the arrangements shown in Figs. 1 to 3, but may have any of a variety of lamination arrangements. In the offset blanket of the present invention, the surface printing layer is made of a mixture of silicone rubber of which surface tension is small and which is hardly wetted with ink, and oil-resisting rubber excellent in oil resistance. This provides excellent transferability of ink from the blanket to a member to be printed thereon, as well as good ink transferability from the printing block to the blanket. Also, the surface printing layer is excellent in oil resistance. Further, the offset blanket of the present invention is advantageously improved in paper discharging properties and retention of paper powder. Thus, the offset blanket of the present invention is suitably used for printing on a transparent member such as filter or display printing, as well as for high-speed printing. The printing rubber rolls of the present invention are used as ink rolls for transferring ink from an ink reservoir to a printing cylinder in offset printing. Particularly, the present rubber rolls are suitable for offset printing using ultraviolet-curing ink, but it is a matter of course that the present rubber rolls may also be used for offset printing using normal oil ink. As mentioned earlier, the rubber rolls of the present invention are made of a mixture of silicone rubber excellent in durability with respect to ultraviolet-curing ink and oil-resisting rubber excellent in rubber strength and ink transferability. Accordingly, even though used in printing using ultraviolet-curing ink, the present rubber rolls can be used for a long period of time while assuring high printing quality. ExamplesThe following description will discuss in more detail the present invention with reference to Examples thereof and Comparative Examples, but it is a matter of course that the present invention should not be limited to such Examples. Example I (Offset Blanket)Study of Blending Proportion of Rubber MaterialsNine different material rubbers were prepared by blending, in nine proportions from 10/90 to 90/10 as shown in Figs. 4 to 6, millable-type silicone rubber (KE8751-U manufactured by Shinetsu Kagaku Company) and NBR (KRYNAC 803 manufactured by Polyser Company) as oil-resisting rubber. There were prepared nine different compound rubbers by blending 100 parts by weight of each of the material rubbers thus prepared, 30 parts by weight of a white filler, 30 parts by weight of dioctylphthalate, 5 parts by weight of zinc oxide, 0.5 part by weight of stearic acid, 1.5 part by weight of AccTT and 2.5 parts by weight of AccMOR. As Comparative Examples, there were prepared, in the same manner as above-mentioned, compound rubbers by respectively using, as the material rubber, 100 parts by weight of silicone rubber alone and 100 parts by weight of NBR alone, as the raw material rubber. Test of Oil ResistanceEach of the compound rubbers above-mentioned were molded and vulcanized to prepare a block of 1 mm x 2 cm x 2 cm. Each of the blocks was immersed in toluene maintained at 40°C. After 24 hours, the volume of each block was measured. Based on the volume VT1 before immersion and the volume VT2 after immersion, the volume increase rate VT (%) due to swelling was calculated according to the following equation. The results are shown in Fig. 4. From the results in Fig. 4, it is found that the smaller the proporiton of silicone rubber is, the greater the oil resistance. Measurement of Ink TransferabilityAs shown in Fig. 1, each of the compound rubbers above-mentioned was laminated, through a primer layer 4 of rubber-type adhesive, on the surface of a supporting layer 1 in which four supporting bases 11 of cotton and a compressive layer 2 of foamed polyurethane were laminated through primer layers 4 of rubber-type adhesive. Each laminated body was vulcanized to prepare an offset blanket having a surface printing layer 3 with thickness of 350 µm. With each offset blanket set to an ink transfer testing machine of Prüfbau Company, the ink transferability T₁ (%) from a printing block to each blanket and the ink transferability T₂ (%) from each blanket to coated paper were measured under the following conditions with the use of black ink (TOYO INK MARK V manufactured by Toyo Ink Company) and coated paper manufactured by Daio Seishi Company. Fig. 5 shows the results of the ink transferability T₁ (%) from the block to each blanket, while Fig. 6 shows the results of the ink transferability T₂ (%) from each blanket to coated paper.Test Condition:Printing pressure600N Printing speed2 to 4 m/s Roll temp.25°C Fed ink amount0.522 Ambient temp.25°C Ambient humidity60% From the results in Fig. 5, it is found that, in each of the blankets presenting a silicone rubber proportion of 2 to 60 % by weight, the ink transferability T₁ % from the block to the blanket is substantially equal to that of the blanket presenting a NBR porportion of 100 % by weight. It is also found that, when the proportion of silicone rubber exceeds 60 % by weight, the ink transferability T₁ % is gradually lowered and that, when the proportion of silicone rubber exceeds 80 % by weight, the ink transferability T₁ % is suddenly lowered. From the results in Fig. 6, it is found that, in each of the blankets presenting a silicone rubber proportion of not less than 2 % by weight, particularly not less than 10 % by weight, the ink transferability T₂ % from the blanket to coated paper is remarkably high as compared with the blanket presenting a NBR proportion of 100 % by weight. Observation of Density VariationsAs to the coated papers obtained in the measurement of ink transferability above-mentioned, the surfaces were visually checked for density variations of the ink layers. It was observed that the offset blankets respectively using silicone rubber alone and NBR alone presented remarkable variations of density, but the offset blankets jointly using silicone rubber and NBR presented no outstanding density variations in the ink layers. The offset blanket using silicone rubber alone was inferior in density variation, blur and the like to the offset blanket using NBR alone. Example 1As shown in Fig. 3, the compound rubber presenting a silicone rubber/NBR proportion of 20/8 prepared in Study of Blending Proportion of Rubber Materials, was laminated, through a primer layer 4 of rubber-type adhesive, on the surface of a supporting layer 1 formed by laminating one supporting base of cotton 11, a compressive layer 2 of foamed polyurethane and a polyester film 10 in this order through primer layers 4 of rubber-type adhesive, the compound rubber being laminated on the supporting layer 1 at its surface at the side of the supporting base 11. The laminated body was vulcanized to prepare an offset blanket having a surface printing layer 3 with a thickness of 350 µm. Comparative Example 1An offset blanket was prepared in the same manner as in Example 1, except for the use of the compound rubber presenting a silicone rubber proportion of 100 % by weight prepared in Study of Blending Proportion of Rubber Materials. Comparative Example 2An offset blanket was prepared in the same manner as in Example 1, except for the use of the compound rubber presenting a NBR proportion of 100 % by weight prepared in Study of Blending Proportion of Rubber Materials. Printing Test 1With each of the offset blankets of Example 1 and Comparative Examples 1, 2 set to a glass plate printing machine (Ector-600 CL manufactured by Koyo Company), a stripe pattern having a line width of 20 µm and a line distance of 20 µm was printed on the surface of a glass plate with the use of an original block of 300 lines and ultraviolet-curing ink (manufactured by Dai-Nihon Ink Company) for glass. The section shapes of the ink layers forming the printed stripe pattern were measured with a non-contact type surface-shape measuring device (Surface Shape Analyzer SAS2010 manufactured by Meishin Koki Company). The glass ink swelling VUV % in the surface printing layer was 9% for Example 1, 17% for Comparative Example 1 and 25% for Comparative Example 2. Results of the measurement of section shapes of the ink layers are shown in Fig. 7 (a) to (c), in which Fig. 7 (a). shows the section shapes of the ink layers obtained with the use of the offset blanket of Example 1, Fig. 7 (b) shows the section shapes of the ink layers obtained with the use of the offset blanket of Comparative Example 1, and Fig. 7 (c) shows the section shapes of the ink layers obtained with the use of the offset blanket of Comparative Example 2. From the results shown in Fig. 7, it is found that, when the offset blanket of Comparative Example 2 having a surface printing layer of NBR alone was used, the ink layer sections presented concavo-convex portions and the ink layers presented a variety of section shapes and heights. Thus, it was found that the ink layers were partially projected and concaved due to cohesive failure. Further, the ink layers presented various shapes at both ends thereof. Thus, it was found that the edges of the ink layers were unclear. When the offset blanket of Comparative Example 1 having a surface printing layer of silicone rubber alone was used, the ink layer sections presented no concavo-convex portions and the ink layers presented substantially equal section shapes and heights. However, the ink layers presented gentle slopes at both ends thereof. Thus, it was found that the edges of the ink layers were unclear. When the offset blanket of Examples 1 having a surface printing layer of a mixture of silicone rubber and NBR, the ink layer sections presented no concavo-convex portions and the ink layers presented substantially equal section shapes and heights. Thus, it was found that the ink layers were neither protruded nor concaved due to cohesive failure. Each ink layer rises sharply at both ends thereof. Thus, it was found that the ink layers were clear at the edges thereof. Printing Test 2With the use of each of the blankets, a printing test was conducted in the same manner as in Printing Test 1, except that a stripe pattern having a line width of 100 µm and a line distance of 100µm was printed on the surface of a glass plate. In this test, each ink layer was measured as to the section shape in a direction at a right angle to the stripe pattern. Fig. 8 (a) shows the section shapes of the ink layers obtained with the use of the offset blanket of Example 1, Fig. 8 (b) shows the section shapes of the ink layers obtained with the use of the offset blanket of Comparative Example 1, and Fig. 8 (c) shows the section shapes of the ink layers obtained with the use of the offset blanket of Comparative Example 2. From the results shown in Fig. 8, it is found that, when the offset blanket of Comparative Example 2 was used, the ink layer sections presented concavo-convex portions and the ink layers presented a variety of section shapes and heights. Thus, it was found that the ink layers were partially protruded and concaved due to cohesive failure. Further, both ends of each ink layer project as exceeding from a predetermined width. Thus, it was found that the edges of the ink layers were unclear. When the offset blanket of Comparative Example 1 was used, the ink layers presented gentle slopes at both ends thereof. Thus, it was found that the edges of the ink layers were unclear. Further, the heights of the ink layers are lower than those of the respective ink layers obtained with the use of the offset blankets of Comparative Example 1 and Example 1 to be discussed later. Thus, it was found that, when the offset blanket of Comparative Example 1 was used, the ink transferability from the block to the blanket was not good, causing the ink amount to be insufficient. It was also found that, when the offset blanket of Examples 1 was used, the ink layer sections presented no concavo-convex portions due to cohesive failure and the ink layers were clear at the edges thereof. Printing Test 3With each of the offset blankets of Example 1 and Comparative Examples 1, 2 set to the glass plate printing machine above-mentioned, a square dot having a length of 300 µm and a width of 250 µm was printed on the surface of a glass plate with the use of an original block of 300 lines and the ultraviolet-curing ink for glass above-mentioned. As to each ink layer forming the square dot, the section of the longer side thereof was measured with the non-contact type surface shape measuring device above-mentioned. Fig. 9 (a) shows the section shape of the ink layer obtained with the use of the offset blanket of Example 1, Fig. 9 (b) shows the section shape of the ink layer obtained with the use of the offset blanket of Comparative Example 1, and Fig. 9 (c) shows the section shape of the ink layer obtained with the use of the offset blanket of Comparative Example 2. From the results shown in Fig. 9, it was found that, when the offset blanket of Comparative Example 2 was used, the ink layer section presented concavo-convex portions. Thus, it was found that the ink layer was partially protruded and concaved due to cohesive failure. Further, both ends of the ink layer outwardly projected as exceeding from a predetermined width. Thus, it was found that the edges of the ink layer were unclear. It was also found that, when the offset blanket of Comparative Example 1 was used, the ink layer section presented concavo-convex portions of which wavelengths were greater than those of the concavo-convex portions in Comparative Example 2. Further, it was found that the height of the ink layer was lower than that of each of the respective ink layers obtained with the use of the offset blankets of Comparative Example 1 and Example 1 to be discussed later. Thus, it was found that, when the offset blanket of Comparative Example 1 was used, the ink transferability from the block to the blanket was not good, causing the ink amount to be insufficient, so that the ink layer section presented concavo-convex portions due to cohesive failure. Further, it was found that the ink layer presented gentle slopes at both ends thereof, so that the edges of the ink layer were unclear. It was found that, when the offset blanket of Examples 1 was used, the ink layer section presented no concavo-convex portions due to cohesive failure and the ink layer was clear at the edges thereof, likewise in Printing Tests 1 and 2. Examples 2 to 9 and Comparative Examples 3, 4Compound rubbers for a surface printing layer were prepared by mixing, in the respective proportions shown in Table 1, millable-type silicone rubber and oil-resisting rubber identical with those used in Study of Blending Proportion of Rubber Materials. More specifically, there were prepared compound rubbers for a surface printing layer by blending 100 parts by weight of each of the raw material rubbers thus prepared, 30 parts by weight of a white filler (Nipsil VN 30), 20 parts by weight of a plasticizer (dioctylphthalate), 1 part by weight of a crosslinking agent (dicumyl peroxide) and 0.3 part by weight of a crosslinking retarder (Sconock N manufactured by Ouchi Sinko Kagaku Company). According to a conventional method, each of the surface printing layers was applied, through a primer, onto a supporting layer including four supporting bases of cotton and a compressive layer, and dried and vulcanized to prepare an offset blanket having a surface printing layer with a thickness of 0.3 mm. Printing Test 4A printing test was conducted under the following conditions with a printing machine (Type 560 manufactured by Ryobi Co., Ltd.) on which each of the offset blankets of Examples 2 to 9 and Comparative Example 3 and 4 was mounted. Table 1 shows test results as measured in the following manner. (1) Net-point ShapeThe shape of each printed net-point was evaluated based on shape coefficient. The shape coefficient is represented by the following formula. As the shape coefficient is nearer to 1, the roundness of the net point is greater so that the net point is evaluated high. In the following formula, the area and peripheral length are obtained by image analysis.Shape Coefficient = (Peripheral Length)² /(4π x Area) (2) Uniformity of Ink Coating Amount at Solid PrintingBy image analysis, the density distribution of each solid printing portion was examined and the standard deviation thereof was obtained. Based on the standard deviation, the uniformity of ink coating amount at solid printing was evaluated. The smaller te standard deviation is, the better the uniformity. O ○ :Standard deviation not more than 8 O :Standard deviation from 10 to 12 ▵ :Standard deviation from 12 to 14 X :Standard deviation not less than 14 (3) Oil ResistanceIn the same manner as mentioned earlier, a block of 1 mm x 2 cm x 2 cm was prepared from each of the compound rubbers above-mentioned. After each block was immersed in toluene at 40°C for 24 hours, the volume increase rate VT as above-mentioned was calculated. The oil resistance was evaluated according to the following criteria: O ○ :VT is not greater than 120%. O :VT is from 120% to 150%. ▵ :VT is from 150% to 175%. X :VT is from 175% to 200%. XX :VT is not less than 200%. (4) Paper Discharging PropertiesThe curl height of ten pieces of coated paper after entirely printed in solid printing was measured. The higher the curl height is, the better the paper discharging properties. (5) Retention of Paper PowderAfter 10,000 pieces were printed, the surface of each offset blanket was visually checked for the amount of paper powder sticked thereto. The evaluation was made according to the following criteria: O :Substantially no paper powder ▵ :Paper powder accumulated in the vicinity of the edges X :Paper powder sticked on the entire surface XX :Paper powder considerably sticked As apparent from Table 1, it is found that, as the proportion of silicone rubber is increased from the proportion of 2% (Example 2), the retention of paper powder and paper discharging properties are greatly improved and the uniformity of ink coating amount at solid printing and net-point shape are also improved. It is also found that, when the proportion of silicone rubber exceeds 80% (Comparative Example 4), the oil resistance is extremely bad and the transferability of ink from the block to the blanket is deteriorated to decrease the amount of ink transferred to paper. This results in low ink density, so that the ink applicability is lowered. From the foregoing, it is found that the proportion of silicone rubber/NBR is preferably in a range from 2/98 to 80/20. Example II (Printing Rubber Roll)Study of Blending Proportion of Rubber MaterialsDifferent raw material rubbers were prepared by blending, in different proportions, millable-type silicone rubber (KE8751-U manufactured by Shinetsu Kagaku Company) and NBR (KRYNAC 803 manufactured by Polyser Company). There were prepared different compound rubbers by blending 100 parts by weight of each of the material rubbers thus prepared, 30 parts by weight of a white filler, 30 parts by weight of dioctylphthalate, 5 parts by weight of zinc oxide, 0.5 part by weight of stearic acid, 1.5 part by weight of AccTT and 2.5 parts by weight of AccMOR. Test of Ink ResistanceEach of the compound rubbers was molded and vulcanized to prepare a block of 1 mm x 2 cm x 2 cm. Each of the blocks was immersed in oil ink maintained at 40°C. After 24 hours, the volume of each block was measured. Based on the volume before immersion and the volume after immersion, the volume increase rate ΔV (%) due to swelling was calculated. For the test, process ink manufactured by Dai-Nihon Ink Co., Ltd. was used as the oil ink. Each of blocks prepared in the same manner as above, was immersed in ultraviolet-curing ink maintained at 40°C. After 24 hours, the volume of each block was measured. In the same manner as above-mentioned, the volume increase rate ΔV (%) due to swelling was calculated. For the test, BEST CURE manufactured by Toka Shikiso Kagaku Co., Ltd. was used as the ultraviolet-curing ink. Fig. 10 shows the test results. From Fig. 10, it was found that, as the proportion of silicone rubber was smaller, the oil resistance was greater, and as the proportion of NBR was smaller, the durability with respect to the ultraviolet-curing ink was greater. Test of Rubber StrengthEach of the compound rubbers was molded and vulcanized to prepare a specimen of JIS (Japanese Industrial Standards) dumbbell No. 3. The tensile strength of each specimen was measured under the conditions of JIS 6302. Fig. 11 shows the test results. From Fig. 11, it is found that, as the proportion of silicone rubber is increased, the strength is lowered. Example 10A raw material rubber was prepared by blending millable-type silicone rubber (KE8751-U manufactured by Sinetsu Kagaku Company) and NBR (KRYNAC 803 manufactured by Polyser Company) as oil resistance rubber in a blending proportion of 20/80 by weight of silicone rubber/NBR. There was prepared compound rubber by blending 100 parts by weight of the material rubber thus prepared, 30 parts by weight of a white filler, 30 parts by weight of dioctylphthalate, 5 parts by weight of zinc oxide, 0.5 part by weight of stearic acid, 1.5 part by weight of AccTT and 2.5 parts by weight of AccMOR. The compound rubber was molded, vulcanized and prepared as a rubber roll having a length of 200 mm and an outer diameter of 50 mm as put on a center shaft having a length of 500 mm and an outer diameter of 10 mm. Comparative Example 5A rubber roll was prepared in the same manner as in Example 10, except for the use of NBR as raw material rubber. (Evaluation Test)Each of the rubber rolls thus prepared was immersed in ultraviolet-curing ink containing an acryl monomer (BEST CURE manufactured by Toka Shikiso Kagaku Co., Ltd.) With the ink maintained at 40°C, each of the rolls was checked for change in outer diameter with the passage of time. Fig. 12 shows the test results. From Fig. 12, it was found that, after 30 days, the roll of Comparative Example 5 which was a conventional rubber roll, was swollen and increased in outer diameter to about 100 mm and, thereafter, a plasticizer was extracted, causing the roll to be decreased in outer diameter. On the other hand, the swelling speed of Example 10 was reduced to about 1/3 of that of Comparative Example 5. Accordingly, the life-time of the roll of Example 10 was lengthened about 3 times that of Comparative Example 5. Example 11A rubber roll was prepared in the same manner as in Example 1, except for the proportion by weight of silicone rubber/NBR set to 60/40. The rubber roll of Example 11 presented durability with respect to ultraviolet-curing ink substantially equal to that of Example 10.
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A printing offset blanket having, on a supporting layer (1), a surface printing layer (3) made of a mixture of silicone rubber and oil-resisting rubber. A printing offset blanket according to Claim 1, wherein weight ratio of silicone rubber/oil-resisting rubber is from 2/98 to 80/20. A printing offset blanket according to claim 1 or claim 2 wherein the oil-resisting rubber is an acryl rubber or an acrylonitrile-butadiene rubber. A printing rubber roll made of a mixture of silicone rubber and oil-resisting rubber. A printing rubber roll according to Claim 4, wherein the oil-resisting rubber is an acryl rubber or an acrylonitrile-butadiene rubber. A printing rubber roll according to claim 4 or claim 5, wherein the weight ratio of silicone rubber/oil-resisting rubber is from 60/40 to 20/80.
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SUMITOMO RUBBER IND; SUMITOMO RUBBER INDUSTRIES LIMITED
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FUCHIKAMI TETSUYA; KAMADA TOSHIO; KONDO YASHUHIKO; MASUDA TSUNEO; OGITA TOSHIKAZU; TOMONO SEIJI; FUCHIKAMI, TETSUYA; KAMADA, TOSHIO; KONDO, YASHUHIKO; MASUDA, TSUNEO; OGITA, TOSHIKAZU; TOMONO, SEIJI
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EP-0489588-B1
| 489,588 |
EP
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B1
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EN
| 19,951,018 | 1,992 | 20,100,220 |
new
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G01N21
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G02B21, G02B17
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G02B21, G01N21, G02B17
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G01N 21/55B, G02B 21/04
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ATR objective and method for sample analysis
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An optical system, apparatus (1) and method includes a visible energy source (2) and a radiant energy source (3), means (6) to direct visible or radiant energy at preselected but variable angles of incidence through an ATR crystal (22) to a sample (26) at a sample plane (35) and means (2) to collect encoded radiant energy reflected or emitted from the sample (26) through the ATR crystal (22) to a detector (25) at preselected but variable angles of reflection or emission. The optical system, apparatus and method may further include a lens (17) or other optical element selectively positioned in the optical path to change the focus of the optical path to initially survey the sample on a movable stage at a focal plane (93) spaced from the sample plane (35). The survey mode permits easy identification of a surface area of interest on the sample (26) to permit that area of interest to be moved into contact with a surface of the ATR crystal (22) at the sample plane (35) for subsequent accurate analysis thereof. The optical system, apparatus and method may have three modes of operation (namely a survey mode, a viewing mode or an analysis mode) passing visible or radiant energy to and from a sample (26) or reference material through an ATR crystal (22).
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The present invention relates, in general, to an optical system and method and, in particular, to an optical system and method utilizing an ATR apparatus. Crystals utilizing total internal reflection or attenuated total reflection (ATR) principles are well known in optical systems for analyzing samples by determining the optical constants thereof and by establishing the physical and chemical composition thereof. Examples of ATR crystals in various optical systems are shown, for example, in U.S. Patent Nos. 4,602,869 and 3,393,603. These ATR crystal optical systems utilise rather complicated optical paths, which limit the flexibility of those systems and limit the type and size of sample that can be analyzed. An example of such an ATR crystal system is disclosed in an article appearing in the June, 1988 issue of the Spectroscopy magazine (pages 96-107). A nano-sampler, apparently offered by Harrick Scientific Corporation, is pictured and described in that article. As pictured, an internal reflection crystal has a fibrous sample positioned against part of a sampling surface. A mask is selectively positioned at, or very near, the sample plane to allow selected energy reflected from the sample to escape from the crystal and pass through the output side of the optical system to a detector. A visible light viewing system is positioned above the sampling surface apparently to allow the sample, sample surface and sample plane to be observed to assist in positioning the sample and mask at the sample plane. The ATR crystal is set up in this optical system to act like a light pipe in directing energy therealong to the angularly positioned sample surface at one end thereof. The Harrick optical system is rather complicated and does not allow any visible light viewing through the ATR crystal to the sample. According to one aspect of the invention, there is provided an optical system for analyzing a sample or reference material comprising: a source of radiant energy for selectively emitting radiant energy along an optical path of the optical system; a source of visible energy for selectively emitting visible light along the optical path; a sample plane having an ATR crystal mounted therein; means for selectively positioning a sample or reference material at the sample plane in contact with one surface of said ATR crystal; means in the optical path for directing and concentrating either visible light or radiant energy through the ATR crystal to the sample plane; means using visible light for selectively viewing in a viewing mode along the optical path through the ATR crystal to a sample or reference material positioned at that sample plane; and means for collecting and detecting radiant energy that has passed through the ATR crystal and been encoded by the sample or reference material in contact therewith to allow analysis of the sample or reference material in an analysis mode by using the encoded radiation collected and detected. According to a second aspect of the invention, there is provided a method of analyzing a sample or reference material comprising the steps of: a. masking an optical path at approximately a Fourier plane or conjugate thereof to a sample plane or conjugate thereof with mask means having apertures therein (1) to selectively direct visible or radiant energy through an ATR crystal at a preselected but variable angle of incidence to a sample or reference material selectively in contact therewith at a sample plane and (2) to selectively collect energy emitted from said ATR crystal and sample or reference material at a preselected but variable angle of reflection or emission; b. viewing the sample or reference material in a viewing mode with visible light passing through the masking means and ATR crystal to the sample or reference material; and c. analyzing the sample or reference material in an analysis mode by detecting encoded radiant energy which has been reflected off or emitted from the sample or reference material and passed through the ATR crystal and masking means. According to a third aspect of the invention, there is provided a method of analyzing a sample or reference material in an optical system comprising the steps of: a. initially viewing with visible light through an ATR crystal to a sample positioned at a focal plane spaced from said ATR crystal; b. initially moving the sample in the focal plane to identify an area of interest on a surface of that sample; c. moving the area of interest of the sample into contact with a surface of the ATR crystal at or adjacent a focal point on a sample plane; d. viewing with visible light through the ATR crystal to the sample at the sample plane to observe the area of interest at a selected angle of incidence; and e. analyzing the sample (1) by passing radiant energy through the ATR crystal to the sample, and (2) by selectively collecting radiant energy reflected or emitted from the sample for analysis at a detector. Preferred embodiments of the present invention provide an optical system, apparatus and method to utilize an ATR crystal in a microscope objective system. A flat or nearly flat surface of the ATR crystal is positioned in the sample plane of the optical system. The sample or reference material may be pressed against the flat crystal surface to maintain intimate contact therebetween. The optical system has three different operational modes: namely, a survey mode; a viewing mode and an analysis mode. In all three of these modes, the visible or radiant energy passes through the ATR crystal to reach the sample. In the survey mode, an optical element, such as a refractive lens, is positioned in the optical path of the optical system to refract visible light passing therethrough. As thus refracted, the visible light passes through the ATR crystal and sample plane to a survey focus at a focal plane spaced from the sample plane. The sample is mounted on a conventional microscope stage and can be moved in the X and Y (or R and ϑ) directions in the focal plane to allow the analyst to easily survey the entire sample field. The surface area of analytic interest can be quickly identified in this survey mode and fixed in the X and Y directions at or immediately adjacent the survey focal point in the focal plane. The stage and sample can then be moved only in the Z direction to bring the surface area of interest on the sample into contact with the flat surface of the ATR crystal at the sample plane. The conventional microscope stage structure can be used to apply pressure to hold the sample surface of interest firmly against the flat ATR crystal surface at the analysis or operative focal point of the optical system in either the viewing or analysis modes. In the viewing mode, the refractive lens or other survey-optical element is removed from the optical path and is replaced by optional inlet and outlet masks. The analyst can then view along that optical path through the inlet mask and ATR crystal to the sample area of interest in contact with the flat surface of the ATR crystal at the operative focal point of the optical system. The angle of incidence to and the angle of emission or reflectance from the ATR crystal and sample can be selectively varied by apertures in the inlet and outlet masks positioned at or near a Fourier plane or a conjugate thereof. The inlet and outlet apertures may be selectively varied in size, shape, number and relative spacial locations according to the analytical study being performed. In the viewing mode, the analyst can look along the optical path through the mask aperture and ATR crystal to see the surface area of interest on the sample at the focal point on the sample plane. The masks can be changed to vary the analysis being made without moving the sample. In the analysis mode, radiant energy passes along the optical path through the first or inlet mask, the inlet half of a reflecting microscope objective and the ATR crystal to the surface area of the sample. Some of the radiant energy is then reflected or emitted from the sample through the crystal, to thereafter pass through the outlet half of the reflecting microscope objective and second or outlet mask to a detector. This optical system allows analysis of small samples using the ATR technique. In addition, the variable angles of incidence and reflection or emission allow for different studies to be performed providing variable depths of radiant energy penetration at the sample. Embodiments of the invention will now be described by way of example and with refence to the accompanying drawings in which: Fig. 1 is a schematic elevation of an optical system set up in the viewing mode with the sample in contact with a surface of the ATR crystal at the sample plane; Fig. 2 is a vertical cross-section of the ATR crystal objective assembly according to one embodiment of the invention, shown in the survey mode with a refractive lens inserted in the optical path; Fig. 3 is a plan view taken generally along the plane 3-3 of Fig. 2 showing the slide selectively located to position the refractive lens in the optical path for the survey mode; Fig. 4 is an enlargement of the ATR crystal, sample and sample stage from the circled area of Fig. 2 showing one surface of the sample positioned at a survey focal plane, which is spaced from the sample plane in the survey mode; Fig. 5 is a vertical cross-section of the ATR objective assembly similar to Fig. 2, but showing the viewing or analysis modes of the ATR objective assembly with the sample being held against the ATR crystal and the inlet and outlet masks being positioned at the Fourier plane; Fig. 6 is a plan view taken generally along the plane 6-6 of Fig. 5 showing the slide selectively located to position the inlet and outlet masks in the optical path; Fig. 7 is an enlargement of the ATR crystal, sample and sample stage from the circled area of Fig. 5 showing one surface of the sample held in contact with the bottom surface of the ATR crystal at the sample plane; Fig. 8 is a vertical cross-section of an ATR objective assembly according to a second embodiment of the present invention shown in the survey mode with a refractive survey lens positioned in a central bore in the secondary optic of the Cassegrain objective; Fig. 9 is a plan view of the ATR objective assembly taken generally along the plane 9-9 of Fig. 8 showing the slide selectively located to position a lens mask in the optical path to direct visible light through the central bore of the secondary optic; Fig. 10 is an enlarged vertical elevation of the ATR crystal, sample and sample stage of the second embodiment in the survey mode with the upper surface of the sample being positioned in a focal plane spaced from the sample plane; and Fig. 11 is a vertical section of the ATR objective assembly of the second embodiment shown in Fig. 8 illustrating the sample positioned in contact with the bottom surface of the ATR crystal and the apertured inlet and outlet masks positioned in the optical path for either the viewing or analysis modes. Turning now in more detail to an embodiment of the: invention and initially to Fig. 1, the optical system and apparatus is indicated generally at 1. The optical system includes a visible light source 2 and a radiant energy source 3. The term radiant energy, as used herein, means any wave band of energy, with mid-range infrared energy being used in the current embodiment. The light source 2 emits a beam of visible light 4 reflected by mirror 5 to pivotal source switching mirror 6. In the full line position shown, mirror 6 reflects the visible light downwardly at a 90° angle along the optical path of the system. The radiant energy source 3 selectively emits a beam 8 of radiant energy. The radiant energy beam 8 is reflected by mirror 9 toward source switching mirror 6. When pivoted to its dashed line position, source switching mirror 6 reflects the radiant energy at a 90° angle downwardly along the optical path of the system. The optical path of the system is split in half along the optical centerline 11. For this purpose, a mirror 12 can be positioned at or adjacent an aperture image plane. The mirror 12 effectively blocks and discards all incoming visible energy 4 or radiant energy 8 on the left of the optical centerline 11 as viewed in Fig. 1. By thus splitting the incoming energy, the visible or radiant energy passing on the right toward the ATR objective moves as a half beam in the direction of arrow 14 along the left side of the optical centerline 11 as viewed in Fig. 1. The optical system 1 permits selective viewing of the inlet visible energy moving along the optical path. For this purpose, a pivotal beam splitter 15 is also positioned along the optical axis. In its position extending across the optical path, the beam splitter 15 permits a portion (approximately one-half) of the visible light 4 from visible energy source 2 to pass therethrough. The beam splitter 15 in such position also permits an analyst to look through a viewing port 13 and utilize the reflective portion of beam splitter 15 to view along the incoming energy path 14. In a radiant energy analysis mode, the beam splitter 15 is pivoted to a position removed from the optical path, as indicated by the reference numeral 15A. The incoming visible or radiant energy passes through an ATR objective assembly, indicated generally at 16. The ATR objective assembly includes, on its input side, either an optical path changing element 17 or inlet mask 18, a secondary optic 20, a primary optic 21, and an ATR crystal 22. The ATR objective assembly, on its output side, includes the ATR crystal 22, the primary optic 21, the secondary optic 20 and either the optical path changing element or a second outlet mask 23. The primary optic 21 and secondary optic 20 are preferably mirrors cooperatively forming a reflecting objective, with the left half thereof as viewed in Fig. 1 being an inlet optic and the right half thereof being an outlet optic. Energy leaving the ATR objective assembly 16 passes in the direction of arrow 24 from the right side of the centerline 11 of the optical system to the left side after imaging at the field stop 34. This energy leaving the ATR objective assembly is reflected off splitting mirror 12 to a detector 25. The detector 25 is used to optically analyze the sample material 26 or reference material 27 selectively positioned against a surface of ATR crystal 22 in the ATR objective assembly 16. The ATR objective assembly 16 is best illustrated in Fig. 2. This ATR objective assembly may have many of the same structural elements as the objective assembly described in copending and co-owned UK. patent application No. 2,2429,77. However, because of the many differences and additional features incorporated in embodiments of the present invention, the entire objective assembly 16 is described for purposes of completeness. The ATR objective assembly 16 includes a microscope connecting tube 29. The outer diameter of the connecting tube at its upper end is provided with threads 30. These threads mate with threads on one of the stations of a rotatable microscope nose piece. The connecting tube is threaded into the microscope nose piece station until properly positioned and held in place by jam nut 31 and lock nut 32. The visible and radiant energy of the optical system passes through the bore of the connecting tube 29. The jam and lock nuts properly position the ATR objective assembly 16 in the optical path of the microscope to establish the proper predetermined distance between the field stop of the optical system, indicated generally at 34 (Fig. 1), and the sample plane 35. A guide holder 37 is positioned around and supported by connecting tube 29. A bore 38 through the guide holder body 37 receives the connecting tube 29. The guide holder 37 has a tapped hole 39 extending radially therethrough. A first optic centering screw 40 is threadedly received in tapped hole 39 and extends into contact at its inner rounded end with the outer diameter of connecting tube 29. By rotation, first centering screw 40 may be radially advanced or retracted relative to connecting tube 29 to provide some radial adjustment for the guide holder 37 relative to the centerline 11 of the optical system. The bottom end of guide holder 37 has a bottom counterbore 42. This counterbore 42 receives a slide guide 43, which is fixedly secured thereto. The slide guide has a longitudinal slide slot 45 extending diametrically therethrough. A center bore 46 extends through the slide guide body, with such bore being concentric with the centerline 11 of the optical system to pass visible or radiant energy therethrough. The secondary optic 20 is mounted to and suspended from the bottom of slide guide 43. For this purpose, mounting spider 48 extends diametrically across the center bore 46 of slide guide 43 and is connected to mounting pin 49 of secondary optic 20 to support that secondary optic in the optical path. By being diametrically oriented and properly positioned, the mounting spider 48 supports the secondary optic 20 in the optical path without significantly interfering with the effective input and output of visible or radiant energy to and from the ATR objective assembly 16. In this regard, the mounting spider 48 defines semi-circular openings on either side thereof consistent with the half beam shape of the inlet and outlet visible and radiant energy. The bottom of guide holder 37 has a radially outwardly extending annular flange 50 thereon. The bottom wall 51 of flange 50 is horizontally aligned with the bottom surface of slot 45 to provide radial access to such slot. The flange 50 also provides support for a rotatable outer ring or collar 52. The outer ring 52 includes a downwardly extending annular skirt 53, which has a threaded internal diameter. The primary optic 21 is received within annular skirt 53 on outer ring 52. The outer diameter of crystal mounting ring 61 has threads thereon to cooperate with the threads on the internal diameter of skirt 53. Therefore, rotation of the crystal mounting ring 61 will, depending upon direction of rotation, either raise or lower the primary optic 21 because the primary optic rests on ring 61. This elevational adjustment of the primary optic 21 may be used to obtain the proper spacial relationship between the primary optic and the secondary optic for proper optical alignment. To provide further adjustment of the ATR objective assembly relative to the centerline of the optical path, outer ring 52 has a threaded hole 54 passing radially through its upper end. Threaded hole 54 receives a second primary optic centering screw 55. Radial advancement or withdrawal of second centering screw 55 can radially adjust the position of the outer ring 52 relative to the guide holder. This radial movement of outer ring 52 also radially adjusts the position of the primary optic 21 relative to the secondary optic 20 to obtain proper centering around the optical centerline 11 of the microscope. A counter bore 57 is provided at the bottom end of annular skirt 53 of outer ring 52. The annular sidewall defined by counter bore 57 has internal threads 58 provided thereon. Threads 58 mate with external threads 59 on crystal mounting ring 61. The crystal mounting ring is threaded into outer ring 52 until its internal lip 62 engages a radially extending external shoulder 63 on primary optic 21. A downwardly extending collar 65 on ATR mounting ring 61 has its radially inner wall threaded, as shown at 66. Threads 68 on the outer upper diameter of annular crystal mounting block 69 mate with threads 66 on the crystal ring 61 to allow the crystal mounting block 69 to be vertically adjusted relative to crystal mounting ring 61. The crystal mounting block 69 has an annular, radially inwardly extending shoulder 71 which supports a radially outwardly extending annular flange 72 on a crystal mounting pan, indicated generally at 73. The bottom wall 75 of crystal mounting pan 73 includes a center hole 76 receiving the ATR crystal, indicated generally at 22. As best shown in Fig. 4, the ATR crystal 22 preferably includes a generally hemispherical upper surface 77, a generally cylindrical side wall 78 and a flat bottom wall 79. The ATR crystal 22 is secured in center hole 76 of the crystal mounting pan 73 in a position to locate the flat bottom wall 79 thereof flush with the lower surface of bottom wall 75. This ATR mounting pan 73 can also be vertically adjusted as necessary to position the bottom wall 79 of ATR crystal 22 in the sample plane 35. For this purpose, rotation of crystal mounting block 69 in one direction or the other will either raise or lower the mounting block 69 and crystal mounting pan 73 carried thereby relative to the crystal mounting ring 61. The mounting pan 73 is either raised or lowered until the bottom wall 79 of ATR crystal 22 lies in sample plane 35 of the optical system. The crystal mounting pan 73 may also be radially adjusted to radially adjust the ATR crystal 22 carried thereby. For this purpose, mounting block 69 is provided with a tapped hole 81 passing radially therethrough. Threaded hole 81 receives a third optic centering screw 82. The inner rounded end of third centering screw 82 engages the outer sidewall surface 83 on crystal mounting pan 73. Radial advancement or withdrawal of the third centering screw 82 can radially adjust the position of the mounting pan 73 and ATR crystal 22 relative to the optical centerline 11 of the optical system. This selective radial adjustment of the ATR crystal permits the optical centerline 11 of the optical system to pass through the center of the crystal 22. The ATR crystal 22 is thus accurately positioned in the optical system for any of its operational modes. For the survey mode, an optical element is inserted into the optical path to deflect or change its direction to create a focus thereof on a focal plane spaced from the sample plane. As shown in Fig. 2, the optical element may be a refractive lens 17 selectively slid into the optical path. For this purpose, a slide 84 may be radially inserted into and withdrawn from slot 45 in slide guide 43. The slide 84 has an elongated rectangular shape in plan view, as best shown in Fig. 3. The width of slide 84 substantially equals the width of guide slot 45 to provide a relatively tight sliding fit therebetween. In addition, some adjustment of the slide 84 may be provided by ball plunger 85 received in tapped hole 86 in slide guide 43. The inner rounded end of ball plunger 85 engages the side of slide 84. Rotation of ball plunger 85 in one direction or the other will advance or retract that plunger relative to slide guide 43 to correspondingly adjust the pressure on the slide 84 engaged thereby. The slide 84 has two (or more) circular receptacles, indicated generally at 87A and 87B. As best shown in Fig. 2, each of these receptacles is defined by a bore 88 and counterbore 88A passing entirely through the slide 86. Each bore 88 and counterbore 88A cooperate to define a bottom lip 89 therebetween protruding slightly radially inwardly to provide support for the optical element and/or the inlet and outlet masks selectively positioned in receptacle 87A or 87B. In the survey mode, the slide 84 is positioned to locate the refractive lens 17 in receptacle 87A in the optical path. With the lens thus positioned, the visible light passing through lens 17 reflects off the secondary optic 20 and main optic 21 and then passes through the ATR crystal 22 as schematically illustrated by lines 91 in Fig. 4. The visible light is focused at survey focal point 92 on focal plane 93. As shown, focal plane 93 is positioned below and spaced from sample plane 35. In the survey mode, one surface 95 of sample 26 is positioned to lie in focal plane 93. A conventional microscope stage 96 supports the sample 26 in such position and can be moved in the X and Y directions within the focal plane 93 to allow the analyst to survey the entire surface area 95 to identify an area of analytic interest. To perform that survey mode function, the analyst views along the optical path through the lens 17, reflecting objective and ATR crystal 22 to the sample surface 95 at focal plane 93. When an area of interest is identified, the X, Y position of the sample area of interest is fixed and the stage 96 is moved in only a Z direction to bring sample surface 95 into contact with flat bottom surface 79 of crystal 22, as shown in Fig. 7. The conventional stage 96 is used to apply pressure and clamp the sample 26 to the crystal 22 to provide intimate and continuous surface contact between sample surface 95 and flat crystal surface 79. This intimate surface contact enhances the accuracy and sensitivity of the objective assembly 16 in the viewing and sampling modes. For these modes, the slide 84 is indexed in the direction of arrow 97 in Fig. 3 to a second position in which receptacle 87B thereon is positioned in the optical path. This new position of slide 84 is illustrated in Fig. 6. Receptacle 87B selectively receives an inlet mask 18 and outlet mask 23, which may be integrally formed in a single disc (as shown in Figs. 3 and 6) or in split discs as schematically shown in Fig. 1. As illustrated, the inlet mask 18 has a semi-circular inlet aperture 98, and the second or outlet mask 23 has a semi-circular outlet aperture 99. Inlet aperture 98 and outlet aperture 99 have the same configuration and radius about the centerline 11 of the optical system and thus specular reflectance studies are performed with this mask arrangement on the sample being analyzed. In addition, as shown, the inlet aperture 98 and outlet aperture 99 are respectively adjacent the outer peripheries of inlet mask 18 and outlet mask 99 whereby the angles of incidence and collection will be at large angles of incidence relative to the sample 26. The shape, number, size and radial position of the inlet and outlet apertures may be mixed and matched as desired for the specific analysis being made. Reference may be had to copending UK Patent Application No. 2,242,977 for a more complete discussion of mixing and matching different apertures for different types of analyses. With the inlet mask 18 and outlet mask 23 in the optical path as illustrated in Fig. 6, the optical system is set up for either the viewing mode or analysis mode. The masks are positioned at a Fourier plane of the optical system. For purposes of the present application, a Fourier plane is defined as a plane having the property that the radial position that a ray intersects that plane has a directly correlated function, normally linear, to the angle of incidence or reflection or emission that the ray will have with the sample plane after passing from or to the objective. In the viewing mode, the analyst can see through viewing port 13 along the optical path through inlet aperture 98, Cassegrain objective and crystal 22 to the surface 95 of the sample 26 positioned at the sample plane. The analyst can thus see the targeted area of interest at the selected angle of incidence through the ATR crystal 22 at the operative focal point on the sample plane 35 prior to beginning analytic studies. This viewing allows the analyst to selectively observe and vary the experiments without moving the sample merely by changing the inlet and outlet apertures used to vary the angle of incidence and reflection or emission. In the analysis mode, a narrow band of radiant energy from source 3 sequentially passes through aperture 98 in inlet mask 18, the reflecting objective and crystal 22 to the sample 96. With the preferred ATR crystal shown, the radiant energy will bounce or reflect off the sample 26 only one time. Some amount of radiant energy will be absorbed by the sample depending upon the material making up the sample. The remainder of the energy will be reflected off and/or emitted from sample 26 through the ATR crystal into the reflecting objective as indicated by the lines 101 in Fig. 7. This reflected or emitted energy leaving ATR crystal 22 reflects off the primary optic 21 and secondary optic 20 and then passes through outlet aperture 99 in second mask 23 on its way to the detector 25. The outlet aperture 99 thus collects a certain selected band of reflected or emitted radiant energy for analysis and blocks all remaining reflected or emitted radiant energy on the outlet side of ATR objective assembly 16. The outlet radiant energy reaching the detector 25 is encoded with information about the sample 26 because of the energy absorbed by the sample at the selected angle of incidence and reflection. The sample material 26 can thus be analyzed utilizing ATR principles on small samples or on small areas of interest on a specific sample by passing radiant energy through and from an ATR crystal. Although the operation of the optical system and apparatus is believed apparent from the above, a brief description of the optical system 1 shown in Figs. 1 through 7 is given below for purposes of completeness. Initially, to set up for the survey mode, the switching mirror 6 is pivoted to its full line position shown in Fig. 1, the beam splitter 15 is positioned across the optical path, the refractive lens 17 is positioned in the optical path, and the top surface 95 of sample 26 or reference material 27 is positioned in focal plane 93. The visible light source 2 is then turned on and the analyst views through sight tube 13. In the survey mode, the analyst sees through the refractive lens 17, reflecting objective and ATR crystal to the surface 95 of sample 26 lying in the focal plane 93. The spectroscopist can manipulate the microscope stage controls to move the stage 96 and thus sample 26 in the X and Y directions. This two-directional movement in the focal plane allows the entire sample surface 95 to be easily surveyed to easily identify an area of analytic interest thereon. The sample is then fixed in the X and Y directions and the stage 96 moved in the Z direction to bring sample surface 95 into intimate, pressed contact with bottom surface 79 on crystal 22, as shown in Figs. 5 and 7. The optical system may then be converted to the viewing mode by indexing slide 84 in the direction of arrow 97 to locate receptacle 87B in the optical path. Inlet mask 18 and outlet mask 23, received in receptacle 87B, respectively have inlet and outlet apertures therein for the analytic study selected. By thus indexing the slide, the inlet mask 18 and outlet mask 23 are positioned in the optical path. The analyst can thus view the selected area of interest on the sample at the selected angle of incidence. Specifically, with visible light source 2 still on, the analyst views through aperture 98, the reflecting objective and ATR crystal 22 to the area of interest on surface 95 of sample 26 located at the focal point 100 on sample plane 35. At the completion of the viewing mode, the optical system is converted to the radiant energy analysis mode. For this purpose, the switching mirror 6 is pivoted to its dotted line position of Fig. 1, the beam splitter 15 is pivoted out of the way to position 15A and the inlet and outlet masks remain in their respective positions in the optical path. Radiant energy source 3 is then available to emit a radiant energy beam 8 which passes along the optical path of the system. Specifically, radiant energy moves in a direction of arrow 14 and sequentially passes through inlet aperture 98, reflecting objective and ATR crystal 22 to the surface area of interest on sample 26 located at focal point 100. Depending upon the sample being analyzed, the sample 26 will absorb some radiant energy and the remaining radiant energy will reflect or be emitted from the sample surface 95 and then pass through the ATR crystal as indicated by lines 101 in Fig. 7. The radiant energy leaving the ATR crystal 22 will reflect off the second half or side of the primary optic 21 and secondary optic 20. The radiant energy passing through outlet aperture 99 in outlet mask 23 will be collected and the rest will be blocked. The collected radiant energy passing through outlet aperture 99 reflects off splitting mirror 12 to detector 25 for analysis of the sample material as discussed above. Other embodiments of this invention are possible as shown, for example, in Figs. 8 through 11. This second embodiment includes many common elements to the first embodiment, with such common elements being identified by the same reference numerals. In the second embodiment, the stem 49A supporting secondary optic 20 has a bore 105 passing therethrough. Bore 105 communicates at its bottom end with a bore 106, passing through secondary optic 20. A refractive lens 17A is positioned in the bore 106, as best shown in Fig. 8. For the survey mode utilizing refractive lens 17A, a lens mask 108 is positioned in receptacle 87A of slide 84. The survey mask 108 has a central aperture or hole 109 having a diameter equal to or slightly smaller than the diameters of bore 105 in stem 49A and bore 106 in secondary optic 20. In the survey mode, hole 109 is centered on optical centerline 11 and is thus in vertical alignment with bores 105 and 106. When slide 84 is located in its first position, survey lens mask 108 is positioned in the optical path for the survey mode, as illustrated in Figs. 8 and 9. Visible light from visible energy source 2 will sequentially pass through hole 109, bore 105, bore 106, refractive lens 17A and crystal 22 in reaching surface 95 of sample 26 at the focal plane 93. The analyst uses this visible light path schematically identified as 91A in Fig. 8 and 10 for the survey mode described above. For the viewing mode or analysis mode, the slide 86 is indexed to its second position locating the inlet mask 18 and outlet mask 23 in the optical path as described above. The viewing and analysis modes of the second embodiment operate as described above and are illustrated in Fig. 11, with the inlet and outlet masks so positioned. It will be apparent from the foregoing that changes may be made in the details of construction and configuration without departing from the scope of the invention as defined in the following claims. For example, the optical path changing element 17 may be any type of optical element inserted in the optical path at any position therealong operative to focus visible light at a focal plane spaced from the sample plane. Furthermore, different ATR crystals can be utilized having different shapes and different operational and optical characteristics, such as multiple bounce or reflection features.
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An optical system for analyzing a sample or reference material comprising: a source of radiant energy for selectively emitting radiant energy along an optical path of the optical system; a source of visible energy for selectively emitting visible light along the optical path; a sample plane having an ATR crystal mounted therein; means for selectively positioning a sample or reference material at the sample plane in contact with one surface of said ATR crystal; means in the optical path for directing and concentrating either visible light or radiant energy through the ATR crystal to the sample plane; means using visible light for selectively viewing in a viewing mode along the optical path through the ATR crystal to a sample or reference material positioned at that sample plane; and means for collecting and detecting radiant energy that has passed through the ATR crystal and been encoded by the sample or reference material in contact therewith to allow analysis of the sample or reference material in an analysis mode by using the encoded radiation collected and detected. The optical system of claim 1 wherein the ATR crystal has a substantially hemispherical entrance surface and a flat surface for contact with the sample or reference material, wherein in use the visible and radiant energy pass through the crystal reflecting off the sample or reference material in contact therewith only once. The optical system of claim 1 or 2 wherein the means for directing and concentrating includes first mask means removably positioned at approximately a Fourier plane or conjugate thereof to the sample plane or conjugate thereof to selectively allow only certain visible or radiant energy to pass therethrough to target that energy at preselected variable angles of incidence to the ATR crystal and sample plane. The optical system of claim 3 wherein the means to collect and detect includes a second mask means removably positioned at approximately a Fourier plane or conjugate thereof to the sample plane or conjugate thereof to selectively allow only certain radiant energy reflected or emitted from the sample to pass therethrough at selected variable angles. The optical system of claim 4 wherein the first and second masks have apertures which may be mixed and matched as desired for the types of analysis studies being performed. The optical system of claim 4 or 5 wherein the means for directing and concentrating includes one half of a mirror objective system positioned between the first mask and sample plane and the means to collect and detect includes the other half of the mirror objective system positioned between the sample plane and second mask. The optical system of any of claims 1 to 6 further including optical path changing means which may be inserted in the optical path to result in the visible light that passes through the ATR crystal being focused at a focal plane spaced from the sample plane to allow the sample or reference material to be visibly surveyed in a survey mode to select an area of interest, the means for positioning movable to place the area of interest into contact with the ATR crystal for subsequent radiant or visual energy analysis. The optical system of claim 7 wherein the optical path changing means includes an optical element to deflect the visible light passing therethrough to create a focal point at the focal plane. The optical system of claim 6 and 7 wherein the optical path changing means includes a lens positioned in a bore in a secondary optic of a Cassegrain objective of said mirror objective system and further includes a third mask selectively positioned in the optical path to direct visible light through said bore and said lens positioned in said bore to refocus the optical path at said focal plane. The optical system of claim 8 wherein the first and second masks are removably mounted at a first position on a slide and a refractive lens is removably mounted as the optical element at a second position on the slide spaced from said first position on a slide, whereby said slide may be moved relative to the optical path alternately to position the refractive lens in the optical path for the survey mode or to position the first and second masks in the optical path for either the viewing mode or analysis mode. The optical system of claim 1 to 6, further including optical path changing means inserted in the optical path to result in the visible light that passes through the ATR crystal being focused at a focal plane spaced from the sample plane to allow the sample or reference material to be visibly surveyed in a survey mode to select an area of interest which can then be moved into contact with the ATR crystal for radiant energy analysis. The optical system of claim 1, 2 or 3 wherein the means for collecting and detecting includes a mask means to selectively allow only certain encoded radiant energy or visible energy to pass therethrough toward a detector. A method of analyzing a sample or reference material comprising the steps of: a. masking an optical path at approximately a Fourier plane or conjugate thereof to a sample plane or conjugate thereof with mask means having apertures therein (1) to selectively direct visible or radiant energy through an ATR crystal at a preselected but variable angle of incidence to a sample or reference material selectively in contact therewith at a sample plane and (2) to selectively collect energy emitted from said ATR crystal and sample or reference material at a preselected but variable angle of reflection or emission; b. viewing the sample or reference material in a viewing mode with visible light passing through the masking means and ATR crystal to the sample or reference material; and c. analyzing the sample or reference material in an analysis mode by detecting encoded radiant energy which has been reflected off or emitted from the sample or reference material and passed through the ATR crystal and masking means. The method of claim 13 including the further step of selectively varying the direction of the optical path to pass visible light through the ATR crystal and sample plane to a focal plane positioned therebelow. The method of claim 13 or 14 including the further steps of viewing the sample or reference material temporarily positioned in the focal plane in a survey mode to identify and position an area of interest on the sample or reference material at a focal point on that focal plane and thereafter moving that area of interest into contact with an ATR crystal surface at the sample plane. A method of analyzing a sample or reference material in an optical system comprising the steps of: (a) initially viewing with visible light through an ATR crystal to a sample positioned at a focal plane spaced from said ATR crystal; (b) initially moving the sample in the focal plane to identify an area of interest on a surface of that sample; (c) moving the area of interest of the sample into contact with a surface of the ATR crystal at or adjacent a focal point on a sample plane; (d) viewing with visible light through the ATR crystal to the sample at the sample plane to observe the area of interest at a selected angle of incidence; and (e) analyzing the sample (1) by passing radiant energy through the ATR crystal to the sample, and (2) by selectively collecting radiant energy reflected or emitted from the sample for analysis at a detector. The method of claim 16 including the further step of (f) varying the angles of incidence to and reflection or emission from the sample by masking with apertures selectively having various sizes, numbers, shapes and positions which can be mixed and matched depending upon the analysis being done.
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SPECTRA TECH INC; SPECTRA-TECH, INC.
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STING DONALD W; STING, DONALD W.
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EP-0489594-B1
| 489,594 |
EP
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B1
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EN
| 19,980,812 | 1,992 | 20,100,220 |
new
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G06T15
| null |
G06T15, G06F3
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G06T 15/40A
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Computer graphics system
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In a computer graphics system, a means and method is provided for initializing and updating a group of pixels contained on a display in blocks. A group of pixels is considered as a block and has a status word associated therewith. This status word maintains a running total of the maximum Z value of any pixel contained within a group or block of pixels. In this manner, once a block of pixels is rendered on to the display screen, a comparison can be made between the current pixels being displayed and a group of pixels which are to be displayed. The minimum Z value of the block of pixels to be displayed is compared with the maximum Z value for the block of pixels currently being displayed. If the current maximum Z value, as stored in the status word, is less than the minimum Z value for the pixels to be displayed, then the block of pixels currently being displayed will all win when compared to the pixels in the block to be displayed. In this case, a full block bypass of the blocks of pixels to be displayed is implemented, thereby saving considerable time and overhead when compared to conventional Z buffer systems that compare Z values for each individual pixel.
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The present invention relates to computer graphics systems having a display with a plurality of pixels thereon and a frame buffer, and to methods of displaying an object thereon.The frame buffer includes Z buffer which is a depth buffer holding a value associated with the depth of each pixel on a display screen and is generally used to remove hidden surfaces or lines when rendering 3-D solids on a display. Conventional Z buffers include one word associated with each displayed pixel. The present invention includes a method of improving both the initialization and updating functions associated with the Z buffer. More particularly, pixels are grouped together in blocks and a status word (Za) is associated with each block. This status word contains the maximum value of any pixel within the block. It should be noted that maximum value refers to maximum depth of a pixel within a display screen, i.e. the maximum distance from the eye of a viewer to the pixel.Conventional Z buffers initialize each pixel position individually when clearing the Z buffer, and updating the Z buffer for new values. That is, at initialization each pixel is set to a Z max value such that any new Z value will be closer to a view of the display than the Z max value. Therefore, any subsequent Z value will win when compared to Z max.To update the Z buffer of conventional systems, the existing value in the Z buffer for each pixel is compared with the new Z value to be written to the same pixel. If the new Z value is less than the value currently in the Z buffer for that pixel, then the new Z value replaces the existing value in the Z buffer. In this manner, pixel representing objects closer to a view of the display are maintained in the Z buffer and objects further from the viewer are obscured. If the existing value in the Z buffer is less than the new value for the object being displayed then the existing value remains in the Z buffer. This procedure is applied to each pixel of each scan-converted object until the entire scene is rendered.In contrast to the prior art, the present invention provides for setting the Za word to a maximum Z value (Z max) such that subsequent Z values for each pixel in the block associated with Za will win (be displayed) when compared with each pixel in the block under consideration. In other words, instead of setting each pixel to z max, only the za word is set to z max and all the pixels in that block are considered to be initialized to z max. In this manner significant time and overhead is saved when initializing a Z buffer. These Za words are initially set to a negative value which indicates that the block has been logically cleared , which means that actual Z values have yet to be determined and written to the Z buffer. The present invention also provides a method which eliminates the need to apply a comparison between a new Z value and an existing Z value for each individual pixel on a display screen.According to the invention, therefore, there is provided a method of displaying objects on a computer graphics system having a display with a plurality of blocks of pixels thereon, the method comprising the steps of: displaying by the pixels within each block, at least a portion of a first object;providing a memory for each block of pixels, and storing in the memory a maximum depth value of the pixel within each respective block having the greatest depth;determining an estimated minimum depth value for a second object to be displayed by at least one pixel in each block by: (a) determining whether the slope of the depth values within the block corresponding to a second object to be displayed is positive or negative;(b) for a positive slope setting an estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed;(c) for a negative slope, setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed, plus the number of pixels in the block multiplied by a delta depth value; comparing the stored maximum depth value with the estimated minimum depth value for each block, and continuing to display the current block of pixels when the stored maximum depth value is less than the estimated minimum depth value.Advantageously, the step of continuing to display comprises a method wherein the step of continuing to display comprises the step of bypassing consideration of the block of pixels corresponding to the object to be displayed.The invention further provides a computer graphics system for displaying objects on a computer graphics system display with at least one block of pixels thereon, the system comprising: means for displaying, by the pixels within the block, at least a portion of a first object;means for storing a maximum depth value for the block, comprising means for providing a memory for each block of pixels, and means for storing in the memory the depth value of the pixel within the block having the greatest depth;means for determining an estimated minimum depth value for a second object to be displayed by at least one pixel in said block comprising: (a) means for determining whether the slope of the depth values within the block corresponding to the object to be displayed is positive or negative;(b) means for a positive slope for setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed;(c) means for a negative slope for setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed, plus the number of pixels in the block multiplied by a delta depth value;means for comparing the stored maximum depth value with the estimated minimum depth value; andmeans for continuing to display the current block of pixels when the stored maximum depth value is less than the estimated minimum depth value.Other features of the invention are defined in the appended claims. How the invention can be carried into effect is hereinafter particularly described with reference to the accompanying drawings in which :- Figure 1 shows a display as part of a system according to the invention, having a block of associated pixels;Figure 2 shows a portion of the system and the display with three blocks of pixels and a line to be displayed;Figures 3A and 3B form a flow chart representing the operation of a system according to the present invention;Figure 4 is a graphical representation of the slope of lines to be drawn and their comparison with the status word Za;Figure 5 is a listing of pseudo-code which is an example of one means of implementing the present invention; andFigure 6 is a schematic diagram showing a computer graphics system on which the present invention may be implemented.A computer graphics system (Figure 6) which may utilize the present invention includes a display or monitor 10, such as a CRT or the like, with digital-to-analog converter (DAC) 20 providing a signal to be displayed thereon. A graphics adapter card 30, or the like, includes frame buffer 22, Z buffer 24 and its associated status word (Za) 26, and rendering hardware 33. A central processing unit (CPU) 31 is provided along with operating system 32 which will contain the actual lines of programming code to be used according to the present invention more efficiently to initialize and update display 10. An application program 34 determines the surfaces and the lines to be displayed on monitor 10.The display monitor 10 (Figure 1), such as a cathode ray tube (CRT) or the like, includes a plurality of pixels which when selectively illuminated define an image being displayed. The number of pixels contained on display 10 will vary depending on the resolution of the display, and in a display as shown with YN x XN pixels, YN and XN are positive numbers which may vary from approximately 400 to 1024. A block 12 includes twelve pixels 14 representative of a block which will have a status word associated therewith.Figure 2 illustrates three separate blocks 1, 2 and 3 of pixels 14 in the display 10, similar to block 12 (Figure 1). Each of the blocks 1, 2 and 3) includes thirty two pixels 14 and the blocks are adjacent to one another. For convenience, only the first four pixels and the last pixel of each block are shown.For each block there is a frame buffer 22 and a Z buffer 24. In addition, the present invention utilizes a Za buffer 26 which is a memory capable of storing status information corresponding to each block of pixels. That is, a memory capable of storing a Z value for each block of pixels must be provided either by additional memory, or utilization of existing unused memory. It can be seen that the Za buffer must be able to store at least one Z value for each block of pixels, where the number of blocks will be equal to the number of pixels on the display divided by the number of pixels per block. An understanding of the present invention, in particular the function of the status word Za in maintaining the maximum Z value for the block, will be facilitated by the following description in which these blocks of pixels will be described as a group of linear pixels along a scan line. However, any block of pixels can be utilized, e.g. if the screen has X rows and Y columns then the status word (Za) has X/number of pixels per row and Y/number of pixels per column. This description will use thirty two pixels per block, arranged linearly and parallel to the Y axis of a cartesian coordinate system. It should be noted that in practice the number of pixels per block will be selected to maximize performance based on criteria such as cost and hardware utilization. Any number of rows and columns can be used and the pixels do not have to be arranged linearly. A line 16 begins within block 1 and ends in block 3, extending from Y1 to Y2. Thus it can be seen that line 16 includes pixels within each of blocks 1, 2 and 3. It should be noted that the present invention contemplates other possible configurations of lines and surfaces to be drawn, as well as other configurations of blocks of pixels.In the following description of the operation of the present invention with reference to Figures 3A and 3B, it is assumed that the line 16 is to be drawn through the pixels 14 of blocks 1, 2 and 3, as shown in Figure 2.At step 1, the parameters of the block being considered must be initialized. In this example, the Y values must be extended along the scan line such that all pixels to be drawn as line 16 are considered consecutively, independent of the number of blocks 1, 2 and 3, or the like which may contain the line. For example, in blocks 1, 2 and 3 as shown in Figure 2, the Y value is initially set to correspond to the first pixel in the block containing the beginning of the line being drawn, Y1. In this case, Y1 corresponds to the third pixel in block 1 and Y2 corresponds to the third pixel in block 3. The line to be drawn between Y1 and Y2 includes all of the pixels contained in block 2. In order to process this line three blocks of pixels need to be considered. First, those pixels contained within the first adjacent block 1 including those pixels which occur prior to the beginning of the line being drawn, i.e. pixels 1 and 2 of block 1, and those pixels lying within the line to be drawn, i.e. pixels 3 to 32 of block 1. Second, pixels 1 to 32 of block 2 must be considered when drawing line 16. Third, the pixels of block 3 must also be considered including those pixels associated with line 16, i.e. pixels 1 to 3, and those pixels not associated with the line, but contained within one of the blocks which has at least one pixel within line 16, i.e. pixels 4 to 32 of block 3.Additionally at step 1, YSTART is set at the left, or beginning pixel of the block being considered, i.e. YSTART is equal to pixel 1. Further, YSTOP is defined as YSTART plus the number of pixels in the block minus one, and equals pixel 32. Any number of pixels can be used for the blocks, but thirty two was chosen to exemplify the present invention and should not be considered a limitation.Step 2 considers the pixels belonging to an intersected block being drawn, i.e. all pixels of a block having any pixels which are intersected by line 16. If Y is not less than or equal to (i.e. more than) YSTOP, then the pixels cannot be included in the block under consideration and the method proceeds to step 10 (Fig.3B) and ends. It should be noted that YSTART is defined as the first pixel in each block of pixels being considered and YSTOP is defined as the last pixel in each block. At step 3, it is determined whether the block under consideration is initialized or uninitialized. That is, a determination is made as to whether the pixels contained within the block have previously been written to with a Z value or are logically cleared , this meaning that Za for the block has a negative value. Specifically, has the Z value for the status word Za for each block been set to a negative value thereby indicating the uninitialized nature of the block of pixels? It should be noted that all blocks having at least one pixel contained in the line being drawn are considered independently of the remaining blocks (subsequently considered) contained on the display 10 regardless of whether a line or surface to be drawn extends into other blocks. If the blocks 1, 2 and 3 are uninitialized, the processing of block 1 continues to step 4 which determines whether the Y value is less than Y1, the starting point of line 16. It can be seen that pixels 1 and 3 of block 1 satisfy step 4 and the method proceeds to step 5 where the frame buffer for the pixel being considered is written to a background colour (as the line has not started) and the Z buffer and status word (Za) for the block are set equal to the Z max value. Thus, the Z buffer for the pixel now contains a value such that it is initialized. The status word Za is also set to Z max so that a running total of the maximum Z value encountered for the pixels in this block is kept. It should also be noted that steps 4 and 5 are looped together by incrementing Y at step 5, i.e. setting Y equal to Y plus one. In this manner, each pixel is considered successively and steps 4 and 5 are continuously repeated while the requirements of step 4 are met. When Y corresponds to pixel 4 of block 1 it can be seen that Y is no longer less than Y1 and the method proceeds to step 6, where it is determined whether Y is less than or equal to the lesser of YSTOP and Y2. YSTOP is the last pixel in the block 1 under consideration, and Y2 is the last pixel in the line being drawn. In this case, YSTOP for block 1 is pixel 32 of block 1. Therefore, it can be seen that step 6 will be satisfied for pixels 3 to 32 of block 1, because Y will be less than or equal to YSTOP for these pixels. For each pixel where the requirements of step 6 are satisfied, the operation proceeds to step 7 where the frame buffer for the first pixel considered as not less than Y1 is set with a colour value for the line being drawn, the Z buffer is set with the Z value for the line being drawn and status word Za is set to the maximum of the current Za value or the current Z value such that the running total of the maximum Z value for the block is maintained. For each subsequent pixel considered as not less than Y1, the frame buffer is set to the colour value of the previous pixel, plus a delta colour value, determined through interpolation, or the like. That is, the frame buffer for each subsequent pixel is set to a colour value equal to the previous colour value plus the delta colour value. Similarly, the Z buffer for subsequently considered pixels is set to Z (for the previous pixel) plus a delta Z value, also determined through interpolation. It can be seen that for the first pixel in each block delta colour and delta Z will be equal to zero. Therefore, for the first pixel the Z buffer is set equal to the Z value and the frame buffer for the first pixel is set equal to the colour value. Once again, Y is incremented by setting it equal to Y+1 and steps 6 and 7 are repeated for each pixel which satisfies the requirements of step 6 (in this case pixels 3 to 32 of block 1), because the operation loops between steps 6 and 7 during the time when Y is less than or equal to the lesser of YSTOP and Y2. When Y is no longer less than or equal to the minimum of YSTOP, or Y2, the operation proceeds to step 8 (Figure 3b) which determines whether Y is less than or equal to YSTOP, which was defined with regard to step 1. Thus when the last pixel of block 1 (pixel 32) has been processed, at step 7, and Y has been incremented such that Y=Y+1, Y is not less than YSTOP in step 8. Therefore, the operation continues to step 28 which determines if blocks are remaining to be processed. If so, the operation returns to step 1 (Fig. 3A). At this time, block 1 of Figure 2 has been processed and pixels 1 and 2 have been written with the background colour while pixels 3 to 32 have been written with the line colour. Additionally, the status word Za for block 1 has been set to the maximum Z value which corresponds to any of the pixels 1 to 32 of block 1. That is, Za is set equal to the maximum Z value for any one of the pixels in the block.Step 1 initializes YSTART for the next block to be considered (block 2) and step 2 determines if Y is less than or equal to YSTOP. Step 3 then determines whether the next block to be processed (block 2) is initialized or uninitialized. Assuming that block 2 is uninitialized, the operation proceeds to step 4 which then determines if Y is less than Y1. In this case, for block 2, Y is the first pixel in block 2 and is not less than Y1. The operation then proceeds to step 6 which determines if Y is less than or equal to the lesser of YSTOP and Y2. Again referring to Figure 2, it can be seen that Y is in fact less than or equal to the lesser of YSTOP (pixel 32 of block 2) and Y2. The operation then continues to step 7 where the status word Za for block 2 is set to the maximum value of Z, to begin keeping the running total of maximum Z values for the block. For the first pixel in block 2, Za will be set to the Z value of pixel 1 and during consideration of subsequent pixels the status word Za will be set with the maximum of its current value, or the Z value for each pixel satisfying step 6. Additionally, the frame buffer is set to the line colour determined by the delta colour (colour = colour + delta colour), Z is set equal to the Z value determined by delta Z (Z = Z + delta Z) and the Z buffer is set equal to Z (Z buffer is effectively set to Z + delta Z). The pixel being considered is then incremented by Y = Y+1 and iterations between steps 6 and 7 will continue so long as the pixels being considered within block 2 satisfy step 6. It can be seen that all the pixels within block 2 are less than or equal to the lesser of YSTOP and Y2 and each pixel within block 2 will undergo the operations set forth in step 7. After pixel 32 of block 2 is processed at step 7 the operation returns to step 6, where it is then determined that Y is no longer less than or equal to the lesser of YSTOP and Y2, because all the Y values corresponding to the pixels in block 2 have been processed. The operation then proceeds to step 8 where it is determined that Y is not less than YSTOP and the operation continues to step 28 and once again return to step 1. Thus, after the processing of block 2, it can be seen that the status word Za for block 2 is set to the maximum Z value encountered for any one of the pixels 1 to 32 contained in block 2, and that each of the pixels 1 to 32 has been written with the line colour for line 16.Once again steps 1 and 2 initialize and determine if Y is less than YSTOP, respectively. Step 3 then determines whether the next block to be processed, in this case block 3, is initialized or uninitialized. Assuming that block 3 is uninitialized the operation continues to step 4 where it is determined that Y is not less than Y1. The operation then proceeds to step 6 where it is determined if Y is less than or equal to the lesser of YSTOP and Y2. For block 3, Y2 is less than YSTOP. Pixels 1, 2 and 3 of block 3 (Fig.12) are less than or equal to Y2 and the frame buffer for each of these pixels is written in step 7 with the line colour (colour = delta colour), the status word Za for block 3 is set to the maximum Z value corresponding to any one of pixels 1 to 3 of block 3, the Z buffer is set to the Z value of each pixel, as determined by delta Z, and the Z value is set equal to the Z + delta Z (the delta Z value being the change between the Z value for the previous pixel being considered and the current pixel being considered) such that for each subsequent pixel, the Z buffer will be set to Z + delta Z. Again, steps 6 and 7 are looped and incremented by Y = Y+1 for each pixel satisfying the requirements of step 6. When pixel 4 of block 3 is encountered, Y is no longer less than or equal to Y2, as Y2 corresponds to pixel 3 of block 3, the last pixel corresponding to the line being drawn. Therefore, the operation continues to step 8 where it is determined if Y is less than or equal to YSTOP. Pixel 4 of block 3 is less than YSTOP (4 is less than 32). Therefore, the operation continues to step 9 where the frame buffer for pixel 4 is written to the background colour, the Z buffer is set to the Z max value and Za is also set to the maximum Z value for any pixel in the block, thereby keeping a running total of the maximum Z value for the entire block. Once again, steps 8 and 9 are looped and each pixel satisfying the requirements of step 8 is incremented. In this case pixels 4 to 32 of block 3 are consecutively processed by steps 8 and 9 until step 8 is no longer satisfied. Once pixel 32 of block 3 is processed and incremented by Y = Y+1, then step 8 is no longer satisfied, as the next pixel is included in a different block, and the process continues to step 28 where it is determined if there are any blocks to process. If so, the process returns to step 1 and the next block is initialized. If there are no blocks remaining to process then the operation proceeds to step 10 and ends.In the preceding description, the blocks are assumed to be uninitialized. Assuming that blocks 1, 2 and 3 have been initialized as they have been processed as described above, the operation must set the parameters of the block (Y to the left of the block at YSTART) again at step 1. It is then determined whether Y is less than or equal to YSTOP at step 2 and if so, the operation continues to step 3. If however, Y is not less than or equal to YSTOP the operation continues to step 10 and ends. Next, at step 3 it is determined whether the blocks are initialized. Assuming that blocks 1, 2 and 3 have been initialized and considering block 1, the operation will proceed to step 11 where it is determined if delta Z is greater than O, i.e. if the Z slope of the line is away from the front of the screen (line 1, Figure 4). A positive slope (delta Z greater than zero) will indicate that the line to be drawn is getting deeper into the screen when considered from left to right (line 1, Figure 4). A negative slope (delta Z is less than zero) means that the line being drawn is becoming shallower as considered from left to right (line 2, Figure 4). An estimate of the minimum Z value in the block for the line to be drawn is then calculated. If delta Z is positive then the operation proceeds to step 13 and the minimum estimated value of Z for the line (ZMIN1) is merely the initial Z value, as the Z value of successive pixels will increase, i.e. be farther from the front of the screen. If delta Z is negative, then the operation proceeds to step 12 and an estimate is made of the minimum Z value for any pixel in the block. As in this case, a block contains 32 pixels, the minimum possible Z value for any pixel in the block (ZMIN2) is the initial Z value (ZMAX2) of the first pixel in the block (that is contained within the line) plus the delta Z value, multiplied by 32 (number of pixels in a block). Thus, it can be seen that for lines to be drawn having a positive slope (line 1, Figure 4) the leftmost pixel will have the minimum Z value (ZMIN1) of the line. But, for lines with a negative slop (line 2, Figure 4), the rightmost pixel will have the minimum Z value (ZMIN2) which must be calculated.Subsequent to step 12 or 13, the operation continues to step 14 where it is determined if the estimated Z value (ZEST) is greater than the Z value within the status word Za for the block being considered. It should be recalled that Za is a representation of the maximum Z value for any pixel within the block and ZEST is a representation of the minimum possible Z value of any pixel in the line being drawn. Comparing these values determines if there is a possibility that part of the line is visible within the block, or if all of the line is hidden by the block. Step 14 addresses the hidden line/hidden surface aspect of the present operation. It can be seen that if the estimated minimum Z value for the block of pixels including the line to be drawn, which was determined at step 12 or 13, is greater than the status word Za (maximum Z value) for the block of pixels which have been previously initialized (written to), then all the pixels in the line currently being drawn have a Z value greater than the value of the status word Za of the previously initialized block of pixels. Therefore, the pixels representing the line to be drawn, and contained within the block currently being considered, are obscured from view by the pixels already contained in the previously initialized block (Figure 4). If ZMIN1 and ZMIN2 (Figure 4) are greater than Za, a full block bypass would be implemented during processing of lines 1 and 2. In this case, a full block bypass is implemented at step 15. That is, all the pixels in the block associated with the status word Za are considered to be closer to a viewer than the pixels in the block having the line currently being drawn and corresponding to the previously determined estimated Z value (ZEST). Therefore, the previously initialized block of pixels are considered to win and be visible to a viewer of display 10. In a full block bypass it is necessary to advance the colour and Z value of the line to their initial values at the beginning of the next block. It can be seen that implementation of a full block bypass will increase the processing speed, as well as reduce overhead associated with a pixel by pixel comparison of Z values. That is, a single comparison at step 14 (ZEST greater than Za?) may allow a total of 32 pixels (in this example) to be processed. If a full block bypass is implemented the operation then proceeds to step 27 where it is determined if there are blocks remaining to process and if so the method returns to step 1. If there are no blocks remaining to process at step 27 then the method ends at step 10.If at step 14, ZEST is not greater than the status word Za for the previously initialized block, then a comparison of the Z values at each pixel location must be implemented and is addressed at steps 14A and 16 to 24 (Figure 3b). Za2 (Figure 4) is not less than ZMIN2, so that a full block bypass cannot be implemented with respect to line 2. In this case a pixel by pixel comparison must be undertaken. In step 14A, the status word Za is set equal to zero because a new maximum value will have to be determined for this block, which will occur during subsequent processing of the pixels at steps 16 to 24.It can be seen that step 16 is analogous to step 4 and considers those pixels of the block being processed where Y is less than Y1. For example, pixels 1 and 2 of block 1 satisfy step 16, as Y is less than Y1. While Y is less than Y1, the method proceeds to step 17 where the status word Za is set equal to the maximum of the current value of Za, or the Z value within the Z buffer corresponding to that pixel. It should be noted that for the initial pixel being processed at step 17, Za will equal zero and be set to the Z buffer value. For subsequent pixels a comparison between Za and the Z buffer will occur. Again, steps 16 and 17 are looped so that each of the pixels satisfying the requirements of step 16 is incremented by Y = Y+1 and consecutively processed. Once pixel 3 of block 1 is encountered then step 16 is no longer satisfied and the process continues to step 18 which is analogous to the previously described step 6, i.e. is Y less than or equal to the lesser of YSTEP and Y2. Step 18 will be satisfied for pixels 3 to 32 of block 1 and the operation then continues to step 19 where a comparison for each pixel is made. That is, a determination is made of whether the Z value currently stored in the Z buffer, for each pixel, is greater than the new Z value for the line being drawn. If step 19 is satisfied, i.e. Z is less than the value in the Z buffer, the pixel is visible and frame buffer and Z buffer must be written with the new Z value at step 20.At step 21, it is determined whether Za needs to be updated because of the new value in the Z buffer. If the value in the Z buffer is greater than Ax, then Za is set equal to the new maximum value in the Z buffer at step 22. At step 22A the colour and Z value of the next pixel is computed, based on the interpolated value given by the delta colour and delta Z as previously discussed. Subsequent to step 22A the operation returns to step 18 which determines whether the next pixel in the block is less than or equal to YSTOP, in a manner as previously discussed.It can be seen that step 18 will address pixels 3 to 32 of block 1 until all the pixels in block 1 have been processed. At that time, the operation will proceed to step 23 and as all the pixels in block 1 have been processed, i.e. pixel 32 is not less than YSTOP, then step 27 determines whether there are blocks remaining to process and if so returns to step 1 or ends at step 10. As there are blocks remaining to process (blocks 2 and 3 of Figure 2), the method returns to step 1 and initializes block 2, step 2 determines whether Y is less than or equal to YSTOP and step 3 determines that block 2 has in fact been initialized. Steps 11 to 13 then determine an estimated Z value ZEST for the pixels in block 2, as previously discussed. Step 14 then compared the ZEST with the status word Za for block 2, which has been previously set to a maximum value in step 7. If a full block bypass is called for, then the operation continues to step 27 to determine if there are blocks remaining to process. If a full block bypass is not possible, then after step 14A, step 16 determines if Y is less than Y1 which will not be the case for block 2, as all the pixels contained therein are associated with line 16. Therefore, the operation continues to step 18 which addresses those pixels with Y values that are less than or equal to the lesser of YSTOP and Y2, which will include all of the pixels of block 2. Steps 18, 19, 20, 21, 22 and 22A are looped (incremented by Y = Y+1) and each pixel in block 2 will be consecutively addressed by steps 18 to 22A in the manner as previously described. Once, pixel 32 of block 2 is processed the operation proceeds back to step 18 and on to step 23 as Y has been incremented by Y+Y=1, therefore Y is not less than YSTOP. Again, step 27 then determines if any blocks are remaining to process and returns the process to step 2 for initialization of block 3. Step 1 initializes block 3, step 2 determines if Y is less than or equal to YSTOP and step 3 determines that block 3 has previously been initialized. Again, steps 11 to 13 calculate an estimated Z value (ZEST) and step 14 determines if a full block bypass is called for. Assuming that a full block bypass is not possible for block 3, the operation continues to step 16 where it is determined that Y is not less than Y1 and proceeds to step 18. It can be seen that for pixels 1 to 3 of block 3, step 18 will be satisfied and these pixels will be processed by the looped steps 18 to 22A, as previously discussed. Once pixel 4 is encountered, step 18 is no longer satisfied and the operation proceeds to step 23, which is similar to step 8, and determines if Y is less than or equal to YSTOP. It can be seen that for pixels 4 to 32 of block 3, step 23 will be satisfied and the status word for block 3 will be set equal to the maximum of the value contained in the Z buffer, or the value currently in the status word Za, whichever is greater. Thus, it can be seen that the Za buffer will contain the maximum value (running total) for any Z value encountered with regard to any pixel contained in the block. Once again, steps 23 and 24 are looped and each pixel satisfying step 23 contained within block 3 will be consecutively processed at step 24. Once the last pixel in block 3 (pixel 32) has been processed and incremented by Y = Y+1, then Y will no longer be less than or equal to YSTOP and the operation proceeds to step 27 which determines if there are any blocks remaining to process. It can be seen that for the described example all the blocks of Figure 2 have been processed and the operation will continue to step 10 and end.Figures 5A and 5B list pseudo-code which exemplifies one means of implementing the present invention. Once skilled in the art will appreciate the simplicity of the present invention when the pseudo-code is viewed in conjunction with the flowchart of Figures 3A and 3B.The present invention contains several advantages over conventional Z buffer display systems. For example, less time and overhead is required initially to set the Z values as only the status word Za for a block of pixels needs to be cleared. Conversely, conventional systems must clear each and every pixel individually. Therefore, rendering an object on the display can begin with less delay, thereby improving the efficiency of Z buffer initialization. Additionally, in complex scenes that are often rendered by graphics systems many objects may be hidden by other previously scan-converted objects, such as lines and surfaces. The present invention provides a means of comparing, through a status word Za, a plurality of pixels which have previously been drawn to the display with a plurality of pixels that are to be drawn to the display. This comparison matches the maximum Z value for the currently drawn pixels with the minimum value for the group of pixel to be displayed and determines whether the currently displayed pixels will win . If so, the currently displayed pixels will remain on the display and another group of pixels to be drawn can then be processed. It can be seen that comparing two groups of pixels with one another saves a great deal of time and overhead when compared with conventional processes which compare each individual pixel contained on a display.Further, in some cases large portions of the screen may never be used for rendering, i.e. the object may be small and centrally located in the screen. In this case refresh logic can detect the condition where the status word Za was set to a negative number (logically cleared) and insert the background colour for those pixels. Therefore, those areas of the Z buffer which are not used and correspond to portions of the screen for which no scene is displayed, are never actually reset or updated, thus saving additional time when rendering objects on a screen.
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A method of displaying objects on a computer graphics system (Fig.6) having a display (10) with a plurality of blocks (1) of pixels (14) thereon, the method comprising the steps of: displaying by the pixels (14) within each block (1), at least a portion of a first object;providing a memory for each block of pixels, and storing in the memory a maximum depth value of the pixel within each respective block having the greatest depth (step 4, 5); characterized bydetermining an estimated minimum depth value for a second object (16) to be displayed by at least one pixel (14) in each block (1) (step 12,13) by: (a) determining whether the slope of the depth values within the block corresponding to a second object (16) to be displayed is positive or negative;(b) for a positive slope setting an estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed;(c) for a negative slope, setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed, plus the number of pixels in the block multiplied by a delta depth value;comparing the stored maximum depth value with the estimated minimum depth value (step 14) for each block, and continuing to display the current block of pixels when the stored maximum depth value is less than the estimated minimum depth value (step 15).A method according to claim 1 wherein the method comprises the steps of comparing the depth values for each pixel in the block corresponding to the first object with the depth value for each pixel in the block corresponding to the second object and drawing the pixel having the minimum Z value to the display. A method according to claim 2, wherein the step of drawing comprises the steps of writing the frame buffer with a background colour for all non-intersected pixels, and writing the frame buffer with a line colour for all intersected pixels having the minimum depth value.A method according to claims 2 or 3, wherein the step of continuing to display comprises the step of bypassing consideration of the block of pixels corresponding to the second object, when drawing the second object, if the stored maximum depth value is less than the estimated minimum depth value.A method according to claim 1, wherein the step of determining comprises the step of determining whether at least one of the pixels contained within the block is intersected by the object.A computer graphics system for displaying objects on a computer graphics system (Fig.6) having a display (10) with at least one block (1) of pixels (14) thereon, the system comprising: means for displaying, by the pixels (14) within the block (1), atleast a portion of a first object;means for storing a maximum depth value for the block (step 4,5), comprising means for providing a memory for each block of pixels, and means for storing in the memory the depth value of the pixel within the block having the greatest depth; characterized bymeans for determining an estimated minimum depth value for a second object (16) to be displayed by at least one pixel (14) in said block (1) (step 12,13) comprising: (a) means for determining whether the slope of the depth values within the block corresponding to the object to be displayed is positive or negative;(b) means for a positive slope for setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed;(c) means for a negative slope for setting the estimated minimum depth value equal to the depth value of the first encountered pixel in the block corresponding to the object to be displayed, plus the number of pixels in the block multiplied by a delta depth value;means for comparing the stored maximum depth value with the estimated minimum depth value (step 14); andmeans for continuing to display the current block of pixels when the stored maximum depth value is less than the estimated minimum depth value (step 15).A system according to claim 6 further comprising means for comparing the depth values for each pixel in the block corresponding to the first object with the depth value for each pixel in the block corresponding to the second object and means for drawing the pixel having the minimum Z value to the display.A system according to claim 7, wherein the means for drawing comprises means for writing the frame buffer with a background colour for all non-intersected pixels, and writing the frame buffer with a line colour for all intersected pixels having the minimum depth value.A system according to claims 6 or 7, wherein the means for continuing to display comprises the means for bypassing consideration of the block of pixels corresponding to the second object, when drawing the second object, if the stored maximum depth value is less than the estimated minimum depth value.A system according to claim 6, wherein the means for determining comprises the means for determining whether at least one of the pixels contained within the block is intersected by the object.
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IBM; INTERNATIONAL BUSINESS MACHINES CORPORATION
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ALBAUGH VIRGIL ANTHONY; URQUHART ROBERT JOHN; ALBAUGH, VIRGIL ANTHONY; URQUHART, ROBERT JOHN
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EP-0489595-B1
| 489,595 |
EP
|
B1
|
EN
| 19,950,614 | 1,992 | 20,100,220 |
new
|
C07D301
|
C07D303
|
C07D301
|
C07D 301/32, M07D301:32
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Propylene oxide purification
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A method for separating methyl formate from lower alkylene oxide such as propylene oxide comprises contacting the impure alkylene oxide with basic ion exchange resin and separating alkylene oxide reduced in methyl formate content.
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Background of the InventionField of the InventionThe present invention relates to the separation of methyl formate from propylene oxide by treatment with basic ion exchange resin. Description of the Prior ArtMonoepoxides such as propylene oxide are highly important chemicals useful in a great number of applications. An important commercial technology for producing the monoepoxides is via the catalytic reaction between the corresponding olefin and an organic hydroperoxide, the hydroperoxide being prepared by hydrocarbon oxidation. See, for example, U.S. Patent 3,351,635. The epoxide product mixtures contain impurities such as methyl formate which are difficult to separate due to very small differences in boiling point between the epoxide and the impurities. In the case of propylene oxide, for example, considerable effort has been devoted to separating the close boiling methyl formate and other impurities. One direction taken by prior workers has been to provide extractive distillation techniques to accomplish the separation. U.S. Patent 3,838,020 shows a dual solvent extractive distillation process. U.S. Patent 3,843,488 shows extraction distillation using a C₈ to C₂₀ hydrocarbon to purify propylene oxide. U.S. Patent 3,909,366 shows extractive distillation purification of propylene oxide using C₆ to C₁₂ aromatic hydrocarbon. U.S. Patent 4,140,588 uses water in extractive distillation purification of propylene oxide. U.S. Patent 3,881,996 uses plural stage distillation to purify propylene oxide. East German Patent Specification 118,873 uses aliphatic alcohols such as tertiary butanol in separating methyl formate from propylene oxide by extractive distillation. U.S. Patent 5 006 206 uses tertiary butyl alcohol and water in the extractive distillation purification of propylene oxide. It has previously been proposed to separate oxygen-containing impurities from the propylene oxide by extractive distillation using lower glycols such as ethylene glycol and propylene glycol. See U.S. Patent 3,578,568 which describes this procedure and which teaches use of solvent in amount to comprise 15 to 50% of the vapor space in the distillation zone. EP-A-0 389 300 describes a similar separation but one which uses much lower solvent concentrations whereby propylene oxide losses are reduced. U.S. Patent No. 3,477,919 teaches a method for purifying propylene oxide contaminated with impurities such as methyl formate which boil near propylene oxide. The methyl formate impurity is removed from the contaminated propylene oxide by reaction with an aqueous slurry of calcium hydroxide. U.S. Patent No. 2,622,060 teaches a process for separating propylene oxide from a crude reaction mixture by treatment with an aqueous alkali metal hydroxide solution. U.S. Patent No. 2,550,847 teaches a process for the purification of propylene oxide in a crude reaction mixture containing methyl formate by subjecting the mixture to strong agitation with an aqueous solution of an alkaline saponifying agent. U.S. Patent No. 3,350,417 teaches a process for purifying propylene oxide comprising parallel and serial stages of distillation and a caustic treatment to simultaneously aldolize acetaldehyde and saponify methyl formate. The solvent used in the reaction step is removed before subsequent caustic treatment. U.S. Patent 4,691,034 removes methyl formate from propylene oxide by contact with an aqueous calcium hydroxide slurry to which a solubilizer has been added. U.S. Patent 4,691,035 removes methyl formate from propylene oxide by contact with a base such as sodium hydroxide in water and glycerol. U.S. Patent 4,692,535 shows the removal of high molecular weight ethers from propylene oxide by treatment with an absorbent such as activated carbon. Despite the efforts of prior workers, work has continued in an effort to further improve the separation of contaminating impurities such as methyl formate from lower alkylene oxides such as propylene oxide. Abstract No 113713g of Chemical Abstracts, Volume 68, 1968 page 10949 reports studies on the catalytic characteristics of MR-type ion-exchange resins for the hydrolysis of ethyl acetate and butyl acetate Brief Description of the InventionIn accordance with the present invention, it has been found that propylene oxide containing methyl formate impurity can be purified by contact with a basic exchange resin. Detailed Description of the InventionThis invention is applicable to the purification of propylene oxide prepared by reaction of an organic hydroperoxide with propylene and containing methyl formate contaminant in amounts of 50 to 1600 ppm by weight, usually 100 to 800 ppm. In accordance with the present invention, a liquid mixture of propylene oxide and methyl formate contaminant is contacted with solid basic ion exchange resin such as Rohm and Haas' Amberlyst® A-21 weak-base ion exchange resin. As a result of this contact, methyl formate is converted to methanol while the formic anion is exchanged with the resin anions and absorbed in the resin. Propylene oxide essentially free of methyl formate is recovered and methanol, formed during the contact, is readily separated. The ion exchange resin can be completely regenerated by contact with aqueous base such as aqueous sodium hydroxide, calcium hydroxide, potassium hydroxide or the like after the formate removal function of the resin has decreased to an unsatisfactory level. While not intending to be bound by theory, it is believed that the methyl formate impurity reacts with water, which is normally present in at least trace quantities in the propylene oxide or which is formed by reaction of acid impurities with the anion exchange resin, to form methanol and formic acid. In especially preferred practice of the invention, the propylene oxide feed to the anion exchange resin contact contains at least the stoichiometric amount of water necessary to react with the contained methyl formate impurity. Such water can be provided by addition thereof where the impure propylene oxide does not contain sufficient water, although normally methyl formate containing propylene oxide feed streams produced by conventional processes contain adequate levels of water for practice of the invention. Generally, excessive amounts of water, e.g. ten times the stoichiometric amount or more, are not advantageous. The invention may be carried out in a continuous or batch-wise fashion. Continuous operation is preferred as is the use of a plurality of ion exchange resin contact zones with one zone being in use while a second is being regenerated. The use of three contact zones is particularly preferred, with two zones in use at the same time, one a lead contact zone and the second a polishing zone, while the third zone is being regenerated. Conditions for the contact involve temperatures in the range of about 10 to 50°C, preferably 15 to 25°C, although temperatures outside these ranges can be used. Ion exchange resins which are employed in practice of the invention are basic anion exchange resins which are well known articles of commerce. Both strong-base resins and weak-base resins can be used, although weak-base resins are preferred by reason of higher capacity. Strong-base resins can be produced by the reaction between chlormethylated styrene-DVB copolymer and a tertiary amine such as trimethyl amine, which results in a resin with quaternary ammonium groups. The principal types of weak-base anion exchangers are amine derivatives of styrene-DVB copolymers, epichlorohydrin-amine condensation products, and amine derivatives of phenol-formaldehyde products, and may contain primary, secondary or tertiary amine groups, or mixtures of some or all of these groups. Weak-base styrene-DVB resins can be made, for example, by aminating chloromethylated copolymer in much the same way that strong-base styrene-DVB resins are made, except that primary or secondary amines are generally used instead of a tertiary amine. U.S. patents which describe the preparation of basic anion resins useful in the present invention include: 4,025,467, 3,791,996, 3,817,878, 3,346,516, 4,082,701, 3,843,566, 3,813,353, 3,812,061, 3,882,053, 3,793,273, 3,296,233, 3,108,922, 3,005,786, 3,637,535 and 4,052,343. The following examples illustrate the invention: Example 1Twenty grams of Rohm and Haas' Amberlyst® A21 weak base anion exchange resin, a styrene/divinyl benzene resin with dimethyl amine functional groups, are placed in a 1.27 centimeter inner diameter and 30 centimeters long glass column. The depth of the resin bed is 24 centimeters and the total resin volume is 30 cubic centimeters. A crude propylene oxide feed containing 450 ppm methyl formate, 0.1 wt% water and other oxygenate and hydrocarbon impurities is fed to the bottom of the column at a volumetric flow rate of 120 cc/hr. The experiment is conducted at ambient temperature and atmospheric pressure. Discrete effluent samples are collected from the top of the column at predetermined intervals, and the samples are analyzed for methyl formate concentration by a gas chromatograph. The results show that for an accumulative effluent volume of about 2000 cc., no methyl formate is detected in the propylene oxide effluent steam. The methyl formate concentration breakthrough or leakage occurs after about 17 hours of continuous operation. After 25 hours of operation with a total effluent volume of about 3000 cc, the methyl formate concentration in the propylene oxide effluent stream is 60 ppm. After 33 hours of operation or an effluent volume of about 4000 cc, the methyl formate concentration in the propylene oxide effluent stream is 150 ppm, and the resin is regenerated. Example 2After completion of the experiment described in Example 1, the ion exchange column is drained to remove the excess of propylene oxide and the resin is regenerated by feeding a 4 wt% sodium hydroxide aqueous solution from the top of column at a volumetric flow rate of 60 cc/hr for two hours at ambient temperature and atmospheric pressure. This step is then followed by water rinse of the bed at 60 cc/hr at ambient temperature for one hour and a nitrogen (50°C) purge step to dry the resins. The experiment described in Example 1 is then repeated. No methyl formate is detected for the first 1950 cc of propylene oxide effluent. About 55 ppm and 170 ppm of methyl formate are detected for the accumulated effluent volumes of 3000 cc and 4000 cc, respectively.
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A method of purifying propylene oxide obtained by the reaction of propylene with an organic hydroperoxide and containing methyl formate contaminant in an amount in the range of 50 to 1600ppm by weight, said method comprising contacting a mixture of the propylene oxide and methyl formate contaminant with a basic anion exchange resin and separating propylene oxide having a reduced content of methyl formate. A method according to claim 1 wherein said basic ion exchange resin is a weak-base anion exchange resin. A method according to any preceding claim wherein the mixture contains at least the stoichiometric amount of water necessary to react with the methyl formate. A method according to any preceding claim wherein the resin is regenerated after said contacting by contact with aqueous base. A method according to claim 4 wherein said base is sodium hydroxide.
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ARCO CHEM TECH; ARCO CHEMICAL TECHNOLOGY, L.P.
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SHIH T THOMAS; SHIH, T. THOMAS
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EP-0489596-B1
| 489,596 |
EP
|
B1
|
EN
| 19,950,412 | 1,992 | 20,100,220 |
new
|
F16K37
| null |
F16K37
|
F16K 37/00G, F16K 37/00
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Monitoring of check valves
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A method and apparatus for nonintrusive monitoring of a check valve (20) provide an accelerometer (24) and an ultrasonic transducer (32) mounted on the check valve body (28). The accelerometer (24) and transducer (32) generate signals corresponding to audible sounds within the check valve (20) and reflected ultrasonic signals transmitted into the check valve (20) by the transducer (32). The signals are simultaneously recorded and then processed to provide a visual representation of conditions within the check valve (20).
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This invention relates to monitoring of check valves. A check valve is a self-actuating, flow limiting device. Its principal moving part, the flapper assembly, consists of a disc supported by a hinged arm. In the normal (open) operating condition, dynamic pressure from the flowing fluid is enough to overcome the weight of the disc, keeping it in the open position. In the fully open position the flapper arm is pressed against a backstop. As the flow velocity decreases, the flapper assembly moves to a new, partially open or equilibrium position relative to fluid flow. When the fluid velocity is low enough, the weight of the disc causes the flapper assembly to be seated. The valve is then in its closed position. A typical nuclear plant has approximately 100 safety related check valves ranging in size from 0.05m (2 inches) to 0.76m (30 inches). The majority of these valves, about 85%, control water flow. The remaining valves control steam or two-phase flow. Studies of safety-related check valves indicate typical problems such as a missing flapper, flapper flutter, backstop tapping, seat tapping, flapper pin and hinge pin wear, and flow leakage. Each of these problems can lead to undesirable consequences in the operation of the nuclear plant. Since the check valves are safety related, periodic monitoring and testing of the valves is essential and is required by the Nuclear Regulatory Commission. Before any non intrusive monitoring system was developed, check valves were disassembled, visually inspected, and then reassembled. The disadvantages of this process are that it is time consuming and the work must often be done in highly radioactive, restrictive spaces. Nonintrusive monitoring systems which the applicants are aware of include the following. US Patents Nos US-A-4,852,416 and US-A-4,782,702 disclose an ultrasonic testing apparatus and method that rely on a single transducer rotatably and pivotally mounted within a housing. The transducer is moved within the housing to achieve variable observation angles for determining the transducer position necessary to detect the position of the flapper assembly. Acoustic monitoring systems record and analyse the noise generated within the valve. An accelerometer mounted on the outside of the valve body detects noise within the valve. This noise is amplified, recorded, and analysed to determine some of the information relating to valve functions. In magnetic field monitoring, a permanent magnet is embedded in the check valve disc assembly. Monitoring of changes in the magnetic field provides information on movement of the disc assembly. Problems with the above systems are as follows. Adjustable transducer mounts are expensive and may be fragile and unreliable in field use, especially in highly radioactive areas where movement of the operator is often limited due to heavy protective clothing and limited space. Operators of the adjustable mounts must also be specially trained in their use. Acoustic monitoring is a passive system and thus cannot be used to detect certain conditions such as disc position or low frequency disc flutter. In some cases the information obtained cannot be used to determine decisively a deficient condition in the valve. The major drawback of magnetic field monitoring is that valves in existing, operating nuclear plants must be disassembled to install the permanent magnet. In view of the deficiencies in the above system and the environment in which the work must be carried out, there is a need for a check valve monitoring apparatus that is able to detect all of the above problems, that is able to determine the position of the flapper assembly, that is nonintrusive and does not require disassembly of the valve, that requires minimum operator training, and that requires minimum time to set up and acquire the data. According to one aspect of the present invention there is provided a method for nonintrusive monitoring of a check valve, the method comprising: mounting an accelerometer on the body of the check valve; mounting an ultrasonic transducer on the body of the check valve; activating said accelerometer to detect audible sounds within the body of the check valve; causing said transducer to emit a series of ultrasonic signals into the body of the check valve and to detect the reflected signals; simultaneously recording signals corresponding to the audible sounds detected by said accelerometer and the reflected signals detected by said transducer; and processing the recorded signals to provide a visual representation of the conditions within the check valve. According to another aspect of the present invention there is provided apparatus for monitoring a check valve, the apparatus comprising: an accelerometer mounted on the check valve; an ultrasonic transducer mounted on the check valve; means for simultaneously recording signals from said accelerometer and said ultrasonic transducer; and means for receiving and processing the recorded signals whereby a visual representation of conditions within the check valve is provided. Preferred embodiments of the present invention address the aforementioned needs in a straightforward manner. What is provided is a dual system approach where the systems are used to complement and cross-check each other. In preferred embodiments, an acoustic system using an accelerometer is mounted on the outside wall of a check valve, and a fixed position transducer is mounted on the external wall of the valve body. Sounds detected by the accelerometer are amplified, digitised and recorded on digital tapes. A series of rapid firing pulses from the transducer and their echoes are also recorded on tape. The recorded signals are then processed to determine the movement and position of the flapper assembly at the time of monitoring. The results of the processing are displayed on a visual display device such as a computer monitor for comparison of the data from each system so that an analyst can determine the condition of the valve assembly. The invention will now be further described, by way of illustrative and non-limiting example, with reference to the single figure which is a schematic diagram of an embodiment of the invention. Check valve monitor apparatus, generally referred to by the numeral 10, comprises an acoustic system 12, an ultrasonic system 14, means 16 for recording signals from the system 12, 14, and means 18 for receiving and processing the recorded data and displaying the processed data. A check valve 20 is positioned in line with a conduit (not shown) for fluid flow therethrough. The principal moving part of the check valve 20 is a disc 22. For ease of illustration, only the disc 22 is shown. However, it should be understood that the disc 22 is hingedly mounted inside the check valve 20 for movement as indicated by the arrows. It is the movement of the disc 22 and the condition of the hinge mounting of the disc 22 that the apparatus 10 is designed to monitor. The acoustic system 12 comprises an accelerometer 24 and an amplifier 26. The accelerometer 24 is mounted on the outside of the body 28 of the check valve 20 by any suitable means, such as by magnetic mounting. Although only one accelerometer is shown for ease of illustration, it should be pointed out that two accelerometers 24 are preferably used. The accelerometer 24 is a passive listening device that detects audible sounds generated within the check valve 20 such as sounds due to fluid flow, tapping of the disc 22 against the valve seat or backstop, and sounds generated by a loose or worn hinge pin on the disc 22. These sounds are converted to electrical signals and transmitted to the amplifier 26 via a signal cable 30. The amplifier 26 amplifies these low level sounds to an appropriate level for recording and listening by the operator. The ultrasonic system 14 comprises an ultrasonic transducer 32 and a transducer controller 34 which are operatively connected via a signal cable 36. The transducer 32 may be mounted on the body 28 by any suitable means, such as by magnetic mounting, or mounting by means of a strap around the body 28, or the transducer 32 may be hand held against the body 28. As in normal transducer use, a couplant is used between the transducer and the body 28 to ensure good transmission of the ultrasonic signal from the transducer 32 into the body 28. In a manner known in the art, the transducer controller 34 calculates the time difference between the transmission and return of the ultrasonic signal to determine the position of the disc 22 relative to the transducer 32 and generates signals accordingly. This information may be visually represented on a display 38 which is normally an oscilloscope. This information can also be recorded for later analysis in a more convenient location. The means 16 for recording signals from the acoustic system 12 and the ultrasonic system 14 receives signals via cables 40 and 42 respectively. The means 16 is preferably a digital tape recorder that is capable of simultaneously recording information received from the systems 12, 14 on separate channels. It is preferred that at least four separate recording channels are available: two for information from the acoustic system 12, one for information from the ultrasonic system 14, and one for information identifying the check valve being monitored. For protection against damage and radiation, the systems 12, 14 and the means 16 are preferably mounted in a protective housing 40 indicated by the dotted lines. The means 18 for receiving, processing and displaying the recorded data comprises an interface device 42, a data processor 44, a keyboard 46, a display device 48, and a printer 50. The interface device 42 is used to make the recorded information received via a cable 52 compatible with the data processor 44. The data processor 44 is preferably a personal computer based system containing a computer program directed to the processing of the recorded information for the purpose of displaying the information on the display device 48 and/or printing the information on the printer 50. The information is displayed and printed in a graph form that synchronises disc movement with time and allows the analyst to compare the information obtained from the systems 12, 14. The display device 48 is preferably a colour monitor, and the printer 50 is preferably a colour printer. The keyboard 46 is used by the analyst to control the processing of the information to analyse and view various conditions of the valve and/or positions of the disc 22. In operation, the accelerometer 24 and the ultrasonic transducer 32 are mounted on the outside of the check valve body 28. As previously mentioned, two accelerometers are preferably used. The transducer controller 34 is used to cause the transducer 32 to send a rapid series of ultrasonic signals into the check valve body 28 which signals are reflected and returned to the transducer 32 and sent to the transducer controller 34. The or each accelerometer 24 simultaneously detects audible sounds within the check valve body 28 and converts the detected sounds into electrical signals that are sent to the amplifier 26. The amplifier 26 amplifies these signals to usable levels. The means 16 simultaneously records the signals from the amplifier 26 and the transducer controller 34 on separate channels for processing and analysis. The means 16 is then connected with the processing means 18 through the interface device 42. The data processor 44 processes the information and provides information on the condition of the valve monitored in the form of a visual display and/or printout.
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A method for nonintrusive monitoring of a check valve (20), the method comprising: mounting an accelerometer (24) on the body (28) of the check valve (20); mounting an ultrasonic transducer (32) on the body (28) of the check valve (20); activating said accelerometer (24) to detect audible sounds within the body (28) of the check valve (20); causing said transducer (32) to emit a series of ultrasonic signals into the body (28) of the check valve (20) and to detect the reflected signals; simultaneously recording signals corresponding to the audible sounds detected by said accelerometer (24) and the reflected signals detected by said transducer (32); and processing the recorded signals to provide a visual representation of the conditions within the check valve (20). Apparatus for monitoring a check valve (20), the apparatus comprising: at least an accelerometer (24) mounted on the check valve (20); an ultrasonic transducer (32) mounted on the check valve (20); means (16) for simultaneously recording signals from said accelerometer (24) and said ultrasonic transducer (32); and means (18) for receiving and processing the recorded signals whereby a visual representation of conditions within the check valve (20) is provided. Apparatus as claimed in claim 2 including two accelerometers (24) mounted on the check valve (20). Apparatus as claimed in claim 2 or claim 3 wherein the said means (16) comprises a digital tape recorder for recording the said signals on separate channels.
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B & W NUCLEAR TECHNOLOGIES INC; B&W NUCLEAR TECHNOLOGIES, INC.
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ATAMAN VEDAT T; AU-YANG MAN KEUNG; KEY MICHAEL W; ATAMAN, VEDAT T.; AU-YANG, MAN KEUNG; KEY, MICHAEL W.
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EP-0489598-B1
| 489,598 |
EP
|
B1
|
EN
| 19,960,904 | 1,992 | 20,100,220 |
new
|
A61M25
|
A61L29, C08L33
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A61L29, A61M25
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A61M 25/06, A61L 29/04B+C08L39/06, A61L 29/04B+C08L33/14, A61L 29/06+C08L71/00, K61M25:06H
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Through the needle catheter
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A through the needle catheter 10 is provided where the needle 15 is splittable after removal and the catheter material is formed from an extremely hydrophilic polymer. Upon removal of the needle, the catheter expands with contact to water and other aqueous solutions, such as blood or intravenous dosages. Upon expansion, the outer diameter of the catheter tube 20 seals the tube within the body tissue preventing leakage from the body tissue around the tube 20. Also, the inner diameter of the catheter tube expands to allow higher infusion flow rates of intravenous fluids into the body.
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Field of the InventionThis invention relates to catheters for use in intravenous medication devices. Specifically, this invention relates to catheters which are placed into the body through a needle. Background of the InventionIntravenous catheters come in basically two forms. First, there are catheters which are emplaced over the introducer needle. After emplacement of the catheter the needle is withdrawn from the center of the catheter and intravenous transfusion is possible. The second type are catheters commonly referred to as through the needle catheters. In these devices, the needle is emplaced into the vein with the catheter inserted inside the hollow needle. After insertion, the needle is withdrawn, usually by splitting the needle apart during withdraw. Thus, the catheter remains within the vein and is able to transfuse immediately upon emplacement of the needle. Through the needle catheters have one very distinct advantage. That is, through the needle catheters are quite easy to insert into the vein because only the needle itself has to be inserted through body tissue. Whereas known needle making techniques afford easy insertion of the through the needle catheter, catheters themselves are somewhat more difficult to insert into the body when they are exposed around the needle. Thus, where possible, through the needle catheters have preference. In contrast, through the needle catheters have two major disadvantages. Removal of the needle is difficult. Because the needle is generally configured to be smaller than the catheter hub, the catheter must be disassembled, or disconnected from the catheter hub so that removal of the needle may take place. Then, the catheter is reassembled to the catheter hub from which infusion was possible. On the other hand, removal may be possible by sliding the needle over the hub connection. This method is less than desirable because the size of the needle increased. Or, the needle could be left in place and the catheter left to remain within the needle during infusion. This is undesirable because it causes reduced catheter size and left a foreign object within the body during infusion. This difficulty has been overcome through use of needles splittable along their diameter, and then removable over the catheter hub. Second, since the catheter tubing must necessarily be smaller than the inner diameter of the needle in a through the needle catheter, the catheter itself presented problems. First, as previously discussed, the catheter maintained a low flow rate. The design of the needle necessarily limited the tube dimensions so that the inner diameter of the tubing became even smaller than the needle, causing such low rates of flow. On the other hand, because such tubing is smaller than the needle outside diameter, after needle removal the catheter may create a poor seal between the catheter outside diameter and the pierced body tissue. This results in leakage problems in the tissue outside the catheter. US-A-4790817 discloses a through-the-needle catheter which expands upon wetting. Summary of the InventionIt is an object of the invention to provide a catheter which prevents leakage caused by improper seal with body tissue. It is further an object of the invention to provide a through the needle catheter which has enhanced flow rate. It is yet another object of the invention to provide a through the needle catheter in which insertion of the catheter remains simple and easy while overcoming the aforesaid problems of through the needle catheters. It is yet another object of the invention in which removal of the needle in this through the needle catheter causes no patient discomfort or tissue trauma while overcoming the aforesaid problems of through the needle catheters. Finally, it is an object of the invention to provide an improved through the needle catheter which is adaptable to all areas of catheter use. These, and other objects of the invention, are accomplished in a through the needle catheter tube comprised of an extremely hydrophilic polymer as defined in claim 1 and which swells and softens upon continuous exposure to water or other aqueous solutions, such as blood and intravenous delivery systems. The improved catheter tube is introduced into the body within the inside diameter of a splittable needle so that the needle is removable upon insertion of the catheter. Upon removal of the needle and during catheter contact with water or other aqueous solutions, the catheter swells so that the catheter tube creates a better seal with the body and eliminates leakage possibilities. In addition, because the catheter tube swells, the inside diameter of the tube increases and therefore the flow rate capabilities of the catheter tube are increased. Because the tube is formed from a hydrophilic polymer as defined in claim 1, an extremely stiff catheter can be inserted through the needle, yet it becomes soft upon insertion into the body for excellent indwelling of the catheter within body tissue. This catheter is useful in all sorts of through the needle catheter areas, such as peripheral intravenous catheters, arterial catheters, single and multilumen central lines, as well as catheters used to deliver drugs or fluids to areas other than the vascular system. The invention as described above, will be better understood by the accompanying Detailed Description of the Drawings taken in conjunction with the Detailed Description of the Invention which follows. Detailed Description of the DrawingsFig. 1 is a perspective view of a typical through the needle catheter device as embodied in the invention; Fig. 2 is an exploded perspective view of Fig. 1; Fig. 3 is a cross-sectional view of the invention taken along lines 3-3 of Fig. 1; Fig. 4 is a cross-sectional view as in Fig. 3 showing the invention emplaced within body tissue; and Fig. 5 is a cross-sectional view of the catheter as in Fig. 3 of the invention placed within body tissue with the splittable needle removed. Detailed Description of the InventionAs seen in Figs. 1 and 2, a typical through the needle catheter device 10 comprises a catheter 20 connected to a catheter hub which is ultimately attachable to a intravenous infusion device. The catheter 10 outer diameter is smaller than the needle 15 into which the catheter is emplaced. The needle 15 is usually attached to a needle hub and is protected by a needle guard before emplacement. In typical present day systems, the needle 15 is also splittable into two halves 15a, 15b along its lengthwise diameter. The needle 15 presents a hollow tubular configuration for insertion within the body, and is better explained in U.S. Patent Nos. 4,957,488 and 4,957,489 assigned to the common assignee of this invention. Generally, typical catheters 20 have been formed from extremely stiff polymers which allow for rather simple insertion within the needle 15 and therefore within the body tissue. These catheters 20 also cause many of the problems encountered as described in the Background of this Invention. On the other hand, as seen in Figs. 3, 4 and 5, the catheter tube of this invention differs from typical through the needle catheter tubes. The catheter tube of this invention is formed from an extremely hydrophilic polymer, namely polyhydroxyethyl(methacrylate) (poly HEMA) or crosslinked polyoxyethylene (poly-ox). Generally, these polymers are also stiff before wetting. All the benefits of typical through the needle catheters are still derived from this catheter when inserted through a needle into tissue. As with typical splittable needles, the needle 15 of this invention also is removable from the body tissue by splitting after insertion. Thus, while the catheter 20 is inserted into the body as seen in Fig. 3, and the needle 15 is originally in the tissue as seen in Fig. 4, the needle 15 is removed by splitting as seen in Fig. 2. Because the catheter 20 is still small and stiff, the needle readily slides over the catheter tube 20. After insertion of the catheter 20 and removal of the needle 15 from the tissue, the hydrophilic aspects of the catheter tube 20 begin to take effect upon wetting, and the catheter tube 20 begins to expand. Upon expansion, the outer diameter of the catheter tube 20 grows to at least fit the evacuated area caused by the removal of the splittable needle 15. Thus, any leakage problems caused by difficiencies in the catheter outside diameter 24 are avoided. As seen in Fig. 5, after removal of the needle and growth of the catheter after wetting of the hydrophilic polymer, the inside 22 of the catheter tube also begins to grow. With this expansion of the inner diameter 22 of the tube, there is no constriction of flow rates for infusion. Therefore, infusion and flow problems are also no longer a difficulty. With a typical catheter tube, cross sectional area will increase by over 50%, improving flow rates by this amount. Accordingly, with the improved material used in this catheter all the difficulties previously encountered by through the needle catheters are removed, allowing for a desirable use of through the needle catheters.
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A catheter assembly comprising: a hollow needle (15), splittable into two halves; and a catheter (20) removably insertable into the hollow needle (15) and connectable to an infusion set; wherein said needle (15) is removable from said catheter assembly after insertion into a patient, and said catheter expands after removal of said needle, characterised in that said catheter is formed from a polymeric material selected from polyhydroxyethyl(methacrylate) , and crosslinked polyoxyethylene . A catheter assembly according to claim 1, further including an infusion set and wherein the infusion set provides infusion immediately after insertion of said needle (15) and during removal of said needle. A catheter assembly according to claim 2 wherein said catheter (20) is attached to a catheter hub attached to said infusion set. A catheter assembly according to any preceding claim wherein said catheter (20) expands more than 50% in cross-section after wetting.
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CRITIKON INC; CRITIKON, INC.
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CAMERON ROBERT; CAMERON, ROBERT
|
EP-0489599-B1
| 489,599 |
EP
|
B1
|
EN
| 19,960,828 | 1,992 | 20,100,220 |
new
|
E04G7
|
E04G1
|
E04G5, E04G7
|
E04G 5/14, E04G 5/16, E04G 7/30C3C
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Scaffolding system
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A scaffolding system of the type comprising interconnected vertical legs (2) and horizontal space frames (4) is described. The legs (2) are provided with socket members (10) and at least one of the chord members of each space frame (4) is provided at either end thereof with first attachment means (20) comprising a pin (28) for insertion into a socket member (10) of a leg to which it is to be attached. The first attachment means (20) additionally include releasable latch means (30) carried on or in the pin (28) and biasing means (36) which, when the pin is inserted into a socket member (10), automatically urges the latch means (30) towards to the locked position. In the locked position a portion of the latch means (30) latches against the socket member (10) to retain the pin (28) therein and movement of the pin (28) within the socket (10) is prevented.
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This invention relates to scaffolding systems. Scaffolding systems generally consist of interconnected horizontal and vertical members. The horizontal and vertical members may both be in the same form, e.g. tubular members or the horizontal members can take the form of a space frame comprising two horizontal chord members interconnected and spaced by bracing members. Scaffolding systems have a multiplicity of uses, a particularly common one of which is to support beams, the beams being used, for example, as a work platform or to support concrete cast thereabove. Scaffolding systems employed for this purpose have to have good structural integrity and a problem which arises with those systems where space frames are employed is how to connect these to the vertical leg members to ensure this. In one known arrangement, the space frames are connected between adjacent vertical members by inserting pins attached to the ends of the chord members of the space frames in sockets provided on the vertical members. A latch member in the form of a plate pivotally mounted on the space frame is then rotated into a position in which it is held between the bottom edge of the socket and the space frame and so serves to prevent the space frame from upward movement relative the socket which would release the pin therefrom. The latching means plate is carried on a face of the space frame and is, therefore, vulnerable to damage both when the system is being transported in its dismantled state and when it is erected and in use. The latching plates do not prevent all movement of the pins in the sockets and so do not provide a rigid connection. They are furthermore vulnerable to incorrect positioning on erection and/or dislodgement in use, in which case they will cease to be effective in any way. Attempts have been made to provide a method of attaching space frames which does not suffer from these disadvantages and which provides a rigid and strong connection between the space frame and the two leg members between which it is secured. For example, British Patent Application GB-A-2234776 describes space frames with end vertical members of T-shaped profile which locate in T-shaped slots provided in the leg members, the two then being bolted together. The problem with this is the need for specially shaped parts which adds to the expense of the system. Furthermore, both in this and in other suggested arrangements, bolting is required. This makes erection a laborious and time-consuming operation and the nuts and bolts can be relatively easily lost. A further disadvantage of all the above-described arrangements is that they do not readily permit the attachment of bracing members across the bays formed by the vertical leg members and the horizontal space frames. Specifically, they do not allow the bracing members to be connected at the points of attachment of the space frames and the vertical leg members. The addition of bracing members at locations off-set from these attachment points can cause the introduction of secondary stresses into the system. European Patent Application EP-A-0427448 (relevant under Article 53(3)-EPC) describes a scaffolding system comprising a diagonal brace with a transverse pin for engaging an aperture in an end fitting of a horizontal cross-member. The pin has an internal snap-action latch which a hooked projection end to engage a complementary configuration on the eye. Danish Patent DK-A-117987 describes a scaffolding system with horizontal space frames including a pair of spaced horizontal chords. At each end of both chords a vertical pin is provided, which pins are received in sockets carried on vertical uprights of the system. Each pin carries therein a rivet shaped part biassed by a spring to protrude from the pin when positioned within a socket and thereby retain the pin therein. In accordance with the invention, a scaffolding system has a plurality of legs which are vertical in use, each provided with identical socket members along the length thereof, and a plurality of space frames, each of which comprises two horizontal chord members interconnected and spaced by bracing members and first attachment means at either end of at least one of the chord members whereby the space frame may be connected between two adjacent vertical legs, the first attachment means comprising a pin for insertion into the socket of a socket member, releasable latch means carried on or in the pin and biassing means which, when the pin is inserted into the socket of a socket member, automatically urges the latch means towards a locked position in which a portion thereof latches against the socket member to retain the pin therein and movement of the pin within the socket is prevented, characterised in that the sockets of the socket members have horizontal axes and in that the axes of the pins of the first attachment means of each space frame are transverse to the plane of the space frame whereby when the frame is connected between two adjacent vertical legs, the pins axes are horizontal. The advantages of this arrangement are that, firstly, the first attachment means are automatically operated so that erection of the system is simpler and quicker. Secondly, they do not require any bolts nor indeed any separate parts which could easily be lost. Thirdly, a rigid and secure connection is provided in which movement of the pin within the socket is prevented and so too, therefore, is movement of the space frame relative the vertical leg to which it is connected. Furthermore, as the latch means is carried on or in the pin, it can be located so that, in use, it is positioned between the vertical member and the space frame and is, therefore, protected. Very preferably the latch means is carried in the pin with the portion thereof which latches against the socket protruding from the pin. The risk of damage to the attachment means, not only when a scaffolding system is erected and in use but also when it is dismantled and being transported, is, therefore, minimized. Suitably the biassing means comprises a spring carried in the pin. The pin is preferably dimensioned such that it will form a close fit with the socket member to thereby provide a rigid and strong connection of the space frame and vertical member. The other chord member of each space frame may also be provided at each end thereof with first attachment means. However, preferably, the other chord member of each space frame is provided at either end thereof with second attachment means comprising a C-shaped end fitting which locates around and cooperates with a portion of a socket member. It has been found that, so long as one of the chord members of each space frame is provided at each end thereof with the first, pin, attachment means, sufficient system stability results from the use of the second, simpler, attachment means at the other chord. The result is a very economical system which is easy to erect and dismantle. A further advantage is that, as will be further described below, the C-shaped end fitting when located around and cooperating with a particular socket member does not interfere with or prevent the securement of a first attachment means to that socket member. Diagonal bracing members provided at an end thereof with a first attachment means can, therefore, be secured to the socket member. In this way the introduction of secondary stresses into the system is avoided. The socket members are suitably arranged in spaced groups, each group comprising two sets of four socket members equi-angularly spaced around a vertical leg, the sets being spaced apart by a distance approximately equal to that between the chord members of a space frame. In a preferred embodiment each socket member comprises a pair of spaced plates, each connected at one end to a vertical leg and formed with an aperture therein dimensioned such that a pin of the first attachment means may be passed therethrough, the apertures being aligned. A ring is secured between the plates with its axis aligned with the apertures therein. The outer radius of the ring is approximately equal to the radius of the inner face of a C-shaped end fitting of the second attachment means. The distance between the ring and the vertical leg to which the socket member is secured is equal to the width of an arm of the C-shaped end fitting. The result is that axial movement of a chord member of a space frame provided with the second attachment means relative the vertical legs between which it is connected is prevented. By also making the spacing between the plates of a socket member approximately equal to the thickness of an arm of the C-shaped end fitting, movement of the chord in the horizontal plane is prevented. The invention will now be further described by way of example with reference to the accompanying drawing in which:- Figure 1 is a side view of part of a scaffolding system in accordance with the invention; Figure 2 is a plan view of the scaffolding system part of Figure 1; Figure 3 is a side view of another part of the scaffolding system of Figure 1; Figure 4 is a side view of a leg of the scaffolding system of Figure 1; and Figure 5 is a side view of a first attachment means of the scaffolding system of Figure 1 which illustrates the operation thereof. The scaffolding system comprises a plurality of vertical legs 2 interconnected by space frames 4. The space frames 4 comprise two horizontal chord members 6 interconnected and spaced by bracing members 8 which may be vertical, as shown, and/or diagonal. The legs 2 are provided with a plurality of groups of sockets 10 along their length, each group consisting of two sets of four equi-angularly spaced sockets 10. The spacing between each set of sockets 10 is approximately equal to that between the two chord members 6 of the space frames 4. The number of groups of sockets 10 provided will obviously depend on the length of the leg 2. As illustrated in Figure 4, only one group of sockets 10 may be provided. Each socket 10 consists of a pair of plates 12 welded, see 14, to the leg 2. Aligned apertures 15 are provided in the plates 12 and a ring 16 whose inner diameter is equal to that of the apertures is welded, see 18, between the plates 12 with its axis aligned with those of the apertures 15. The set of sockets 10 which are uppermost has the apertures 15 in the upper halves of the plates 12, whilst the set which is lowermost has the apertures 15 in the lower halves of the plates 12. Figure 1 shows the top chord 6a of a space frame 4. This is provided at either end with first attachment means 20 shown in detail in Figure 5. The first attachment means 20 comprises a body having a generally annular boss 22 by which it is welded, see 24, to the end of the chord member 6a. An integral bracket portion 26 of the boss 22 mounts a hollow pin 28 which extends transversely to the plane of the space frame 4. A hook-like latch member 30 is mounted in the interior of the pin 28. The latch member 30 has a hooked projecting nib 32 which protrudes through a slot provided in the wall of the pin 28. The other end of the latch member 30 is pivotally mounted on, for example, a Bissel pin 34 connected between opposite walls of the pin 28. A torsion spring 36 is mounted between an internal surface of the pin 28 and the latch member 30 and around the pivot pin 34. The torsion spring 36 urges the latch member 30 to the position illustrated in Figure 5 in which the nib 32 projects from the pin 28. Adjacent the pivot pin 34, the latch member 20 has an integral operating arm 38 which projects laterally from the pin 28 through a slot in the wall of the latter as shown in Figure 1. The operating arm projects towards the chord member 6a of the bracing frame 4 and is disposed between a pair of protective ribs or flanges 40 on the latching member 20. When the pin 28 of the latching member 20 is inserted through apertures 15 and ring 16 of a socket member 10, the nib 32 is pushed into the pin 28 against the bias of spring 36, the nib 32 being provided with a tapered leading surface to facilitate this movement. When the pin 28 has been fully inserted, the spring 36 will cause the nib 32 to revert to the position in which it projects through the slot in the pin 28 so causing it to engage the plate 12 on the opposite side of the socket member 10 to that from which the pin 28 was inserted. The pin 28 will, therefore, be positively retained within the socket member 10. Furthermore, as illustrated in Figure 5, the pin 28 is a close fit within the ring 16, whilst the distance between the bracket 26 and the tip of the nib 32 is equal to that between the two plates 12 of the socket member 10. Thus a rigid connection will be provided at which there will be little movement of the parts. To release the space frame 4, the arm 38 is pressed towards the chord 6a to cause the nib 32 to be withdrawn into the pin 28 against the bias of the spring 36. Pin 28 can then be withdrawn from the ring 16. Figure 3 shows the lower chord 6b of a space frame 4. This is provided with second attachment means 42 at either end thereof. The attachment means 42 comprises an annular boss 44 by which it is welded, see 46, to the end of the chord member 6b. Integrally formed with the annular boss 44 is a C-shaped end fitting 48 with an inner circular face of the same radius as the exterior of ring 16. The width of the outer arm 50 of the C-shaped end fitting 48 is equal to the distance between the ring 16 of the socket member 10 and the face of the leg 2 to which the socket member 10 is attached. The thickness of the C-shaped end fitting is equal to the distance between the plates 12 of the socket member 10. The result of this is that the C-shaped end fitting 48 will locate around the ring 16 with its far arm 50 held in the plane transverse to the axis of the leg 2 by the plates 12, the ring 16 and the leg 2. The prevents any movement of the end fitting 48 within this plane and thus provides a secure and rigid connection between the lower chord 6b and the leg 2. The form of the socket members 10 and of the second attachments means 42 allows a bracing member 52 to be additionally attached between the point of connection of a leg 2 and the lower chord 6b of a space frame 4 and a head or base jack carried on an adjacent leg. The diagonal bracing member 52 is provided at one end thereof with a first attachment means 20. The pin thereof can be inserted through the ring 16 without interference from the end fitting 48 of the second attachment means 42 provided at the ends of the lower chord 6b of the space frame 4. By attaching the diagonal bracing member 52 at the point of connection of the space frame 4 and vertical leg 2, the introduction of secondary stresses into the system is avoided. The space frame 4 can be easily and securely attached between two vertical legs 2 by pinning its upper chord 6a to two aligned socket members 10 with the first attachment means 20, and latching its lower chord 6b between two further aligned socket members 10 by locating the end fittings 48 of the second attachment means provided at either end thereof around the rings 16 of the socket members 10. It will be appreciated that the opposite arrangement could be employed, that is, first attachment means could be provided at either end of the lower chord 6b with second attachment means being provided at either end of the upper chord 6a. Diagonal bracing members 52 can be attached at those socket members where a space frame chord is connected by second attachment means. Furthermore, the diagonal bracing members could instead be provided with a suitable form of the second attachment means so that these could be attached at socket members where a space frame chord is secured by first attachment means.
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A scaffolding system having a plurality of legs (2) which are vertical in use, each provided with identical socket members (10) along the length thereof, and a plurality of space frames (4), each of which comprises two horizontal chord members (6) interconnected and spaced by bracing members (8) and first attachment means (20) at either end of at least one of the chord members whereby the space frame (4) may be connected between two adjacent vertical legs (2), the first attachment means (20) comprising a pin (28) for insertion into the socket of a socket member (10), releasable latch means (30, 32) carried on or in the pin (28) and biassing means (36) which, when the pin (28) is inserted into the socket of a socket member (10), automatically urges the latch means (30, 32) towards a locked position in which a portion (32) thereof latches against the socket member (10) to retain the pin (28) therein and movement of the pin (28) within the socket is prevented, characterised in that the sockets of the socket members (10) have horizontal axes and in that the axes of the pins (28) of the first attachment means (20) of each space frame (4) are transverse to the plane of the space frame (4) whereby when the frame (4) is connected between two adjacent vertical legs (2), the pins axes are horizontal. A scaffolding system as claimed in Claim 1 wherein first attachment means (20) are also provided at each end of the other chord member (6) of each space frame (4). A scaffolding system as claimed in Claim 1 wherein the other chord member (6) of each space frame (4) is provided at either end thereof with second attachment means (42) comprising a C-shaped end fitting (48) which locates around and cooperates with a portion of a socket member (10). A scaffolding system as claimed in any preceding Claim wherein the socket members (10) of each vertical leg (2) are arranged in spaced groups, each group comprising two sets of four socket members (10) equi-angularly spaced around the leg (2), the sets being spaced apart by a distance approximately equal to that between the chord members (6) of a space frame (4). A scaffolding system as claimed in any preceding Claim wherein each socket member (10) comprises a pair of spaced plates (12), each connected at one end to a vertical leg (2) and being formed with an aperture (15) therein dimensioned such that a pin (28) of the first attachment means (20) may be passed therethrough, the apertures (15) being aligned. A scaffolding system as claimed in Claim 5 as dependent on either Claim 3 or Claim 4 wherein the distance between the plates (12) is equal to the thickness of at least the arms (50) of the C-shaped end fittings (48). A scaffolding system as claimed in Claim 5 or Claim 6 wherein each socket member (10) further includes a ring (16) secured between the plates (12) with its axis aligned with that of the apertures (15) therein. A scaffolding system as claimed in Claim 6 or Claim 7 as dependent on either Claim 3 or Claim 4 wherein each C-shaped end fitting (48) has a part circular inner face, the radius of which is equal to the outer radius of each ring (16). A scaffolding system as claimed in either Claim 6 or 8 or Claim 7 when dependent on either Claim 3 or Claim 4 wherein the ring (16) of each socket member (10) is carried by the plates (12) at a distance from the vertical leg (2) to which these are secured equal to the width of an arm (50) of each C-shaped end fitting (48). A scaffolding system as claimed in any one of Claims 3 to 9 including bracing members (52) provided at one end thereof with first attachment means (20).
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LEADA ACROW LTD; LEADA ACROW LIMITED (REG. N 2766044)
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HOLLAND JOHN; HOLLAND, JOHN
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EP-0489601-B1
| 489,601 |
EP
|
B1
|
EN
| 19,971,105 | 1,992 | 20,100,220 |
new
|
G01N27
|
G01N27
|
G01N27
|
G01N 27/36, G01N 27/403B, G01N 27/414
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Small glass electrode and process for preparation thereof
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A small glass electrode and process for preparation thereof are disclosed. This small glass electrode is characterized in that said glass electrode, which has a bonded structure comprises a reference electrode composed of silver/silver chloride, a glass substrate having a pad embedded therein, said pad being composed of gold or platinum and circuit-connected to the reference electrode, and a silicon substrate having a (100) plane selectively etched by the anisotropic etching technique and comprising a groove for injecting an electrolyte composed of an aqueous solution containing chlorine such as KCℓ, or HCℓ, at least one hole for holding the electrolyte and a glass film formed in a portion corresponding to the reference electrode. By this structure, the small glass electrode can be easily manufactured at a low cost.
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The present invention relates to a glass electrode and a process for the preparation thereof. More particularly, the present invention relates to a small glass electrode formed by utilizing a micro-machining technique and a process for the preparation thereof. A glass electrode is widely and generally used as a sensor for determining the hydrogen ion (H+) concentration in an aqueous solution. The determination of the H+ concentration is required not only in ordinary chemical experiments but also in fermentation control and in the medical field. Furthermore, a biosensor fabricated by combining a glass electrode with either enzymes or microorganisms can be used for determining various chemical compounds. For example, glucose reacts with dissolved oxygen and is oxidized to gluconolactone with the aid of a catalyst called glucose oxidase. If the change in the H+ concentration during this reaction is measured, the glucose concentration can be determined from this change. According to a similar principle, the concentration of urea in a sample can be determined. In a glass electrode, the H+ concentration is measured by utilizing the electroconductivity of glass. Namely, the phenomenon is utilized that, when a glass film having a thickness of about 100 µm and an electric resistance of several hundred MΩ is placed in a solution, a voltage difference is produced according to the pH value of the solution. Fig. 1 of the accompanying drawings illustrates the structure of the sensing portion of a conventional glass electrode, which comprises a reference electrode 2 composed of silver/silver chloride (Ag/AgCl), an internal solution 4 such as a potassium chloride (KCl) solution having a certain concentration, and a spherical sensing glass film 6 formed at the end. When this glass electrode is immersed in a solution containing H+, in response to the active quantity (ai) of H+, a potential is generated according to the Nernst equation: E = const + (RT/F)ℓnai wherein E represents the potential of the glass electrode, R represents the gas constant, T represents the absolute temperature, and F is the Faraday constant. Accordingly, the H+ concentration is determined by the above equation. However, the commercially-available glass electrode, as shown in Fig. 1, has a size similar to that of a fountain pen, and is formed by glazing, and is therefore expensive. An ion-sensitive electric field effect transistor (abbreviated to ISFET ) has been developed as a small H+ concentration sensor. Since a photolithographic technique of a semiconductor is utilized for the formation of this sensor, the size of the sensor can be reduced. When a device, such as an ISFET, is immersed in an aqueous solution, insulation of the substrate is important. Accordingly, many elements formed on a silicon (Si) substrate are diced into chips and a silicon nitride (Si3N4) film is formed on the peripheries of the chips to effect insulation, or an SOS (silicon-on-sapphire) substrate is used. Alternatively, a method is used in which a thin film transistor (TFT) is formed on a glass substrate. However, these methods mean that a rise in the price cannot be avoided and therefore, the sensor cannot be manufactured at a low price. The conventional glass electrode formed by glazing is large in size and is expensive. An ISFET formed by the photolithography of an Si substrate requires insulation and a rise in the price is inevitable owing to the necessity of providing this insulation. Under this background, development of another method of providing a practical glass electrode of small size and low price is desired. EP-A-0269031 discloses a glass electrode having the features of the preamble of claim 1. It is an object of the present invention to provide a small glass electrode capable of overcoming the foregoing problems and a process for the preparation thereof. In accordance with a first aspect of the present invention, there is provided a glass electrode comprising: a glass substrate having a reference electrode, a pad for external electrical connection and a lead-in line connecting the reference electrode and the pad; a substrate having a hole therein for holding a fluid electrolyte, the substrate being bonded to the glass substrate such that the hole is located adjacent the reference electrode; and a glass sensing film covering and sealing the hole on the surface of the substrate opposite the surface thereof bonded to the glass substrate, characterised in that the substrate is a semiconductor substrate having a groove for injection of electrolyte in the surface thereof bounded to the glass substrate, the hole and the groove being anisotopically etched in the semiconductor substrate, and the reference electrode, pad and lead-in line being embedded in the glass substrate. The glass film may have a multiple-layer (for example, two-layer) structure. In accordance with a second aspect of the present invention, there is provided a process for the preparation of a glass electrode, comprising: selectively etching a glass substrate; forming, on the etched portion of the glass substrate, a reference electrode of silver/silver chloride and, circuit-connected to the reference electrode, a pad of gold or platinum; subjecting a substrate face of a silicon substrate having a plane to anisotropic etching to form in the substrate face a hole for holding a fluid electrolyte and a groove for injection of electrolyte; forming a glass sensing film on the face of the silicon substrate opposite the substrate face by partially removing a silicon oxide film left on that face such that the hole is covered and sealed with a silicon oxide film and converting the silicon oxide film to a glass film; and bonding together the etched surface of the glass substrate and the substrate face of the silicon substrate such that the hole is located adjacent the reference electrode. In accordance with a third aspect of the present invention, there is provided a process for the preparation of a glass electrode, which comprises: selectively etching a glass substrate; forming, on the etched portion of the glass substrate, a reference electrode of silver/silver chloride and, circuit-connected to the reference electrode, a pad of gold or platinum; subjecting a substrate face of a silicon substrate having a plane to anisotropic etching to form in the substrate face a hole for holding a fluid electrolyte and a groove for injection of electrolyte; removing a silicon oxide film left on the silicon substrate after etching; forming a glass sensing film on the face of the silicon substrate opposite the substrate face to cover and seal the hole, and bonding together the etched surface of the glass substrate and the substrate face of the silicon substrate such that the hole is located adjacent the reference electrode. The process of the second and third aspects of the present invention may further comprise a step of injecting the electrolyte into the hole from the injecting groove according to need. Accordingly, a small glass electrode having an electrolyte injected in the hole is included within the scope of the present invention. The present invention enables a glass electrode having a small size to be provided. For a better understanding of the invention, and to show how the same may be carried into effect, reference will now be made, by way of example only, to the accompanying drawings, in which: Fig. 1 is a sectional view illustrating a conventional glass electrode; Fig. 2(A) is a plan view showing a glass substrate of a glass electrode according to one embodiment of the present invention, Fig. 2(B) is a plan view showing an Si substrate of the glass electrode of this embodiment, and Fig. 2(C) is a plan view showing the glass substrate and Si substrate shown in Figs. 2(A) and 2(B) bonded together to form a glass electrode; Fig. 3(A) is a sectional view taken along line X-X' of Fig. 2(C), and Fig. 3(B) is a sectional view showing a modification of the glass electrode according to the present invention; Figs. 4(A)-(F) are diagrams illustrating steps in the production of a glass electrode according to one embodiment of the present invention; Fig. 5(A) is a plan view showing a glass substrate of a glass electrode according to another embodiment of the present invention, Fig. 5(B) is a plan view showing an Si substrate of the glass electrode of this embodiment, and Fig. 5(C) is a plan view showing the glass substrate and Si substrate shown in Figs. 5(A) and 5(B) bonded together to form a glass electrode; Fig. 6 is a sectional view taken along line X-X' of Fig. 5(C) ; Figs. 7(A)-(F) are diagrams illustrating steps in the production of a glass electrode according to another embodiment of the present invention; Fig. 8(A) is a plan view showing a glass substrate of a glass electrode according to still another embodiment of the present invention, Fig. 8(B) is a plan view showing an Si substrate of the glass electrode of this embodiment, and Fig. 8(C) is a plan view showing the glass substrate and Si substrate shown in Figs. 8(A) and 8(B) bonded together to form a glass electrode; Fig. 9 is a sectional view taken along line X-X' of Fig. 8(C); Figs. 10(A)-(F) are diagrams illustrating steps in the production of a glass electrode according to still another embodiment of the present invention; Fig. 11 is a graph illustrating a response curve of a glass electrode in accordance with the present invention; and Fig. 12 is a graph illustrating the relationship between the change of the H+ concentration and the change of the electrode potential in a glass electrode in accordance with the present invention. The present inventors have already succeeded in providing a practically utilizable small Clark oxygen electrode by applying the micro-machining technique to an Si substrate (US-A-4975175). This small oxygen electrode is often used in relation to medical treatment. In this case, the oxygen concentration is measured relative to the H+ concentration, rather than the oxygen concentration alone. Accordingly, the practical utilization of the micro-machining technique to produce a small glass electrode was tried. The following plan describes this utilization by the present inventors: (1) The size of the glass electrode now used as the H+ concentration sensor and found to operate well, is reduced. (2) At least one holding hole formed by anisotropic etching of an Si substrate is used as a vessel for storing an electrolyte. (3) A glass film formed by heat oxidation or sputtering is used as a sensing film (sensing element) responding to the H+ concentration. (4) A reference electrode is formed on a glass substrate, and the glass substrate and Si substrate are bonded and integrated by the anodic bonding method. (5) A reference electrode composed of Ag/AgCl, a lead-in line and a pad are embedded in the glass substrate. The glass substrate to be bonded to the Si substrate is required to adhere tightly to the Si substrate not only in the course of cooling from the anode bonding treatment temperature, i.e. about 250°C, to normal temperature but also in the atmosphere in which it is to be used. For this purpose, it is required that the glass substrate should (1) have a thermal expansion coefficient approximate to that of Si, (2) be composed of a glass having a low softening point, and (3) have a high resistance to thermal stress. In view of the foregoing, Pyrex glass or lead glass is preferably used. This glass alone can be used as the substrate, or this glass can be used in a state bonded to other glass substrates or Si substrates. Under this background, a glass electrode is formed by using the micro-machining technique according to the present invention. In one embodiment of the present invention, a thin glass film acting as the sensing film is formed by utilizing at least a part of an SiO2 film obtained by wet oxidation of an Si wafer. However, when a sensing film having an increased strength is desired, the sensing film is formed by bonding a glass film to be Si substrate. The thickness of the SiO2 film formed by wet oxidation of the silicon wafer is about 1 µm at most, and it is impossible to increase the film thickness. Accordingly, when a film with an increased strength is required, a glass substrate is first etched to form a glass film having a desired thickness, the silicon oxide film left on the surface of the silicon substrate is removed, and then, the glass film is bonded to the bottom portion of the holding hole. In this embodiment of the present invention, the strength of the glass film acting as the sensing film is increased. Therefore, the yield is improved and the glass electrode can be used without breaking. In the glass electrodes of the present invention, the sensitivity to H+ concentration is in practice sufficiently high. However, when a glass electrode having a further enhanced sensitivity is desired, a glass electrode having a structure described below can be adopted. The voltage generated at the glass electrode is generally represented by the following Nernst equation: E = constant - 0.059pH However, this equation is a theoretical formula, and it is not easy to construct the glass electrode so that the potential in accordance with this equation is obtained. When a sensing film is formed by using Pyrex glass having a thickness of about 50 µm, the gradient coefficient -0.059 (-59 mV) of the Nernst equation is about -0.03 (-30 mV). Therefore, in accordance with certain embodiments of the present invention, the glass material is improved. Lithium (Li) glass, sodium-calcium (Na-Ca) glass and the like are known as glass for a glass electrode. However, in view of their heat resistance and strength, these materials cannot be used as the sensing film for a small glass electrode. The reasons are as follows. (1) A heat treatment at about 800°C is necessary for bonding to the Si substrate, and the heat resistance of these glass materials is insufficient. (2) A considerable strain is left after heat bonding, but the glass materials cannot resist this strain. According to one embodiment of the present invention, a double-layer film obtained by forming a film of a glass having excellent characteristics, such as a lithium glass or a sodium-calcium glass, by sputtering or vacuum deposition on a film of a glass insufficient in characteristics required for the sensing film, such as a Pyrex glass, is used as the sensing film, whereby a glass electrode satisfying substantially the requirement of the Nernst equation can be obtained. In the present invention, it is sufficient if at least one holding hole is formed. However, if a plurality of holding holes are formed and glass films are bonded thereto, the risk of breaking the glass film is effectively reduced. In the process of the present invention, bonding of the glass substrate and the silicon substrate is accomplished, for example, by a method of heating and bonding both substrates, a method using an adhesive or an anodic bonding method. From a practical viewpoint, the anode bonding method is preferably adopted. The present invention will now be described in detail with reference to the following examples that by no means limit the scope of the invention. Example 1Fig. 2(A) is a plan view showing a glass substrate 10 of a glass electrode according to one embodiment of the present invention, Fig. 2(B) is a plan view showing an Si substrate 20 of the glass electrode according to this embodiment, and Fig. 2(C) is a plan view showing the complete glass electrode of this embodiment of the present invention, formed by reversing the glass substrate onto the Si substrate 20 and bonding the respective substrates together. A reference electrode 12 composed of Ag/AgCl, a lead-in line 14 composed of Au and a pad 16 composed of Au are embedded in the glass substrate 10. The substrate face of the Si substrate 20 is the (100) plane. The Si substrate 20 is subjected to anisotropic etching, whereby a groove 22 for injecting an electrolyte, an electrolyte-holding hole 24 and a glass film 26 acting as the sensing film on at least a part of the hole 24 are formed. Incidentally, the groove only can also be made by a separate anisotropic etching operation. In Fig. 2(C), the broken line indicates the interior of the glass electrode, the pad 16 and glass film 26 being visible on the side of the Si substrate 20. Fig. 3(A) is a view showing a section taken along the line X-X' in Fig. 2(C). As is seen from Fig. 3(A), the glass sensing film 26 is formed in the bottom portion of the etched Si substrate 20, i.e. the surface of the Si substrate 20 which is opposite the surface which is bonded to the glass substrate 10. Fig. 3(B) is a sectional view showing a modification of the electrode of Example 1, in which the Si substrate is also etched from the bottom surface, so that the sensing film 26 is formed slightly on the inner side of the Si substrate. Fig. 4 illustrates the steps of one method for preparing a glass electrode in accordance with the present invention. One embodiment of the preparation process will now be described with reference to Fig. 2 and Fig. 4. Formation of Glass Substrate:A negative photoresist is spin-coated on the surface of a Pyrex glass substrate (Iwaki 7740) having a diameter of 5.08 cm (2 inches) and a thickness of 500 µm and is heated and dried at 150°C for 30 minutes. Regions for the formation of a plurality of reference electrodes 12, lead-in lines 14 and pads 16 are windowed and exposed by photolithography, and the same resist is similarly coated and dried on the back surface. Then, the glass substrate is immersed in a mixed solution comprising 50% hydrofluoric acid (HF), concentrated nitric acid (HNO3) and ammonium fluoride [(NH4)F] at a ratio of 1/1/8 for 80 minutes to etch the glass substrate in a depth of 3 µm. Then, the resist is peeled by using a mixed solution comprising sulphuric acid (H2SO4) and hydrogen peroxide (H2O2) at a ratio of 2/1 [see Fig. 4(A)]. Then, the glass substrate 10 is sufficiently washed with a mixed solution of H2O2 and ammonia (NH4OH) and pure water, and is then dried. Then, an Au film is vacuum-deposited on the glass substrate 10. Since Au adheres very poorly to glass, a very thin chromium (Cr) film is vacuum-deposited on the glass substrate in advance to improve adhesiveness. The thickness of the Cr film is 40 nm (400 Å) and the thickness of the Au film is 400 nm (4000 Å). Then, a positive resist film (DFRP-5000 supplied by Tokyo Oka) is spin-coated on the regions for forming reference electrodes 12, lead-in lines 14 and pads 16 by photolithography. Then, the Au film and Cr film are selectively etched to form a reference electrode pattern comprising reference electrodes 12, lead-in lines 14 and pads 16. The Au-etching solution is formed by dissolving 4 g of KI and 1 g of I2 in 40 ml of water, and the Cr-etching solution is formed by dissolving 0.5 g of NaOH and 1 g of K3Fe(CN)6 in 4 ml of water. Then, silver (Ag) is vacuum-deposited on the portion for forming the reference electrode 12 and, in the same manner as described above, coating of a positive resist, heat-drying, light exposure and development are carried out to coat the resist only on the reference electrode-forming portion. Then, Ag etching is conducted and the resist is dissolved and removed, whereby a silver film is formed on the reference electrode-forming portion. The Ag-etching solution comprises 29% NH4OH, 31% H2O2 and pure water at a ratio of 1/1/20. Then, the entire substrate is sufficiently washed with pure water and immersed in a 0.1 M solution of FeCl3 for 10 minutes to form a thin AgCl layer on the surface of the Ag. Then, the entire substrate is sufficiently washed with pure water to complete reference electrodes 12, lead-in lines 14 and pads 16 [Fig. 4(B)]. Formation of Si Substrate:An Si substrate 20 having a (100) plane as the substrate face and having a thickness of 350 µm and a diameter of 5.08 cm (2 inches) is prepared, sufficiently washed with a mixed solution of H2O2 and NH4OH and pure water, and dried. The Si substrate 20 is subjected to wet oxidation at 1050°C for 200 minutes to form an SiO2 film 28 having a thickness of 1 µm on the entire surface thereof. A negative resist (0MR-83 supplied by Tokyo Oka) having a viscosity of 60 cP is coated on the surface of the Si substrate, and light exposure, development and rinsing are carried out to form a resist pattern on the substrate. Then, the Si substrate 20 is immersed in a mixed solution comprising 50% HF and 40% NH4F at a ratio of 1/6 and the exposed portion of SiO2 is etched and removed to form a holding hole [see Fig. 4(C)] in the SiO2. Then, the resist film is peeled in a mixed solution comprising sulphuric acid and hydrogen peroxide at a ratio of 2/1. Then, the Si substrate 20 is immersed in 35% KOH at 80°C and anisotropic etching of silicon is carried out. This forms an electrolyte-holding hole 24 in the reference electrode portion at the position of the holding hole. A glass film 26 acting as the sensing film is formed in the bottom portion of the holding hole 24 by utilizing an SiO2 film 28 having a thickness of 1 µm, formed by wet oxidation. If the SiO2 used as the mask is left on the surface of the Si substrate 20, a higher temperature is necessary for the anodic bonding. Therefore, SiO2 other than the glass film 26 is completely removed by photolithography using a mixed solution comprising 50% HF and 40% NH4F at a ratio of 1/6. Thus, a vessel portion for storing an electrolyte is completed [see Fig. 4(D)]. Bonding of Glass Substrate and Si Substrate:The thus-prepared glass substrate 10 and Si substrate 20 are immersed in pure water, sufficiently washed under ultrasonic vibrations and dried. Both substrates are bonded and a voltage of 1200 V is applied at a temperature of 250°C between the substrates, so that the Si substrate 20 is located on the positive side and the glass substrate 10 is located on the negative side, whereby anodic bonding of the glass substrate and the silicon substrate is effected [see Fig. 4(E)]. The plurality of glass electrode elements formed on the substrate are cut out into chips by using a dicing saw to obtain a plurality of small glass electrodes. When a small glass electrode obtained in this way is used, an electrolyte is introduced into the interior of the electrode according to the following method. A beaker is charged with 0.1 M hydrochloric acid aqueous solution or an aqueous potassium chloride buffer solution containing a phosphoric acid (electrolyte). The glass electrode is entirely immersed in the electrolyte and the entire system including the beaker is placed in a sealed vessel. Then, deaeration of the sealed vessel is carried out by means of a vacuum pump. After bubbles have ceased to come out of the hole 22 for injecting the electrolyte 30, air is introduced into the vessel. The hole 22 can be filled with an epoxy resin. By the above operation, the electrolyte 30 is introduced into the inner space of the electrode, whereby a small glass electrode is obtained [see Fig. 4(F)]. According to this embodiment, a fine glass electrode can be prepared by using the micro-machining technique while maintaining a wafer-like shape. Accordingly, reduction of the cost is possible. Furthermore, since the glass electrode can be stored in a dry state, storage over a long period is possible. Example 2Another embodiment of the process for preparing a glass electrode in accordance with the present invention will now be described. Fig. 5(A) is a plan view showing a glass substrate of the glass electrode according to this embodiment of the present invention, Fig. 5(B) is a plane view showing an Si substrate of the glass electrode according to this embodiment, and Fig. 5(C) is a plane view showing the glass electrode formed by bonding together the glass substrate and Si substrate shown in Figs. 5(A) and 5(B). Fig. 6 is a diagram illustrating the section taken along line X-X' in Fig. 5(C). Fig. 7 is a diagram illustrating steps of forming the glass electrode according to this embodiment of the present invention. In Figs. 5 to 7, reference numerals represent the same members as in Figs. 1 to 4 unless otherwise indicated. The manner in which the glass substrate is formed is the same as that described in Example 1. Accordingly, the description of this is omitted. Furthermore, the Si substrate is prepared substantially in the same manner as described in Example 1, except that a part of the SiO2 film is not utilized as the glass film acting as the sensing film, the SiO2 film being entirely removed. Bonding of Glass Film to Si Substrate:A Pyrex glass film (Iwaki 7740) is etched in a mixed solution comprising 50% HF and concentrated HNO3 at a ratio of 2/1 to obtain a film having a thickness of about 50 µm, and the film is sufficiently washed to obtain a glass film 26A acting as the sensing film. The glass film 26A is placed on the surface of the Si substrate 20 (formed by perforating the Si substrate by anisotropic etching) and heated at 800°C to effect bonding [see Fig. 7(D)]. Bonding of the thus-prepared glass substrate and Si substrate [Fig. 7(E)] and injection of the electrolyte [Fig. 7(F)] are carried out in the same manner as described in Example 1. According to this embodiment of the present invention, the strength of the glass film of the formed glass electrode is increased and hence the yield is increased. The glass electrode is advantageous over the conventional glass electrode in that it is less prone to breaking during use. Example 3A further embodiment of the process for preparing a glass electrode in accordance with the present invention will now be described. Fig. 8(A) is a plane view showing a glass substrate of the glass electrode according to this embodiment of the present invention, Fig. 8(B) is a plane view showing an Si substrate of the glass electrode according to this embodiment, and Fig. 8(C) is a plane view showing the glass electrode formed by bonding together the glass substrate and Si substrate shown in Figs. 8(A) and 8(B). Fig. 9 is a diagram illustrating the section taken along the line X-X' in Fig. 8(C). Fig. 10 is a diagram illustrating steps of forming the glass electrode according to this embodiment of the present invention. In Figs. 8 to 10, reference numerals represent the same members as in Figs. 1 to 4, unless otherwise indicated. The manner in which the glass substrate is formed is the same as described in Example 1. Accordingly, the description of this is omitted. Furthermore, the Si substrate is prepared substantially in the same manner as described in Example 1, except that a part of the SiO2 film is not utilized as the glass film acting as the sensing film, the SiO2 film being entirely removed. Bonding of Glass Film to Si substrate:A Pyrex glass film (Iwaki 7740) is etched in a mixed solution comprising 50% HF and concentrated HNO3 at a ratio of 2/1 to obtain a film having a thickness of, for example, 20-150 µm, in this case 50 µm, and the film is sufficiently washed to obtain a first glass film 29A constituting a film acting as the sensing film. The first glass film 29A is placed on the back surface of an Si substrate 20 having a perforated or piercing holding hole 24, formed by anisotropic etching of an Si substrate, and heated at 750°C to effect bonding of the first glass film 29A to the Si substrate 20. Then, the Si substrate having the first glass film 29A formed thereon is set in a sputtering device and a sodium-calcium Na-Ca glass is sputtered to a thickness of 500 nm to form a second glass film 29B on the first glass film 29A, whereby a glass film 26B acting as the sensing film is obtained [see Fig. 10(D)]. Bonding of the thus-prepared glass substrate and Si substrate [Fig. 10(E)] and injection of an electrolyte [Fig. 10(F)] are carried out in the same manner as described in Example 1, whereby a small glass electrode is obtained. The characteristics of the small glass electrode obtained in Example 3 are evaluated according to the following method. The evaluation is performed by monitoring changes of the potential of the glass electrode relative to the potential of an external reference electrode of silver/silver chloride by using an electrometer. For examining changes of the potential relative to changes of the pH value, the sensing portion of the electrode is immersed in a 10 mM TRIS (Trimethyl aminomethane) solution, and HCl is added to reduce the pH value. At each pH value, the potential of the glass electrode is examined. The experiment is conducted at 25°C. The response curve obtained when the pH value of the external buffer solution is changed is shown in Fig. 11. As is seen from Fig. 11, a very clear response curve is obtained. When the pH value is changed, the small glass electrode immediately shows a change and the 90% response time is 10 seconds. The change in the electrode potential observed when the pH value is changed is shown in Fig. 12. It can be seen that a linear relation is established between the electrode potential and the pH over a broad pH value range of from 2 to 10. The gradient of the linear relation is a value approximate to -59 mV/pH of the theoretical value of the Nernst equation at 25°C.
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A glass electrode comprising: a glass substrate (10) having a reference electrode (12), a pad (16) for external electrical connection and a lead-in line (14) connecting the reference electrode (12) and the pad (16); a substrate (20) having a hole (24) therein for holding a fluid electrolyte, the substrate (20) being bonded to the glass substrate (10) such that the hole (24) is located adjacent the reference electrode (12); and a glass sensing film (26;26A;26B) covering and sealing the hole (24) on the surface of the substrate (20) opposite the surface thereof bonded to the glass substrate (10), characterised in that the substrate (20) is a semiconductor substrate having a groove for injection of electrolyte in the surface thereof bounded to the glass substrate (10), the hole (24) and the groove (22) being anisotopically etched in the semiconductor substrate (20), and the reference electrode (12), pad (16) and lead-in line (14) being embedded in the glass substrate (10). A glass electrode as claimed in claim 1, wherein the glass film (26B) comprises two layers (29A,29B) of glass. A glass electrode as claimed in claim 1 or claim 2, wherein the semiconductor substrate (20) is a (100) oriented silicon substrate, the surface thereof bonded to the glass substrate (10). A glass electrode as claimed in claim 1, 2 or 3, wherein the reference electrode (12) is of silver or silver/silver chloride. A glass electrode as claimed in any one of claims 1 to 4, wherein the pad (14) and the lead-in line (16) are of gold or platinum. A glass electrode as claimed in any preceding claim, further comprising an electrolyte injected into the electrolyte-holding hole (24) from the groove (22). A glass electrode as claimed in claim 6, wherein the electrolyte is an aqueous electrolyte solution. A glass electrode as claimed in claim 6 or claim 7, wherein the electrolyte is porous or sol-like material containing an aqueous electrolyte solution. A process for the preparation of a glass electrode, comprising: selectively etching a glass substrate (10); forming, on the etched portion of the glass substrate (10), a reference electrode (12) of silver/silver chloride and, circuit-connected to the reference electrode (12), a pad (14) of gold or platinum; subjecting a silicon substrate (20) having a (100) plane as the substrate face to anisotropic etching to form in the substrate face a hole (24) for holding a fluid electrolyte and a groove (22) for injection of electrolyte; forming a glass sensing film (26) on the face of the silicon substrate (20) opposite the substrate face by partially removing a silicon oxide film left on that face such that the hole (24) is covered and sealed with a silicon oxide film and converting the silicon oxide film to a glass film; and bonding together the etched surface of the glass substrate (10) and the substrate face of the silicon substrate (20) such that the hole (24) is located adjacent the reference electrode (12). A process for the preparation of a glass electrode, which comprises: selectively etching a glass substrate (10); forming, on the etched portion of the glass substrate (10), a reference electrode (12) of silver/silver chloride and, circuit-connected to the reference electrode (12), a pad (14) of gold or platinum; subjecting a silicon substrate (20) having a (100) plane as the substrate face to anisotropic etching to form in the substrate face a hole (24) for holding a fluid electrolyte and a groove (22) for injection of electrolyte; removing a silicon oxide film left on the silicon substrate (20) after etching; forming a glass sensing film (26A;26B) on the face of the silicon substrate (20) opposite the substrate face to cover and seal the hole (24), and bonding together the etched surface of the glass substrate (10) and the substrate face of the silicon substrate (20) such that the hole (24) is located adjacent the reference electrode (12). A process as claimed in claim 10, wherein the glass sensing film (26A) is formed by bonding a glass film on the face of the silicon substrate (20) opposite the substrate face. A process as claimed in claim 10, wherein the glass sensing film (26B) is formed by bonding a lower glass layer (29A) on the face of the silicon substrate (20) opposite the substrate face and then forming, on the lower glass layer (29A), an upper glass layer (29B) made of sodium-calcium (Na-Ca) glass or lithium (Li) glass by sputtering or vacuum deposition. A process as claimed in any one of claims 9 to 12, wherein the glass substrate (10) is bonded to the silicon substrate (20) by anodic bonding. A process as claimed in any one of claims 9 to 13, further comprising injecting an electrolyte into the hole (24) via the groove (22).
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FUJITSU LTD; FUJITSU LIMITED
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KOJIMA NAOMI; SUGAMA AKIO; SUZUKI HIROAKI; KOJIMA, NAOMI; SUGAMA, AKIO; SUZUKI, HIROAKI; Kojima, Naomi, c/o FUJITSU LIMITED; Sugama, Akio, c/o FUJITSU LIMITED; Suzuki, Hiroaki, c/o FUJITSU LIMITED
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EP-0489602-B1
| 489,602 |
EP
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B1
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EN
| 19,960,626 | 1,992 | 20,100,220 |
new
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G01N33
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C12Q1, B01D61, A61M5, G01N21
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G01N15, G01N33, G01N21
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S01N15:06A3, G01N 21/76B, S01N15:06A3B, G01N 15/06A3B, G01N 33/50D6
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Filtration arrangement
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There is provided a rapid method and apparatus for analysing particulate matter of biological origin using luminescent detection techniques. A fluid is filtered through a membrane and the membrane holding the particulate matter is subjected to luminescence detection.
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This invention relates to methods of preparing and analysing particulate matter of biological origin by luminescence detection. There are many fluids both biological and non-biological which contain substances which may require analysis either using a luminometer or other luminescence detection methods. The fluids may be biological e.g. blood, blood components, milk, colostrum, urine, tissue and tumour disaggregates and exudates, lymph, ascites fluid, cerebrospinal fluid, bile and other secretions and excretions of living organisms or non-biological e.g. fresh water (rivers, lakes, ponds), sea water, industrial effluent, leachates. The substances may be particulates of cellular or non-cellular varieties such as leucocytes, platelets, components from tissue disaggregates, components from tumours, protozoa, small invertebrates, algae including blue greens, gametes and generally any other particulate material of a biological origin which can be separated from its carrier fluid. Much information can be obtained for example from measuring light emission from particles such as leucocytes. This light emission can be enhanced by adding luminogenic materials such as Pholasin (TM) and light can be measured in various ways. Pholasin reacts with oxygen radicals and other oxidants to produce light and leucocytes and other cells produce oxygen radicals when activated. There is a rapidly growing interest in the involvement of oxygen radicals in oncology, cardiology, rheumatology, asthma, ageing, autoimmune diseases and diabetes mellitus for example. In addition, there are the potentially damaging effects of cells activated during renal dialysis or reperfusion of organs during surgery. Other areas include study and assessment of disease activity in inflammatory diseases and for distinguishing between inflammation and infection, these areas being of particular interest to rheumatologists and haemotologists. A quantitative measure of particulate activity, for example the activity of leucocytes, would therefore be a valuable diagnostic tool. In order to obtain quantitative results that can be used in diagnostic and comparative studies, it is essential that: a constant proportion of certain particles (preferably 100%) is removed from a fixed volume of fluid which might contain a mixture of particles; that the particles are not damaged in the process; that whatever treatment the particles experience during any manipulation can be repeated in an identical fashion on particles from another sample of fluid; that all parameters can be controlled so that the results can be compared and related to known factors. There are known methods for separating particles, such as leucocytes, from blood, for example, for subsequent use in analysis. Such methods include multistep procedures including sedimentation with dextran, followed by separation on density gradients. These procedures involve centrifugation, mixing, incubating and sometimes lysis of unwanted red blood cells. They take a number of hours to complete, involve skilled operatives and subject the cells to uncontrollable variables which may inadvertently affect their subsequent response to analytical procedures (Boyum, A. (1968) Isolation of mononuclear cells and granulocytes from human blood. Scand. J. Clin. Lab. Invest. 21, Supple 97 (paper IV), 77-89). In addition the process has to be conducted in a laboratory and thus cannot be used in general medical or veterinary practice, at the bedside, in the field or in an outpatient clinic for example. In response to the need for a rapid, simple and reliable method of isolating leucocytes from whole blood a simpler method was introduced (Ferrante, A. and Thong, Y. H. (1980) Optimal conditions for simultaneous purification of mononuclear and polymorphonuclear leucocytes from human peripheral blood by the HypaqueFicoll method. J Immunol Methods. 35, 109117), which involved layering whole blood on to a mixture of Ficoll and sodium and/or meglumine diatrizoate prepared to specific densities, centrifuging the tube and collecting layers of leucocytes which were washed with centrifugation 2 to 3 more times. This 'improved' method which, enabled leucocytes to be separated, washed and ready for analysis in about 1 to 2 hours still required a skilled operative and the need for a centrifuge. Also, it was not possible to carry out the procedure simultaneously on more than a very few samples (less than 4) and the method is not suitable for most bloods other than human, does not work efficiently on blood from people with, for example: juvenile rheumatoid arthritis, microcytic hypochromic anaemia. The method may fail or give variable results if an individual was receiving aspirin, indomethacin, prednisone or aurothioglucose, or other drugs in the treatment of bronchial congestion, immunodeficiency anaemia and other diseases. An improved method, designed to enable leucocytes to be separated from these 'difficult' bloods was developed (Ferrante, A., James, D. W., Betts, W. H. and Cleland, L. G. (1982) Rapid singlestep method for purification of polymorphonuclear leucocytes from blood of patients with rheumatoid arthritis. Clin exp. Immunol 47 749752) in which the viscosity of the density medium was changed. The results of this improved method are still variable and not useful for quantifiable and comparative results. In all the methods, even the improved ones, the cells are subjected at times to adverse conditions. And while it might be theoretically possible for a trained operative to work in precisely the same manner at each separation, the differences in the blood make it impossible for the blood from different people and at different states of a disease to behave in precisely the same manner. And it is impracticable, even for trained operatives, to standardise the ways they perform the various manipulations involved in the procedure. The method is therefore only suited to the separation of leucocytes from whole normal blood. EP-A-0101398 discloses a method of concentrating and measuring unicellular organisms. The organisms are collected on a filter membrane, lysed and the adenosine triphosphate (ATP) released from the cells is detected using a luminometer by reaction with luminescence reagents. WO88/07584 describes a method and apparatus for detection and quantification of bacteria. Bacterial ATP is removed from the cells by lysis and is detected by means of a light emitting reaction. DE-A-2804117 teaches a method which involves the selective lysis of non-microbial and microbial cells to determine, by luminescence, the presence and amount of non-microbial and microbial cells in a sample. Patent Abstracts of Japan, 14, 1990, no. 232(C-0719) discloses the use of a filter to remove bacteria from water and the analysis of the bacteria by lysis to release ATP which is reacted with luminescence reagents. EP-A-0335244 describes a material and device useful in solid-phase binding assays to determine the presence or amount of an analyte in a test sample. The material and device comprise a reaction site having procedural controls and an analyte binding area capable of being simultaneously contacted by the sample and reagent used in the performance of the assay. Pall Corporation in US 4925572 and US 4880548 disclose filters for depleting the leucocyte concentration of whole blood and for reducing the concentration of leucocytes from platelet concentrates. These filters are used on-line during blood or platelet transfusions, whereby the filtrate which contains the red blood cells or the platelets is allowed to enter the circulation of the patient while the leucocytes are retained by the membrane. According to a first aspect of the present invention there is provided a method of analysing the leucocytes in a leucocyte-containing biological fluid comprising the steps of: (i) passing said biological fluid through a filter material capable of holding said leucocytes by adsorption; (ii) treating the filter material together with the held leucocytes with one or more luminogenic materials; and (iii) subjecting the treated filter material with the held leucocytes to analysis by luminescence detection. Preferably said analysis involves a luminometer and said membrane may be placed in a luminometer cuvette or a microtitre plate prior to insertion into the luminometer. In the method leucocytes from a known volume of whole blood are separated simply and rapidly from the rest of the blood components on to a filter support from which useful, quantitative and comparative measurements of light emission can be made. The measurement of light, or other parameters, can be made a very short time, preferably within two minutes, after collection of blood. The procedure can be performed on blood from people excluded from the methods described above and also from blood from nonhuman species, which also do not separate properly using the above improved methods. The fluid from which the leucocytes are separated can in addition to blood be milk, urine, cerebrospinal fluid and any other fluid in which such particles are found. The method can also be applied to the separation of particles other than leucocytes and any substances that adheres to the membrane and can be analysed. In a preferred method there is included the step of treating the leucocytes held by the membrane with a luminescent material which reacts with certain chemicals in or produced by the particulate matter. It is also possible that more than one luminescent material is used and these luminescent materials may be applied before or after the membrane is inserted in the luminometer. In preferred methods said certain chemicals are radicals, such as superoxide, O2 and the luminescent materials may be chosen from the from the following examples, PHOLASIN, luminol, lucigenin. Other chemicals such as ATP react with firefly luciferin plus firefly luciferase whereas bacterial luciferase is the preferred luminogenic reagent when analysing for NADPH and NADH. Conveniently, the leucocytes held by the membrane are washed prior to being treated with said one or more luminescent materials. Examples of the washing substances are buffered or unbuffered salt solutions, blood serum, plasma. In a further embodiment the fluid passes through other membranes, each of which is adapted to prevent the through flow of other preselected substances. Preferably the fluid passed through the filter by gravity or increased pressure on the fluid or reduced pressure on the downstream side or a combination of these, or by the capillary attraction of an absorptive pad held against the underside of the filter. According to a second aspect of the present invention there is provided a filter device for filtering a leucocyte-containing biological fluid, said device containing a filter material through which, in use, the fluid is passed to leave the leucocytes, the filter material being capable of holding said leucocytes by adsorption and being adapted for use in luminescence detection apparatus to enable the leucocytes held of the filter material to be analysed. Preferably the filter material is removable from the device for use with the luminescence detection apparatus. In a preferred embodiment the filter material has a Critical Wetting Surface Tension greater than 53 dynes/cm. Another arrangement has the filter material held between two separable parts. Conveniently the filter material sits on a perforated support and may have its edges sealed or clamped between upper and lower frames. Clearly the device may have more than one filter material for removing different substances from the fluid. Embodiments of the invention will now be described in more detail. The description makes reference to the accompanying drawings in which: Figure 1(a) is a sectional view of a filter arrangement according to an aspect of the present invention. Figure 1(b) is a sectional view of an alternative part of the filter arrangement shown in figure 1(a). Figure 2(a) to (c) show various types of membrane for use in the filter arrangements, Figures 3(a) to (c) are diagrammatic section views of a syringe. This does not form part of the present invention, Figure 4 is a perspective view from above of a further filter arrangement according to the present invention, and Figure 5 is a perspective view from below of part of a still further filter arrangement according to the present invention. It is often necessary to remove substances, such as cellular and/or non-cellular particulates or other dissolved substances, from a carrier fluid which may be biological or non-biological, so that the substance can be analysed. The fluids are collected in a number of ways which could range from a syringe to a beaker. The fluid is then passed through a filter arrangement 10 as shown. In figure 1(a) the filter arrangement 10 comprises a funnel 11 having a perforated support 12 on which sits a membrane 13 the latter having a greater diameter than that of the perforated plate. A tubular reservoir 14 is attached to the funnel for gravity filtration of the fluid and the size of the membrane 13 is such that it is held in position by the reservoir 14 when the reservoir is screwed into place. In figure 1(b) there is shown an alternative reservoir provided with a Luer fitting 15. As will be readily appreciated the fluid is able to pass through the membrane either under gravity or by applying an increased pressure to the liquid or by reducing the pressure on the downstream side of the membrane. Clearly it is also possible to use a combination of these techniques as is well known. More than one membrane could be employed, the purpose of such a technique being to collect different substances on different membranes. The construction of such a modification is not described because it clearly involves putting the membranes downstream from one another. Similarly each membrane can be made up of a number of layers of suitable materials. The membranes themselves will not be discussed in detail. Membranes or other filters are well known to remove certain substances so as to purify the fluid which passes through the filter unhindered. however, Pall Corporation have invented certain membranes for using in obtaining blood and platelet concentrate which is free of leucocytes which are retained on the filter membrane by adsorption. However, bacteria and other substances are retained by careful regulation of the pore sizes in the membrane, less than 0.2 µm in the case of bacteria. With the figure 1 arrangements in which the membrane 13 is removable, the membrane will ideally be supplied in the form of individual units of the correct shape. This may be circular, rectangular or any other suitable shape. If a number of layers of filter material are used for each membrane then they may be left loose at the edges (figure 2(a)) or they may be sealed in some suitable way for example by melting, by using a filler 18 (figure 2(b)) or by clamping the edges between two frames 19 (figure 2(c)). Once the fluid has been filtered, the substance may be washed so as to remove any part of the fluid which could interfere with subsequent use of the membrane. Such washing fluids may include buffered or unbuffered salt solutions or biological fluids such as blood serum or plasma. One particular type of analysis which is of interest is luminometry although it will be realised that many other methods of analysis are envisaged. Where the membrane is removable from the filter arrangement the membrane is then placed in a luminometer cuvette or microtitre plate or any other suitable receptable from which light can be detected. when inserted into the luminometer the upstream side of the membrane should face the light detector in the luminometer. If using a microtitre plate, the membrane should conform to the shape of the wells in the plate. When measuring light emitted from the substance retained by the membrane, the membrane is treated or immersed in a base liquid which includes one or more luminescent materials such as PHOLASIN (Trade Mark), luminol, lucigenin, firely luciferase plus firely luciferin, and bacterial luciferase for example. The principles of analysis by luminescence are well known. Luminescent materials emit light in response to certain chemicals. One such chemical which stimulates PHOLASIN is superoxide, 02 radical. Obviously the luminescent material chosen depends on the features which you wish to detect and analyse. More than one luminescent material can be present in the base liquid if desired so as to monitor different chemicals. Various measurements can then be taken on the luminometer such as the resting glow of the luminescent material, the glow caused by metabolites of the substance under analysis, the resting glow of other luminescent materials together with any glow caused by metabolites. Also, other substances could be introduced to the membrane whilst in the luminometer so as to activate certain other chemicals which could result in a different glow for measurement. For example, leucocytes are activated by a number of substances such as phorbol myristate acetate, tumor necrosis factor, opsonised serum, opsonised zymosan, a suspension of latex particles. The luminometer can be used to monitor the progress of the reactions. The measurements made can give diagnostic indications of the physiological or pathological state of a patient. The membranes and the substances retained thereon are ready for analysis within minutes of the collection of the fluid. The process can readily be conducted in situ and therefore removes the expensive and time consuming step of sending the fluid to a specialised laboratory. The apparatus could be supplied in kit form comprising say a syringe to obtain the fluid, a filter arrangement to isolate the substance of interest on the membrane and luminescent material to enable the membrane to be treated after insertion into a luminometer, portable luminometers being readily available. Clearly however suitable adaptions will be necessary to enable the kit to be used with all commercially available luminometers. A further filter arrangement is shown in figure 4 and comprises a piece of membrane 13 which is attached (removably or immovably) to a support. The support may be in the form of a rigid strip 20 with rectangular holes cut in it at intervals and below which is attached the membrane. Other hole shapes are of course possible. The support 20 may have an extension in the form of a flange 22 adapted to be held by forceps. The flange can be removed by cutting when the strip has been placed in the luminometer cuvette, thus obviating the need for the strip to be handled in any way. At the end of the filtration, and subsequent washing of the membrane 13, i) if the membrane were removably attached to its support, the membrane would be removed from its support, perhaps by peeling, and placed in the luminometer cuvette; ii) if the membrane were immovably attached to its support, the support would be cut along guide lines 23 in such a way as to free a section of it containing the membrane from the rest of the support and this section would be placed in the luminometer cuvette. A relatively thick absorptive pad 24 is held under the filter assembly so that fluid added to the membrane would pass through the membrane, after leaving the desired components in or on the membrane, and be absorbed by capillary attraction into the absorptive pad 24. The absorptive pad 24 would itself be contained in a structure or enclosure 25 that would allow none of the absorbed fluid to spill from the sides or bottom of the pad other than into this enclosure 25. Alternatively this structure could form an integral part of the absorptive pad, such that the pad 24 is formed with impermeable side and bottom Walls. In another arrangement (not shown) the membrane, or sections of the membrane, may be held between two layers of supporting material in which are formed opposed holes for the passage of the fluid through the membrane and into the absorptive pad. In this case the appropriate piece of membrane would be removed from between the sandwich after filtration and washing and placed in the luminometer cuvette. In another possible arrangement shown in figure 5 the support 20 may be in the form of a strip 20 containing a number of wells 26, perhaps six. Figure 5 is of such a structure and shows one well viewed from underneath, this figure is to no particular scale. Each well has a hole 21, perhaps rectangular, at the bottom, below which the membrane 13 is attached. If the luminometry is to be carried out in a micotitre plate luminometer the filtration device may consist of a microtitre plate strip or block in which the base of each well is furnished with a piece of the membrane as in the other devices described above. After filtration and washing of the samples, the strip or block is placed into a similar but shorter strip or block with the bottoms of the wells entire so that further flow of fluid through the membrane is prevented. This compound structure is then placed in the microtitre plate reader, perhaps after the addition of appropriate reagents to each of the wells. The techniques described can also be used to test milk for various reasons. One reason is to analyse the leucocytes which are present in milk to gain information about certain diseases in the animals, for example mastitis in cows. Milk producers can claim a premium if their product reaches certain standards. Data can therefore be obtained almost instantaneously in situ, without the need for skilled labour. Such techniques will also have obvious benefits in third world countries where alternative facilities for testing may not be available. Also milk can be tested in this way to assess under - or over - pasteurisation by for example analysing the concentration of various enzymes. Bacterial contamination could also be monitored at the same time. Another application for this invention is for the rapid determination of leucocytes in urine as part of a luminescent urinary tract infection screening kit. The activity of any leucocytes present in the urine and adsorbed on to the membrane will be assessed with the luminogenic reagent Pholasin or other suitable reagents. The invention will provide a simple, rapid measure of pyuria and its relation to bacteriuria. It will lead to simplification of the luminescent test for determining bacteria in urine, eliminating the requirement to destroy any ATP from somatic cells which might be present. Elimination of such a step will increase both the speed and reliability of that test. Figure 3(a) shows a syringe 30 having a barrel 31 and an inlet 32 through which liquid is drawn when a plunger 33 is withdrawn. The plunger 33 being pulled back by rod 34 attached thereto. A pin 35 is disposed within the rod 34 so that when the syringe 30 has been filled, the plunger can be pierced. The fluid in the syringe can then flow out under gravity. This is advantageous because it is not always desirable to eject the fluid under pressure by depressing the plunger. Clearly other ways of exposing the fluid at the plunger end to atmospheric pressure, for example the rod 34 may be attached to the plunger 33 by means of a screw thread passing through the plunger as shown in figure 3(b) by means of a bayonet fitting plunger are possible and need not be confined within the rod 34. Figure 3(c) shows another syringe 30 in which the rod 34 is in the form of a cylinder which surrounds the pin 35. In use, when the syringe is held vertically so that the contents can be allowed to flow out at a rate controlled by the pin 35, another fluid is introduced into the cylinder 34. If the second fluid is of lower density than the contents of the syringe it will flow into the barrel and flush out the barrel of the syringe. When this second liquid impinges on the filter it will act as a washing liquid to wash away any substances not intended to be retained by the filter material. A similar adaptation could be made to the other syringe embodiments mentioned.
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A method of analysing the leucocytes in a leucocyte-containing biological fluid comprising the steps of: (i) passing said biological fluid through a filter material capable of holding said leucocytes by adsorption; (ii) treating the filter material together with the held leucocytes with one or more luminogenic materials; and (iii) subjecting the treated filter material with the held leucocytes to analysis by luminescence detection. A method as claimed in claim 1 , wherein the filter material with the held leucocytes is introduced into a luminometer. A method as claimed in claim 1 or claim 2, wherein the filter material with the held leucocytes is placed in a luminometer cuvette or on a microtitre plate prior to insertion into the luminometer. A method as claimed in any one of claims 1 to 3, wherein the leucocytes held by the filter material are washed before being treated with the one or more luminogenic materials. A method as claimed in any one of claims 1 to 4, further comprising the step of drawing the fluid through the filter material by use of an absorptive pad disposed below the membrane. A filter device for filtering a leucocyte-containing biological fluid, said device containing a filter material through which, in use, the fluid is passed to leave the leucocytes on the filter material, the filter material being capable of holding said leucocytes by adsorption and being adapted for use in luminescence detection apparatus to enable the leucocytes held on the filter material to be analysed. A filter device as claimed in claim 6, wherein the filter material is removable from the device prior to use in the luminescence detection apparatus. A filter device as claimed in claim 6 or claim 7, wherein the filter material is attached to a support means. A filter device as claimed in claim 8, wherein the support means comprises a plate having at least one hole below which the filter material extends thereby to constitute one or more filtering stations. A filter device as claimed in claim 9, wherein the filter material is removable from the plate prior to insertion in the luminescence detection apparatus. A filter device as claimed in claim 9 or claim 10, wherein the plate is formed with at least one well, said at least one hole being formed in the base of said at least one well. A filter device as claimed in any one of claims 6 to 11, wherein an absorptive pad is disposed below the filter material to draw the fluid through the filter material. An analysis kit comprising the filter device of any one of claims 6 to 12, portable luminescence detection apparatus and means for introducing a biological fluid containing leucocytes to the filter device.
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KNIGHT SCIENT LTD; KNIGHT SCIENTIFIC LIMITED
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KNIGHT JANICE HOPE; KNIGHT ROBERT HIPWELL; KNIGHT, JANICE HOPE; KNIGHT, ROBERT HIPWELL
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EP-0489605-B1
| 489,605 |
EP
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B1
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EN
| 19,960,925 | 1,992 | 20,100,220 |
new
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D06F13
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D06F17
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D06F17, D06F13, D06F23
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D06F 17/00, D06F 13/00, D06F 23/04
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Washing machine with roller type agitator
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A washing machine comprising a roller type agitator and an auto-balancer. The roller type agitator (10) is provided at the lower portion inside the washing tub (3) and includes at least one roller (14) rotatably mounted thereto in order to generate water flow and provide a bending and stretching action and a squeezing action for said laundry articles and a smooth circulation of washing water. The auto-balancer (20) is provided at the upper portion inside the washing tub (3) and includes a plurality of washing protrusions (21). The roller includes a plurality of washing water ports (14b,14c) at the circumferential outer surface and both side surface thereof, respectively. The present invention can provide a washing machine which can provide a good washing effect and an excellent washability irrespective of the quantity of the laundry articles and the volume of the laundry article.
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The present invention relates to a washing machine according to the preamble of claim 1. Such a machine is disclosed for instance in document GB-A-2 145 435. Generally, known washing machines are classified according to the type of agitator into three types, the rotary vane wheel type as shown in FIG. 1, the pulsator (agitator vane wheel) type as shown in FIG. 2 and the rotary tub vane wheel type as shown in FIG. 3. As shown in FIG. 1, the washing machine of the rotary vane wheel type, in which the laundry articles, particularly clothes, are washed by a frictional effect generated from contacting with vanes 41 of the vane wheel 40, a bending and stretching effect provided by the water flow, can efficiently wash a small quantity of laundry articles as a result of an active water flow, while it can not efficiently wash a large quantity of laundry articles as the generation of the water flow is deficient so that the laundry articles may not be sufficiently circulated. Therefore, this type of washing machine has a disadvantage that it can efficiently wash a part of the laundry articles within the range of contacting with the vanes 41 but can not efficiently wash the other part of the laundry articles behind the range of contact. As shown in FIG. 2, the washing machine of the pulsator type includes a washing rod 44, which washing rod 44 provided at the center of the pulsator 43 and adapted to generate a rotating water flow and an upward and downward circulating water flow in cooperation with the agitating vanes 45 in order to activate the circulation of the laundry articles and improve the washability by providing a mechanical action generated among the agitating vanes 45, the washing rod 44 and the laundry articles. However, it has been known that this type of washing machine had disadvantages that the washability thereof is relatively lower than that of the above-mentioned washing machine of the rotary vane wheel type, there was an inconvenience in putting in and taking out the laundry articles and also in case of washing the large quantity of laundry articles or a large volume of laundry article because of the disturbance by the washing rod 44 provided at the center of the pulsator 43. As shown in FIG. 3, the washing machine of the rotary tub vane wheel type in which the laundry articles are circulated accompanying with the washing water in circulation by the viscous friction generated from the contact with the side wall 51 of the rotary tub vane wheel 50 washes the laundry articles by using the frictional contact with the side wall 54, the difference in the respective speeds of the washing water and the laundry articles during the reversed rotation. However, in case of reversed rotation, there is only an intermittent circulation of the laundry articles with a small difference in the relative speed between the washing water and the laundry articles for a little time until reaching the normal speed in the reversed rotation. Thus, there are disadvantages that the washing effect is not good, furthermore, the circulation of the laundry articles is more deficient in case of the large quantity washing so that the washing effect is deteriorated. As described above, the known washing machines have several drawbacks, such as relatively low washing effect, an unequal washing, a bad washing in case of the large quantity washing and a large volume of laundry article (a blanket, bed clothes and the like) and the fabric damage in case of small quantity washing. In effort to solve the above-mentioned drawbacks, the inventors of the present application have proposed several types of washing machines which could considerably improve the washing effect in comparison with the above-mentioned washing machines. Generally, the washing machine comprises a washing section wherein the laundry articles are directly subject to the washing operation in the washing water, a driving section for driving said washing section and a supporting section for supporting said washing and driving sections. In addition, the washing section, comprising several washing elements, is the most important part because it influences the washing effect much more than any other sections. In accordance, the washing effect will considerably ameliorate by providing a newly proposed washing elements, such as washing tub and agitating member and the like, having improved structures, respectively. In result, the inventors proposed several washing machines having agitating members provided with rollers, respectively, thereby making it possible to improve the washing effect. A machine of that type, described in Korean Utility Model Application No. 89-16983 published June 28, 1991, includes an auxiliary agitator provided at the lower part inside the washing and dehydrating tub (hereinafter, referred to simply as the washing tub), said agitator equipped with rollers at side wall thereof. As shown in Fig. 4 which is an elevational sectional view of this washing machine, the washing machine comprises a driving motor 62 installed at a side out of the bottom of the outer tub 61, a conventional clutch C provided at the center of the outer tub 61 and having a washing shaft 64, including at upper portion an agitator vane wheel 63, and a dehydrating shaft 66 adapted for driving the washing tub 65 to rotate, said driving motor 62 driving the clutch C to carry out the washing and dehydrating operations. There is provided at the lower portion of the washing tub 65 a diametrically enlarged section 67, which section 67 has a larger inner diameter than that of the upper portion of the washing tub 65 and is provided with a rubber ring 68 mounted to the inner surface thereof. The washing shaft 64 of the clutch C is provided with an agitating tub 69 supported by a bearing 70 at an upper portion thereof, said agitating tub 69 having a plurality of rollers 71 rotatably mounted at the side wall of the agitating tub 69 and rotating according to the frictional power provided by the contact with the rubber ring 68. The agitating tub 69 has a sun gear 72 formed at the lowermost portion thereof and engaging with a connecting planet gear 74, which planet gear 74 in turn engages with a driving sun gear 73 fixedly mounted under the bearing 70 to a lower portion of the washing shaft 64 of the clutch C. However, this type of washing machine must have the diametrically enlarged section at the lower portion of the washing tub, for equipping with the agitating tub, and be provided with the driving mechanism, having a relatively complex structure, so that it may have little compatibility with the conventional washing machine. Furthermore, the agitating tub of this washing machine is provided with the rollers at the upper side wall thereof so that the agitating force may be weaker than that of a machine having agitator provided with rollers directly mounted thereto. It is an object of the present invention to provide a washing machine with a roller type agitator which can equally wash the laundry articles and provide an improved washability without any fabric damage irrespective of the fabric quantity. It is another object of the present invention to provide a washing machine with a roller type agitator which can provide a good washing effect in case of washing a large volume of laundry article, such as blanket and bed clothes. It is still another object of the present invention to provide a washing machine with a roller type agitator which can accomplish the compactness of the washing tub in comparison with the washing capacity. In accordance with the present invention, the above-mentioned objects can be accomplished by providing a washing machine according to the characterizing part of claim 1. Other features of the invention are defined in the dependent claims. The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIGS. 1 to 3 are views showing embodiments of an agitator equipped to a known washing machine, in which: FIG. 1 is a schematic perspective view showing a rotary vane wheel type agitator; FIG. 2 is a front view showing a pulsator (agitator vane wheel) type agitator; and FIG. 3 is a partially broken inner perspective view showing a rotary tub vane wheel type agitator; FIG. 4 is an elevational sectional view showing another washing machine proposed by the inventors of this invention; FIGS. 5 to 7 are views each showing an embodiment of a washing machine with a roller type agitator in accordance with the present invention, in which: FIG. 5 is an elevational sectional view showing the whole structure of the washing machine; FIGS. 6A to 6E are sectional views showing embodiments of a rotator base, respectively; and FIGS. 7A and 7B are sectional views showing embodiments of an auto-balancer, respectively; FIGS. 8 to 10 are views showing embodiments of an agitator in accordance with the present invention, respectively, in which: FIGS. 8A and 8B are a plane view of an agitator comprising a disc rotator, agitating vanes and rollers, and an elevational sectional view taken along the line A-A of FIG. 8A, respectively; FIGS. 9A and 9B are a plane view of an agitator provided with a washing rod vertically formed on the center of the disc rotator shown in FIGS. 8, and an elevational sectional view taken along the line B-B of FIG. 9A, respectively; and FIG. 10 is an elevational sectional view of an agitator comprising an agitating tub provided with rollers at the lower portion thereof; FIG. 11 is an elevational sectional view showing another embodiment of a washing machine with a roller type agitator in accordance with the present invention; FIGS. 12A and 12B are an enlarged plane view of the agitator of FIG. 11 and a cross sectional view of the roller of FIG. 12A, respectively; FIGS. 13A and 13B are a schematic view showing another embodiment of an agitator comprising a mountainous rotator having rollers in accordance with the present invention, and a plane view of the agitator of FIG. 13A, respectively; FIGS. 14A and 14B are schematic side views showing embodiments of a roller in accordance with the present invention, respectively; FIG. 15 is an elevational sectional view showing a washing machine provided with another embodiment of a washing tub in accordance with the present invention; and FIG. 16 is a partially broken elevational sectional view of a double tub type of washing machine provided with an agitator in accordance with the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSReferring now to FIG. 5 which is an elevational sectional view showing the whole structure of the washing machine in accordance with this invention, the washing machine with roller type agitator comprising a housing 1, an imperforate outer tub 2 installed inside said housing 1, a washing and dehydrating tub 3 (hereinafter, referred to simply as a washing tub) rotatably mounted inside said outer tub 2 and adapted for washing and dehydrating the laundry articles, a roller type agitator 10 rotatably mounted at the lower center of said washing tub 3, an auto-balancer 20 equipped at the upper portion of said washing tub 3 and a driving mechanism 30 adapted for driving said roller type agitator 10 and said washing tub 3 to rotate. The roller type agitator 10 comprises a rotator 11, provided with a central bearing 12 and a peripheral bearing 13, and at least one roller 14 rotatably mounted by means of rotation shaft to the rotator 11 between said central and peripheral bearings 12 and 13, said roller 14 desirably having a plurality of washing protrusions 14a formed as protruded on the outer surface thereof. However, the provision of the washing protrusions 14a is not indispensable. Like the conventional washing machine, the driving mechanism 30 comprises a clutch 33 mounted under the bottom center of the outer tub 2 and having a washing shaft 31 and a dehydrating shaft 32, a reversible driving motor 34 fixed to said outer tub 2 at a side of said clutch 33 and having a motor pulley 35 connected to a clutch pulley 36 of said clutch 33 by means of a belt 37. The washing shaft 31 supports the central bearing 12 inserted thereonto and secured by means of a set screw, and the dehydrating shaft 32 supports a radial reinforcement 3a engaging therewith and secured to the lower surface of the washing tub 3 so that according to the power transmitting control by the clutch 33 for the rotational power from the driving motor 34 the washing and dehydrating shafts 31 and 32 may selectively rotate and the agitator 10 and the washing tub 3 may in turn rotate selectively. In the drawing, the reference numeral 4 denotes an outer tub cover; 3a denotes an wedge type annular protrusion formed as protruded at the inner surface of the washing tub 3; 5 denotes a top cover; 6 denotes a main door; 7 denotes a drain pipe; and 8 denotes a drain valve. In operation, the above-mentioned washing machine has respective operations different from each other in respective cases of large quantity washing and small quantity washing, therefore, the operations thereof will be separately described hereinafter. In a washing operation for the large quantity of laundry articles, the laundry articles C accompanying with the washing water putted in the washing tub 3 will directly contact with the rollers 14 as the agitator 10 is biased downwardly by the weight of said laundry articles C as shown in FIG. 5. In addition, the circulation speed of the laundry articles C is so different that a part thereof directly contacting with said rollers 14 of the rotating agitator 10 may have a relatively high speed circulation but another part thereof contacting with the auto-balancer 20 may have relatively lower speed circulation as result of the frictional contact with a plurality of washing protrusions 21 of the auto-balancer 20 and the inertia force induced by the weight of the laundry articles C. Therefore, the laundry articles C intend to stop circulating while the washing tub 3 intends to rotate so that because of the contact frictional power the rollers 14 of the agitator 10 may roll in the opposite direction to the rotational direction of the agitator 10. At this time, the laundry articles C are subject to the intensive bending and stretching action induced by the contact frictional power, generated from the contact of the laundry articles C with the rollers 14, and the circulation speed difference between the upper and lower parts of said laundry articles C. In result, simultaneously with displacing its washing position in the direction of a->b->c->d, a surface point P of the laundry articles C rolls in the vicinity of the rollers 14 in order to circulate inside the washing tub 3. Also, the circulating speed of the laundry articles C is relatively rapid at the outside than that of the inside, thereby causing the rolling action of the laundry articles C to be more intensive at the outside than the inside. Accordingly, the circulation of the laundry articles C, which first actively circulated only in the vicinity of the rollers 14 of the agitator 10, gradually spreads to the whole laundry articles C so that the whole laundry articles C can well circulate. In addition, the laundry articles C which was entangled in the reversed rotation of the agitator 10 will be unravelled in the forward rotation of the agitator 10, simultaneously with displacement thereof such as a part of the articles C around the inside moves to the outside, while another part thereof around the outside moves to the inside so that the whole laundry articles C can be equally washed and also a good washing effect can be obtained. On the other hand, in case of small quantity washing, the roller type agitator 10 of this washing machine, which agitator can provide a relatively intensive water flow in comparison with the hitherto used washing machine provided with the rotary vane wheel type, pulsator (agitator vane wheel) type or the rotary tub vane wheel type agitator, pulls downwardly, in the forward rotation of said agitator 10, the laundry articles C by means of the intensive water flow generated from the rolling action of the rollers 14 in order to cause almost of all laundry articles C to circulate around the lower portion of the washing tub 3 near the agitator 10. However, as the agitator 10 changes its rotational direction from the forward direction to the reversed direction, the laundry articles C will rise intermittently because there is no pulling force acting thereon as a result of the counterbalancing the water flows in accordance with the interfering action between the forward and reversed directional water flows, and thereafter, the laundry articles C will be again pulled downwardly by the intensive reversed directional water flow as the agitator 10 rotates in reversed direction at high speed. Thus, there may be an upward and downward circulation of the laundry articles C, and furthermore, an inward and outward circulation, that is to say rightward and leftward circulation of the laundry articles C, thereby causing the whole laundry articles C to be equally washed and a good washing effect to be obtained. As described above, it is well noted that the washing machine with a roller type agitator in accordance with this invention can provide, irrespective of the quantity of the laundry articles, an equal and excellent washing effect for the whole laundry articles without any fabric damage as a result of the rolling action by the rollers 14 of the agitator 10. Hereinafter, the various embodiments of a washing machine with roller type agitator in accordance with the present invention will be more detailedly described. Referring first to FIGS. 6A to 6E which are sectional views showing several embodiments of a rotator base 11 in accordance with the present invention, respectively, the first embodiment of a rotator base shown in FIG. 6A comprises a horizontal surface 11a, the second embodiment of a rotator base shown in FIG. 6B comprises a U-shaped base comprising a horizontal bottom surface 11a and upwardly and outwardly inclined side surface walla 11b, the third embodiment of a rotator base shown in FIG. 6C comprises a reversed U-shaped base comprising a horizontal bottom surface 11a and downwardly and outwardly inclined side surface walls 11c, the fourth embodiment of a rotator base shown in FIG. 6D comprises a V-shaped base comprising upwardly and outwardly inclined side surfaces 11d, and the fifth embodiment of a rotator base shown in FIG. 6E comprises a reversed V-shaped base comprising downwardly and outwardly inclined side surfaces 11e. However, the rotator base 11 may be constructed as formed another type beside the above-mentioned types within the scope of this invention. The rollers 14 may be installed to the horizontal surfaces 11a or the inclined side walls 11b,11c,11d and 11e of the rotator base 11 in order to comprise an agitator 10, and the washing effect of the agitator 10 is different in accordance with the type of the agitator comprising a rotator base and rollers, while the general washing effect similar to that of the washing machine shown in FIG. 5 can be obtained irrespective of the difference of the type of the agitator. FIGS. 7A and 7B are sectional views showing another embodiments of an auto-balancer in accordance with the invention, respectively. The auto-balancer 20 may have another type of a washing protrusion 22 mounted at the inner surface thereof as shown in FIG. 7A or still another type of washing protrusion 23 mounted at the lower surface thereof as shown in FIG. 7B, even though these types of washing protrusions each may provide a relatively lower washing effect than that of the washing protrusions 21 shown in FIG. 5. Turning next to FIGS. 8A and 8B which are a plane view of another embodiment of an agitator comprising a disc rotator, agitating vanes and rollers in accordance with the present invention, and an elevational sectional view taken along the line A-A of FIG. 8A, respectively, this type of agitator 10 comprises a circular rotator base 11 and a plurality of rollers and washing vanes 14 and 15, which rollers and washing vanes 14 and 15 are radially and alternately arranged and spaced apart from one another on said rotator base 11, respectively, each said washing vane 15 formed as lowered than the base surface of said rotator base 11. FIGS. 9A and 9B are a plane view of still another embodiment of an agitator 10 in accordance with the present invention, and an elevational sectional view taken along the line B-B of FIG. 9A, respectively. This type of agitator 10 comprises a circular rotator base 11 and a washing rod 16 vertically formed on the center of said rotator base 11, a plurality of rollers and washing vanes 14 and 17 radially and alternately arranged and spaced apart from one another on said rotator base 11, respectively, which washing vanes 17 each extrudes radially and outwardly from the lower portion of said washing rod 16, said washing rod 16 having at the side surface thereof washing protrusions 17′ formed as extruding outwardly. Still another embodiment of an agitator 10 in accordance with this invention is shown in FIGS. 10 which is an elevational sectional view. This type of agitator 10 comprises an agitating tub base 11 provided with rollers 14 at the lower portion thereof and a side wall 18 upwardly and outwardly extending and having an optimum height. The agitators 10 shown in FIGS. 8 to 10 can be adapted to the conventional types of washing machines without difficulty in order to improve the washability. Turning next to FIGS. 11 and 12 which each shows a washing machine provided with still another embodiment of an agitator, this type of agitator 10 comprises a rotator base and a plurality of rollers and washing vanes 14 and 15, which rollers and washing vanes 14 and 15 are radially and alternately arranged and spaced apart from one another on said rotator base, respectively, each said washing vane 15 formed as lowered than the height of each said roller 14, therefore, this type of agitator 10 is generally similar to that of FIGS. 8A and 8B. As shown in FIGS. 8A and 8B, it is desirable to form each washing vane 15 as lowered than the height of the upper surface of the rotator base 11. However, the washing vane 15 may be formed as lowered than the height of each roller 14 as described above in conjunction with FIGS. 11 and 12. In addition, each roller 14 is provided at the circumferential outer surface and both side surfaces thereof with a plurality of washing water inlet and outlet ports 14b and 14c, respectively, so as to generate the turbulent water flow simultaneous with reducing the fluid resistance thereof. It is desirable to form the water outlet ports 14c, provided at both side surfaces of each roller 14, as enlarged than the water inlet ports 14b formed at the circumferential outer surface thereof. Also, the auto-balancer 20 is, as shown in FIG. 5, provided with a plurality of washing protrusions 21 at the lower inner portion thereof. The washing machine shown in FIG. 11 has respective washing operations in accordance with the quantity of the laundry articles C, large quantity and small quantity washing operations. In other words, the laundry articles C positioned between the auto-balancer 20 and the agitator 10, as shown in FIGS. 11 and 17, will be subject to the rolling action provided by the rotation of the agitator 10 simultaneously with being circulated accompanying with the water flow, and also subject to the bending and stretching action and the scrubbing action each provided by the washing protrusions 21 of the auto-balancer 20 and the rollers of the agitator 10, thereby causing the laundry articles to be washed efficiently. At this time, the washing vanes 15 of the agitator 10 generate a vortex flow which can also improve the washing effect. The rollers 14 are, additionally, mainly subject to the rolling and frictional action induced by the contact with the laundry articles C, while the water flow is mainly generated by the washing vanes 15 each having relatively small size so that the necessary torque for driving the agitator 10 may be small, resulting in reducing the output of the driving motor 33, thereby making it possible to use a relatively small capacity of driving motor. Also, the water level in case of the small quantity washing is relatively lower so that the washing effect may be influenced by the auto-balancer 20 very little but the heart style water flow generated by the washing vanes 15 of the agitator 10. However, the size of each roller 14 is considerably larger than that of the washing vanes 15 so that the roller 14 may decisively influence on the circulation of the laundry articles C. Simultaneously with passing through the washing water inlet ports 14b provided on the circumferential outer surface of the rollers 14 the water flow generated by the washing vanes 15 becomes more intensive turbulent flow so that the washing effect may be improved. Because of providing the washing water inlet and outlet ports on the outer and both side surfaces of each roller 14, relatively larger outlet ports 14c on both side surfaces and relatively smaller inlet ports 14b on the circumferential outer surface, the washing water can efficiently enter the water inlet ports 14b of the circumferential outer surface in case of the rotation of the agitator 10, while the washing water inside each roller 14 can easily go out of said roller 14 through the water outlet ports 14c as a result of the centrifugal force generated by the rotation of the agitator 10. In accordance, the washing machine shown in FIGS. 11 and 12 can reduce the fluid resistance resulting from providing the washing water inlet and outlet ports 14b and 14c on the outer and both side surfaces of the rollers 14, which fluid resistance may be generated by the rollers. Thus, the necessary torque for rotating the agitator 10 during the washing operation can be reduced so that it may be possible to use a relatively small capacity of driving motor. Also, the washability of the washing machine of FIGS. 11 and 12 can be considerably improved by the efficient water flow despite using the relatively small capacity of driving motor, which driving motor will output a relatively small power so as to provide a relatively small input energy for the agitator. Additionally, the above-mentioned washing machine, in comparison with the relatively lower washability because of the little difference in the relative speed between the washing water and the laundry articles generated from the rotational flow provided by the known washing machines, provides an advantage of improving the washability as a result of providing the intensive turbulent flow. FIGS. 13A and 13B are a schematic view showing a washing machine provided with still another embodiment of an agitator in accordance with the present invention and a plane view of the agitator of FIG.13A, respectively. The agitator 10 comprises a mountainous rotator 11 provided with rollers 14, which rollers 14 are radially arranged and spaced apart from one another and also inclined to the inner surface of the washing tub 3 at a predetermined angle . The washing machine of FIGS. 13 can provide, in washing operation, an intensive upward and downward water flow of the washing water resulting from the inclined arrangement of the rollers 14 to the inner surface of the washing tub 3. Turning next to FIGS. 14A and 14B which are schematic side views showing embodiments of a roller in accordance with the present invention, respectively, the rollers 14 may be constructed as conical shaped shown in FIG. 14A or ball shaped shown in FIG. 14B beside the cylindrical shaped roller. However, the rollers 14 may be constructed as another shaped roller beside the shapes shown in FIGS. 14. FIG. 15 is an elevational sectional view showing a washing machine provided with another embodiment of a washing tub in accordance with the present invention. The washing tub 3 includes an auto-balancer 20, provided with a plurality of washing protrusions 22 formed as spaced apart from one another at the under surface thereof, and a plurality of reversed triangular shaped washing protrusions 24, each said reversed triangular shaped washing protrusion 24 formed as gradually and downwardly become narrow and extending from each said washing protrusion 22 of the auto-balancer 20 so as to be integrally formed therewith. The washing tub 3 of FIG. 15 can considerably improve the washability as a result of the washing protrusions 24. Turning next to FIG. 16 which is a partially broken elevational sectional view of a double tub type of washing machine provided with an agitator in accordance with the present invention, the washing machine comprises a washing tub 3′ arranged at a side inside the housing 1′ and a dehydrating tub 3″ arranged at the other side, which washing tub 3′ is provided with a roller type agitator 10 on the bottom and a driving mechanism 30 equipped under the bottom thereof. This type of washing machine is an embodiment in which the roller type agitator 10 according to this invention is applied to the conventional double tub type of washing machine, which type washing machine washes the laundry articles in the washing tub 3′ and then dehydrates the washed articles in the dehydrating tub 3″. As above-mentioned, the washing machine in accordance with the present invention can provide a good washing effect and an excellent washability irrespective of the quantity of the laundry. In other words, the laundry articles C in case of large quantity washing are efficiently washed by the bending and stretching action accompanying with the smooth circulation generated by the interaction among the roller type agitator 10, the washing protrusions 21, 22 and 23 of the auto-balancer 20 and the washing protrusions 24 of the washing tub 3, thereby causing the washing effect to be improved and making it possible to equally wash the laundry articles. In addition, there may happen little fabric damage because of the rolling action of the rollers 14 during the contact of the laundry articles C with the rollers 14 of the agitator 10, and furthermore, it is possible to obtain a good washing effect, which is similar to that in case of the large quantity washing, in case of washing the large volume of laundry article such as a blanket and a bed clothes. Also, the laundry articles C in case of small quantity washing can be washed accompanying with a smooth circulation, which circulation moving inwardly, outwardly, upwardly and downwardly, by means of the rollers 14 of the agitator 10 during the forward and reversed directional rotation of the roller type agitator 10, thereby causing the washing effect to be improved and making it possible to equally wash the laundry articles.
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A washing machine comprising a housing (1), a washing tub (3) provided with a plurality of washing protrusions (21) at an upper portion thereof, a driving mechanism (30) for providing power for washing, an agitator (10) provided inside said washing tub (3) and adapted for agitating laundry articles, characterized in that said agitator (10) comprises a roller type agitator provided with at least one roller (14) rotatably mounted thereto, each said roller (14) having a plurality of washing protrusions (14a) and/or water ports (14b, 14c) at the circumferential outer surface and both side surfaces thereof, so as to generate turbulent water flow, to stretch and squeeze said laundry articles and to smooth circulation of washing water. A washing machine with a roller type agitator as claimed in claim 1, characterized in that said roller type agitator comprises a circular rotator base (11) having a plurality of washing vanes (15) and rollers (14) provided thereon, said washing vanes and rollers being radially and alternately arranged and spaced apart from one another. A washing machine with a roller type agitator as claimed in Ciaim 1, characterized in that said roller type agitator comprises a circular rotator base (11) and a washing rod (16) vertically formed on the center of said rotator base, said rotator base having a plurality of rollers (14) and washing vanes (17) radially and alternately arranged and spaced apart from one another, said washing rod having at the side surface thereof washing protrusions (17′) extruded outwardly. A washing machine with a roller type agitator as claimed in claim 1, characterized in that said roller type agitator comprises an agitating tub base (11) provided with rollers (14) at the lower portion thereof and a washing side wall (18) extending from the periphery of said base. A washing machine with a roller type agitator as claimed in Claim 1, characterized in that said roller type agitator comprises a mountainous rotator (11, figure 13) provided with rollers (14) thereon, which rollers are radially arranged and spaced apart from one another and also inclined to the inner surface of the washing tub (3) at a predetermined angle (). A washing machine with a roller type agitator as claimed in Claim 1, characterized in that each of said plurality of washing protrusions (21) at the upper portion of the washing tub (3) is formed as gradually and downwardly becoming narrow. A washing machine with a roller type agitator as claimed in Claim 1, characterized in that said washing tub is provided with an auto-balancer (20) at an upper portion thereof, said auto-balancer including a plurality of washing protrusions (22) formed as spaced apart from one another. A washing machine with a roller type agitator as claimed in Claim 1, wherein said rotator base (11) of said agitator (10) comprises a horizontal surface plate (11a), V-shaped inclined surface plates (11d) or reversed V-shaped inclined surface plates (11e), said rollers mounted to said surface plate. A washing machine with a roller type agitator as claimed in Claim 1, wherein said rotator base (11) of said agitator (10) comprises a horizontal bottom (11a) and inclined side walls extending upwardly (11b) or downwardly (11c) from said horizontal bottom, said rollers (14) mounted to said horizontal bottom or said inclined side walls. A washing machine with a roller type agitator as claimed in Claim 1, wherein each said roller (14) of said agitator (10) comprises a cylindrical shaped roller, a conical shaped roller or a ball shaped roller. A washing machine with a roller type agitator as claimed in Claim 1, wherein said agitator includes a plurality of rollers (14) and washing vanes (15) which are radially and alternately arranged, each said washing vane being formed as low as the height of each said roller. A washing machine with a roller type agitator as claimed in Claim 1, wherein said water ports (14c) provided at both side surfaces of each said roller (14) are larger than said water ports (14b) provided at the circumferential outer surface of each said roller.
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LG ELECTRONICS INC; LG ELECTRONICS INC.
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JUNG IN CHEOL; PARK KWAN RYONG; REW JAE CHEOL; JUNG, IN CHEOL; PARK, KWAN RYONG; REW, JAE CHEOL
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EP-0489611-B1
| 489,611 |
EP
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B1
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EN
| 19,970,507 | 1,992 | 20,100,220 |
new
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C09K3
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C08G18
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C09K3, C09J175, C08G18, C08L75
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C08G 18/10+18/30D, M09K200:06B, C09K 3/10D14, C09J 175/04+C, M08G190:00, C08G 18/10+18/32B8R
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Two-component polyurethane sealants, a process for preparing them and their use for bonding a windscreen
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Two-component polyurethane sealants, comprising (A) a pasty polyurethane component containing a polyurethane prepolymer having free isocyanate groups, and a curing agent, and (B) a pasty solvent-containing component, where component (A) contains at least one latent, solvent-activatable curing agent which can be activated by means of solvents, and component (B) contains a polar, aprotic solvent and water reversibly bonded to a carrier substance which liberates water in a delayed manner after components (A) and (B) have been mixed. They are prepared by mixing components (A) and (B) using a static mixer, having only from 15 to 75 % of the number of mixing elements necessary for achieving homogeneous mixing of components (A) and (B) in the ratio by volume of 1:1. Application to a method for bonding a windscreen.
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The invention relates to two-component polyurethane sealants, in particular for the direct glazing of motor vehicle windscreens, comprising (A) a pasty polyurethane component containing a polyurethane prepolymer having free isocyanate groups, and a curing agent, and (B) a pasty component. Sealants of this type have been disclosed in GB-A-1 104 831 and EP-A-371 370, the curing agent being liberated by water and component (B) containing water as essential constituent. The invention also relates to a process for preparing such sealants and a particular component (B) for use in such sealants. A fundamental problem of sealants of this type is that, on the one hand, the processing time must be sufficiently long to ensure flawless processing of the sealant before it cures, but, on the other hand, the curing must, for obvious reasons, take place as rapidly as possible when processing is complete. Finally, the polyurethane component (A) must also have an adequate shelf life. Although the known two-component polyurethane sealants have sufficient strength, for example, one hour after mixing, the processing time is, however, too short, which means problems can arise even during mixing of components (A) and (B) due to premature gelling of the sealants. It has now been found that a particularly favourable behaviour with respect to processing time and curing rate is obtained in two-component polyurethane sealants of the type mentioned above if the curing agent of component (A) is solvent-activable and component (B) contains solvents and water reversibly bonded to a carrier substance, which liberates water in a delayed manner after components (A) and (B) have been mixed. The invention accordingly provides two-component polyurethane sealants, in particular for the direct glazing of motor vehicle windscreens, comprising (A) a pasty polyurethane component containing a polyurethane prepolymer having free isocyanate groups, and a curing agent, and (B) a pasty solvent-containing component, characterized in that component (A) contains a latent curing agent which can be activated by means of solvents, and component (B) contains a polar, aprotic solvent and water, reversibly bonded to a carrier substance which liberates water in a delayed manner after components (A) and (B) have been mixed. As shown by the examples below, the sealants according to the invention have, on the one hand an entirely adequate processing time or gelling time of from about 5 to 10 minutes, while, on the other hand, a shear strength of approximately 0.1 N/mm2 is achieved after one hour and virtually the final shear strength of about 4 N/mm2 is achieved after 24 hours. In component (B), the carrier substance ensures that a delayed release of water takes place, which results in an extension of the processing time, but neverless with a rapid achievement of the final strength. Suitable carrier substances for binding water in component (B) are all substances which are capable of reversibly binding water and liberating water in a delayed manner after components (A) and (B) have been mixed. Examples of preferred carrier substances are ground cellulose, starch and cork. The carrier substance is preferably finely particulate, so that, for example, at least 50 % of the particles have a size of less than 40µm. Examples of suitable commercial products are cellulose powder or native potato starch. Ground cellulose and starch are capable of reversibly binding water up to a maximum ratio by weight of 1:1. In a preferred embodiment, the carrier substance is dispersed in an inert viscous liquid in order to achieve the desired pasty consistency. Suitable viscous liquids here are in principle all those which do not react, in particular, with the isocyanate groups of the polyurethane prepolymer of component (A) and also have no other disadvantageous effect on the cured sealant. The inert viscous liquids are preferably plasticisers for the cured sealant, preference being given to alkylsulphonic acid esters methylstyrene adducts and phtalic acid esters. Examples of suitable commercial products are alkylsulphonic acid esters of phenol or cresol, ACTREL® 400 (product of the addition reaction of methylstyrene and binuclear, partially hydrogenated aromatics) from ESSO and benzyl butyl phtalate. Component (B) contains a polar, aprotic solvent, such as, for example, n-butyrolactone, γ-butyrolactone, chlorobenzene, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, N-methylpyrrolidone, tetrahydrofuran or N-vinylpyrrolidone. In addition to said solvent, component (B) also contains water, in an amount of at most 10 % by weight, preferably less than 5 %, based on the total weight of component (B). Furthermore, component (B) preferably contains a thixotropic agent, carbon black being particularly preferred. Component (B) may also contain further conventional additives and processing aids, such as catalysts, dyes, pigments, fillers or wetting agents. In a preferred embodiment, component (B) contains a wetting agent. Wetting agents contribute to compatibility and thus improve the smoothness of the sealant. Preferred examples of suitable wetting agents are sorbitan monolaurate and polyoxyethylene (10) oleyl alcohol. Suitable polyurethane prepolymers are known to persons skilled in the art. These prepolymers contain terminal free isocyanate groups, which are capable of reacting both with the curing agent present in component (A) and with water introduced through component (B), with enlargement of the molecule and curing. This involves the following reactions occurring simultaneously. The solvent from component (B) activates the curing agent, the latter reacting with the polyurethane prepolymer ; however, water present in component (B) can also react directly with the isocyanate groups. The curing agent of component (A) is preferably a complexed amine. A preferred complexed amine is the NaCl complex compound of 4,4'-diaminophenylmethane. Suitable curing agents of component (A) are also amine complexes with sodium bromide, sodium iodide, sodium nitrite, lithium chloride, lithium bromide, lithium iodide, lithium nitrite or sodium cyanide, amine complex compounds of the alkali metal or alkaline earth metal salt type and microencapsulated, solvent-activatable polyamines or polyols. Solvent-activatable curing agents of this type are disclosed in EP-A-0 351 728. In a further preferred embodiment, component (A) contains a thixotropic agent, with carbon black being particularly preferred. Although the isocyanate groups of the polyurethane prepolymer are also capable of reacting with water of atmospheric moisture, the main reaction, due to the early shear strength which is desired, is the crosslinking reaction with water liberated from the carrier substance of component (B) or with the solvent-activated curing agent in component (A). The ratios can be selected so that there is either a stoichiometric excess or a substoichiometric amount of free NCO groups relative to the reactive groups present in the curing agent. The former case is preferred since the processing time can then be better adjusted via the water/carrier substance ratio and the amount of water in component (B). If the solvent-activatable curing agent is used in a substoichiometric amount, the curing rate in the sealants according to the invention can be controlled, within certain limits which are of practical importance, by the ratio of carrier substance to water. Both components (A) and (B) are in pasty form, i.e. are not free-flowing. In addition to the pasty consistency of components (A) and (B), the non-Newtonian properties (thixotropic behaviour) also play a part in the mixing behaviour of the components. Control may in each case be effected through the choice of the type and amount of the inert viscous liquid and of the thixotropic agent. As far as the amount of component (B) relative to component (A) is concerned, the molar amounts of curing agent on the one hand and the free isocyanate groups in component (A) on the other hand must again be taken into account, preference being given, as stated above, to a stoichiometric excess of NCO. In the sealants according to the invention, component (A) contains from about 20 to 80 parts by weight, preferably from 35 to 55 parts by weight, in particular from 40 to 45 parts by weight, based on 100 parts by weight of component (A), of the polyurethane prepolymer, and from 20 to 120 eq-%, preferably from 40 to 80 eq-%, in each case based on the number of equivalents of isocyanate in the polyurethane prepolymer, of the curing agent. If component (A) contains a thixotropic agent, the latter is present in such amounts that the material is firm and not free-flowing. In the case of carbon black, amounts of about 7 parts by weight per 100 parts by weight of component (A) are generally necessary for this purpose. Component (B) contains the carrier substance in an amount sufficient for complete binding of water. The ratio between the carrier substance and water is generally from about 1:0.25 to 1:1, preferably from 1:0.5 to 1:0.8. The carrier substance (with water bonded thereto) is preferably dispersed in an inert viscous liquid. If component (B) contains a thixotropic agent, for example carbon black, the latter is preferably present in such amounts that a pasty consistency is produced. To this end, amounts of about 7 to 25 % by weight, based on component (B), are generally sufficient. Preferably components (A) and (B) are employed in a ratio by volume of at least 2 : 1, and more preferably from about 5 : 1 to 100 : 1. The invention furthermore relates to a process for preparing a sealant as hereinabove described, especially those where components (A) and (B) are employed in a ratio by volume of at least 2:1, comprising mixing components (A) and (B) using a static mixer, which process is characterized in that the said static mixer has only from about 15 to 75 % of the number of mixing elements necessary for achieving homogeneous mixing of components (A) and (B) in the ratio by volume of 1:1. In a preferred embodiment, mixing is carried out using a static mixer which has only from 40 to 50 % of the number of mixing elements necessary to mix components (A) and (B) homogeneously in the ratio by volume of 1:1. In a further embodiment, a component (B) which contains water in free form and not bonded to a carrier substance is used in the mixing process. In order to ensure an appropriate processing time it is necessary in this case to use a component (A) with low reactivity. In a specific embodiment, a component (B) which contains no water is employed in the mixing process. Neverless, the curing agent is, here too, used in substoichiometric amounts, since the curing reaction otherwise proceeds too rapidly. Complete curing is effected by atmospheric moisture in this case. The static mixer used for mixing preferably has an internal diameter in the range from about 5 to 30 mm, in particular in the range from 10 to 20 mm. Statics mixers, also known as motionless mixers, have non-moving, i.e. static, guide or mixing elements built into the flow channel. In this respect, see Perry's Chemical Engineers Handbook, 6th Edition (1984), 19-22 to 19-23. Particularly preferred static mixer designs are the Kenics® mixer and the Package® mixer. Preference is given to a Kenics® mixer which has only from 4 to 18, in particular from 8 to 12, mixing elements instead of the at least 24 mixing elements necessary to homogeneously mix components (A) and (B) in the ratio by volume of 1:1. If a Package® mixer is used, it preferably has only from 4 to 21, in particular from 11 to 14, mixing elements instead of the at least 28 mixing elements necessary to homogeneously mix components (A) and (B) in the ratio by volume of 1:1. In the process of the invention, mixing of components (A) and (B) is not continued until homogeneity is achieved. The reduced number of mixing elements in the mixer allows the operating pressure to be reduced, so that satisfactory discharge rates are possible using conventional spray guns. Processing by means of shortened static mixer results in a less than homogeneous state. As a consequence, due to the limitation on the diffusion, the curing agent of component (A) is not displaced in a sudden manner by the solvent of component (B), which in turn means that curing, preferably amine curing, of the polyurethane prepolymer only sets in gradually, while, on the other hand, the diffusing water from component (B) is itself also capable of reacting with the isocyanate groups. Overall, this achieves a particularly balanced ratio between processing time and early shear strength. The sealants according to the present invention are especially advantageous and designed for bonding windscreens of cars and automotives, and more particularly those cars with directly glazed windows. Therefore according to the present invention we provide a method for bonding a windscreen by applying a two-component polyurethane sealant comprising (A) a pasty polyurethane component containing a polyurethane prepolymer having free isocyanate groups, and a latent curing agent which can be activated by means of solvents and (B) a pasty component containing a polar, aprotic solvent and water, reversibly bonded to a carrier substance which liberates water in a delayed manner after components (A) and (B) have been mixed. In further detail, components (A) and (B) of the polyurethane sealant used in the said method will be as described hereinabove. The examples below illustrate the invention. Unless otherwise stated, parts are by weight. I - Preparation of component (A1)21.35 parts of octyl decyl phtalate (WITAMOL® 118 from HÜLS AG), 7.143 parts of diphenylmethane 4,4'-diisocyanate (DESMODUR® 44MS from BAYER AG), 21.69 parts of polypropylene oxide triol (DESMOPHEN® 1919U from BAYER AG), 11.21 parts of polypropylene oxide diol (DESMOPHEN® 1900U from BAYER AG), 0.10 part of p-toluenesulphonamide and 21.00 parts of carbon black (ELFTEX® 465 from CABOT) are dispersed over the course of 30 minutes. 0.1 part of Bi catalyst (COSCAT 83 from ERBSLÖH) and 7.565 parts of octyl decyl phtalate (WITAMOL® 118) were then added, and the mixture was stirred for one hour. 0.2 part of Bi catalyst (COSCAT 83), 0.032 part of tosyl isocyanate (BAYER AG), 7.305 parts of octyl decyl phtalate (WITAMOL® 118) and 5.53 parts of the NaCl complex of 4,4'-diaminophenylmethane (CAYTUR® 21 from UNIROYAL) were then stirred in at room temperature. The pasty mixture obtained is transferred into cartridges (in the absence of air). II - Préparation of a component (A2)As far Al, but only 0.56 times the amount of amine was employed. III - Preparation of a component (B1)22.5 parts of carbon black (ELFTEX® 465), 3.6 parts of water, 4.5 parts of cellulose (XX-01® from MIKRO-TECHNIK) and 74.4 parts of butyrolactone are dispersed for 30 minutes. The pasty mixture obtained is transferred into cartridges. IV - Preparation of a component (B2)23.75 parts of carbon black (ELFTEX ® 465), 1.1 parts of water, 1.375 parts of cellulose (XX-01®) 38.702 parts of butyrolactone, 38.762 parts of phenol alkylsulphonic acid ester (MESAMOLL® from BAYER AG) were dispersed for 30 minutes. The pasty mixture obtained is transferred into cartridges. V - Preparation of a component (B3)96.4 parts of butyrolactone are mixed with 3.6 parts of water and transferred into cartridges. Application of the adhesive using a Kenics® mixerA cartridge containing component (A) and a cartridge containing component (B) (cartridge length 150 mm, diameter 46 mm (component (A)) or 17.2 mm ( component (B) ), A : B volume ratio = 100:14) were connected, via an adaptor, to a Kenics® mixer (diameter 13 mm) having 12 elements. The cartridges attached to the mixer were placed in a twin-cartridge hand gun (model HILTI P2000 ), and the adhesive was forced out onto primed steel test specimens (primer : Primer Clear®, BOSTIK ; bonded area : 25 x 10 mm with a film thickness of 2 mm). Pot time B1 B2 B3 A12 min5 mininadequate mixing A25 min10 mininadequate mixing Shear strength (as a function of the curing time) : Combination Curing time at room temperature 1 h 24 h 7 days A1/B10.34 N/mm21.9 N/mm22.9 N/mm2A1/B2 0.6 5.0 5.4 A2/B1 0.09 4.0 4.5 A2/B20.07 3.8 4.5 Application of the adhesive using a Package® mixerThe appplication was carried out in the same manner as described above, but, instead of the Kenics® mixer, a Package® mixer (TAH Industries No. 020-064, diameter 18.75 mm) having 14 mixing zones was connected to the two cartridges. Pot time B1 B2 B3 A12 min5 mininadequate mixing A25 min10 mininadequate mixing Shear strength (as a function of the curing time) : Combination Curing time at room temperature 1 h 24 h 3 days A1/B10.3 N/mm21.5 N/mm22.8 N/mm2A1/B20.1 3.5 4.0 A2/B10.09 3.4 3.9 A2/B20.06 3.2 3.8 Tables I and III show that mixing of the pure solvent mixture B3 with the pasty component A does not take place since the viscosity and consistency of the two components is different. It can be seen from Tables II and IV that the shear strength of the combinations A1/B1 and A1/B2 is sufficiently high after only 1 hour.
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Two-component polyurethane sealants, comprising (A) a pasty polyurethane component containing a polyurethane prepolymer having free isocyanate groups, and a curing agent, and (B) a pasty solvent-containing component, where component (A) contains at least one latent, solvent-activable curing agent, and component (B) contains a polar, aprotic solvent and water reversibly bonded to a carrier substance which liberates water in a delayed manner after components (A) and (B) have been mixed. Sealant according to Claim 1, characterized in that the polar, aprotic solvent is selected from n-butyrolactone, γ-butyrolactone, chlorobenzene, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, N-methylpyrrolidone, tetrahydrofuran and N-vinylpyrrolidone. Sealant according to Claim 1 or 2, characterized in that the carrier substance is selected from ground cellulose, starch and cork. Sealant according to one of claims 1 to 3, characterized in that the carrier substance is dispersed in an inert viscous liquid. Sealant according to one of claim 4, characterized in that the viscous liquid is a plasticiser for the cured sealant. Sealant according to Claim 5, characterized in that the plasticiser is selected from alkylsulphonic acid esters, methylstyrene adducts and phtalic acid esters. Sealant according to one of claims 1 to 6, characterized in that component (B) further contains a thixotropic agent. Sealant according to one of claims 1 to 7, characterized in that component (B) further contains additives and processing aids. Sealant according to Claim 8, characterized in that component (B) contains a wetting agent. Sealant according to one of claims 1 to 9, characterized in that component (A) contains a complexed amine as curing agent. Sealant according to claim 10, characterized in that the complexed amine is an amine complex compound of the alkali metal or alkaline earth metal salt type. Sealant according to claim 11, characterized in that the complexed amine is the NaCl complex compound of 4,4'-diaminophenylmethane. Sealant according to claim 11, characterized in that the complexed amine is an amine complex with sodium bromide, sodium iodide, sodium nitrite, lithium chloride, lithium bromide, lithium iodide, lithium nitrite or sodium cyanide. Sealant according to one of claims 1 to 9, characterized in that component (A) contains, as curing agent, microencapsulated, solvent-activable polyamines or polyols. Sealant according to one claims 1 to 14, characterized in that component (A) contains a thixotropic agent. Sealant according to claim 15 or claim 7, characterized in that the thixotropic agent is carbon black, pyrogenic silica or a urea compound. Sealant according to any of claims 1 to 16, characterized in that components (A) and (B) are employed in a ratio by volume of at least 2:1. Sealant according to claim 17, characterized in that components (A) and (B) are employed in a ratio by volume in the range from 5:1 to 100:1. Process for preparing a sealant according to claim 17, comprising mixing components (A) and (B) using a static mixer, characterized in that the said static mixer has only from 15 to 75 % of the number of mixing elements necessary for achieving homogeneous mixing of components (A) and (B) in the ratio by volume of 1:1. Process according to Claim 19, characterized in that the said static mixer has only from 40 to 50 % of the number of mixing elements necessary to homogeneously mix components (A) and (B) in the ratio by volume of 1:1. Process according to one of Claim 19 and 20, characterized in that the said static mixer has an internal diameter of from 5 to 30 mm. Process according to one of Claims 19 and 21, characterized in that a Kenics™ mixer which has only from 4 to 18 mixing elements or a Package™ mixer which has from 4 to 21 mixing elements is used. A method for bonding a windscreen by applying a two-component polyurethane sealant according to any of claims 1 to 16.
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JOINT FRANCAIS; LE JOINT FRANCAIS SNC
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MULLER BODO; PIESTERT GERHARD; MULLER, BODO; PIESTERT, GERHARD
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EP-0489619-B8
| 489,619 |
EP
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B8
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EN
| 20,070,509 | 1,992 | 20,100,220 |
new
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H04M3
| null |
H04M3, H04Q3, H04Q11
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H04Q 3/62F1, H04Q 11/04S
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Private branch exchange
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A method of deciding whether an extension terminal is called or not is provided. The kind of communication is recognized on the basis of a set-up message received from the ISDN. Whether the extension terminal is called or not is decided on the basis of the result of comparison between the kind of the extension terminal and the kind of the communication recognized. There is also provided a private branch exchange comprising: a detector to detect a reception from an analog external line; a digital interface to connect a terminal corresponding to a procedure for a digital line; and a judging circuit to judge whether the terminal corresponds to a procedure for an analog line or not, wherein when the judging circuit decides that the terminal corresponds to the procedure for the analog line when the reception is detected by the detector, the digital interface transmits the set-up message to the terminal.
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BACKGROUND OF THE INVENTIONField of the inventionThe invention relates to a private branch exchange which can cope with services of the ISDN.Related Background ArtA private branch exchange is known from document Sonderausgabe belcom report und Siemens-Magazin COM , entitled ISDN im Büro-Hicom - Anwendernutzen und Technik des ISDN-Kommunikationssystems HICOM , from Siemens Aktiengesellschaft, Berlin and Munich. 1985. ISBN 3-8009-3846-4.According to a conventional private branch exchange, when a call is received from an ISDN line, all of digital terminals which have been preset in correspondence to the line are allowed to ring. When a call is received from an analog line, all of analog terminals which have been preset in correspondence to the line are allowed to ring.In the conventional private branch exchange, therefore, even when a transmission terminal notifies information indicating that it wants to execute a communication as a telephone through the ISDN, not only the digital telephones but also the G4 facsimiles are allowed to ring. Consequent when the G4 facsimile responds to a call reception, the communication cannot be performed.On the other hand, in the conventional private branch exchange, even when a transmission terminal notifies information indicating that it wants to perform a data communication through the ISDN, not only the G4 facsimiles but also the digital telephones which can perform only the communication are allowed to ring. Therefore, when such a digital telephone responds to a call reception, the data communication cannot be performed.In the conventional private exchange, when a G3/G4 facsimile having both of the G3 and G4 functions is connected to an extension digital interface, in the case where a call is received from the G3 facsimile through the analog line, the G3/G4 facsimile cannot be allowed to respond to the call reception.Document EP-A-0 341 687 is related to a private branch exchange connected to the ISDN. The private branch exchange comprises a control unit, in which is formed an incoming information to be received by an extension terminal. This incoming information includes the line accessing number, which is displayed on the extension terminal.SUMMARY OF THE INVENTIONThe invention provides a private branch exchange in accordance with claim 1 and a method for controlling a private branch exchange in accordance with claim 6.It is an object of the invention to improve a private branch exchange which can cope with services of the ISDN.Another object of the invention is to provide a private branch exchange which calls an extension terminal having the function to execute a communication of the designated kind in the services of the ISDN.Still another object of the invention is to provide a private branch exchange which analyzes reception information received from the ISDN and doesn't call a data communication terminal in the case where an information transmission ability of a transmission ability information element relates to a voice.Further another object of the invention is to provide a private branch exchange which analyzes reception information received from the ISDN and doesn't call a terminal which doesn't have the G3 communicating function in the case where an information transmission ability of a transmission ability information element relates to an audio of 3.1 kHz and high-order layer characteristic identification data of a high-order layer consistency information element relates to G3.Further another object of the invention is to provide a private branch exchange which analyzes reception information received from the ISDN and doesn't call an extension terminal which doesn't have the data communicating function in the case where an information transmission ability of a transmission ability information element relates to a non-limited digital.Further another object of the invention is to provide a private branch exchange which calls an extension terminal corresponding to both of a procedure for an analog line and a procedure for a digital line in the case where a call is received from the analog line.The above and other objects and features of the present invention will become apparent from the following detailed description and the appended claims with reference to the accompanying drawings.BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a block diagram of an apparatus embodying the invention:Fig. 2 is a block diagram of an analog line interface of the apparatus embodying the invention;Fig. 3 is a block diagram of an ISDN-T point interface of the apparatus embodying the invention:Fig. 4 is a block diagram of an ISDN-S point interface of the apparatus embodying the invention;Figs. 5 to 8 are flowcharts for embodying the invention;Fig. 9 is a communication schematic sequence of the ISDN; andFig. 10 shows an information format of messages of the ISDN.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Fig. 1 is a block diagram showing a system construction of the invention. In the diagram, reference numeral 100 denotes a main apparatus of a telephone exchange; 102 an analog telephone network, 104 an ISDN (Integrated service digital network) as a digital public network and 105 an analog line interface which is connected to the analog telephone network 102 through a line 101. An exchange method in the embodiment uses a time-sharing method. Therefore, the analog line I/F 105 is connected to an exchange unit 112 through an up PCM highway 106 and a down PCM highway 107. Reference numeral 108 denotes an ISDN-T point interface which is connected to the ISDN 104 through a line 103.The ISDN-T point interface 108 is connected to the exchange unit 112 though an up PCM highway 109 and a down PCM highway 110.Reference numeral 113 denotes an ISDN-S point interface which has the function to enclose ISDN terminals for extensions and encloses a G3/G4 facsimile 190 through a line 129. The ISDN-S point interface 113 is connected to the exchange unit 112 through a down PCM highway 114 and an up PCM highway 115. Reference numeral 116 denotes a similar ISDN-S point interface to enclose an ISDN telephone 132 through a line 131 in the embodiment. The ISDN-S point interface 116 is also connected to the exchange unit 112 through PCM highways 117 and 118.Reference numeral 119 denotes a special telephone interface to enclose a special extension telephone 134 only for use in the system through a line 133 for an extension. The special telephone interface 119 is connected to the exchange unit 112 through PCM highways 120 and 121. The special extension telephone 134 also includes a telephone having the function to connect an SLT (single line telephone: telephone for an analog public network).Reference numeral 122 denotes an ordinary telephone interface to enclose a G3 facsimile 135 through a line 135. The ordinary telephone interface 122 is connected to the exchange unit 122 through PCM highways 129 and 124. A ringer generation unit 127 generates a call signal of 16 Hz and 75 Vrme. A tone generation unit 111 is connected to the exchange unit 112 through a PCM highway 128 and generates various kinds of service tones to extension terminals. Reference numeral 126 denotes a main control unit to control the whole system. The main control unit 128 is connected to each of the above interfaces and the exchange unit 112 though a control bus 125. Reference numeral 126M denotes a memory in which information which is necessary for the main control unit 126 to control the whole system is stored. The information stored in the memory 126M includes information indicating which extension terminal is connected to which extension position and the like. Each of the interfaces 113, 116, 119, and 122 can connect a plurality of extension terminals having the same function. Fig. 2 is a block diagram of the analog line interface 105 of the embodiment. In the diagram, reference numerals 101a and 101b denote lines from the analog telephone network 102. Reference numeral 200 denotes a reception detection unit to detect a call reception from the analog telephone network. A detection signal is sent to a control unit 211 through a signal line 209. Reference numeral 201 denotes a relay to form a DC loop by a reception response. The relay 201 is driven by the control unit 211 through a signal line 212. Reference numeral 202 denotes a DC loop circuit for the response mentioned above and 203 indicates a capacitor to cut a DC current. Reference numeral 204 denotes a hybrid transformer to execute a two-wire/four-wire conversion of an AC signal; 205 a receiving amplifier for converting the level of the AC signal from the hybrid transformer 204 and supplying to a codec 208; 207 a transmitting amplifier for converting the level of an AC signal from the codec 208 and supplying to the hybrid transformer 204; and 206 a balancing network serving as a matching circuit to eliminate a leakage of the AC signal from the transmitting amplifier to the receiving amplifier. The codec 208 is a circuit to convert the analog signal into the PCM (pulse code modulation) signal and to convert the PCM signal into the analog signal, respectively. The codec 208 is connected to the exchange unit 112 through the down PCM highway 107 and the up PCM highway 108.Fig. 3 is a block diagram of the ISDN-T point interface in the embodiment. In the diagram, reference numerals 103a, 103b, 103c, and 103d denote lines from the ISDN 104. Reference numeral 302 denotes a processing unit of layers 1 and 2. The processing unit 302 is connected to the lines through transformers 300 and 301.Reference numeral 303 denotes a distribution unit to separate and distribute B1 and B2 channels from the down PCM highway 110. The separated and distributed B1 channel signal is connected to the layer 1-2 processing unit 302 through a signal line 304. The B2 channel signal is connected to the layer 1-2 processing unit 302 through a signal line 305.Reference numeral 306 denotes a multiplexing unit to multiplex the separated B1 and B2 channels. The B1 channel signal from the layer 1-2 processing unit 302 is supplied to the multiplexing unit 306 through a signal line 307. The B2 channel signal from the processing unit 302 is supplied to the multiplexing unit 306 through a signal line 308. The B1 and B2 channel signals are multiplexed by the multiplexing unit 306 and a multiplexed signal is sent to the up PCM highway 109. A timing generation unit 310 supplied a timing signal to the distribution unit 303 and the multiplexing unit 306 through a signal line 309.A control unit 312 controls the ISDN-T point interface and is connected to the layer 1-2 processing unit 302 and a memory unit 313 through a control line 311 and is also connected to the main control unit 126 through the control bus 125.The layer 1-2 processing unit 302 sate a call from the ISDN 104 and transfers to the main control unit 128.Fig. 4 is a block diagram of the ISDN-S point interface of the embodiment. In the diagram, reference numerals 129a, 129b, 129c, and 129d denote lines which are connected to the G3/G4 facsimile 130. Reference numeral 408 denotes a processing unit of the layers 1 and 2. The processing unit 408 is connected to the lines through transformers 409 and 410.Reference numeral 400 denotes a distribution unit to separate and distribute the B1 and B2 channels from the down PCM highway 114. The separated and distributed B1 channel signal is supplied to the layer 1-2 processing unit 408 through a signal line 401. The B2 channel signal is supplied to the processing unit 408 through a signal line 402. Reference numeral 403 denotes a multiplexing unit to multiplex the separated B1 and B2 channel signals. The B1 channel signal from the processing unit 408 is supplied to the multiplexing unit 403 through a signal line 404, while the B2 channel signal is supplied to the multiplexing unit 403 through a signal line 405. The B1 and B2 channel signals are multiplexed by the multiplexing unit 403 and a multiplexed signal is sent to the up PCM highway 115. Reference numeral 407 denotes a timing generation unit to supply a timing signal to the distribution unit 400 and the multiplexing unit 403 through a signal line 406.A control unit 413 controls the ISDN-S point interface and is connected to the layer 1-2 processing unit 408 and a memory unit 414 through a control line 412. The control unit 413 is also connected to the main control unit through the control bus 125.Reference numeral 411 denotes a power supplying circuit unit (feeder unit) to supply a power source to the G3/G4 facsimile 130.The operation of the main control unit 125 will now be described in accordance with a flowchart shown in Fig. 5.When the main control unit 126 detects the call reception. In step S500, the kind of line is discriminated in step S501. When the kind of line indicates the call reception from the PSTN 102, step S502 follows. When it indicates the call reception from the ISDN 104, step S513 follows.The call reception from the PSTN 102 is detected by the reception detection unit 200 in Fig. 2 and a detection signal is sent to the control unit 211 through the signal line 209. The detection signal is subsequently transmitted to the main control unit 126 through the control bus 125, so that the call reception from the PSTN 102 is detected by the main control unit 126.On the other hand, a detection signal of the call reception from the ISDN 104 is transmitted through the reception lines 103c and 103d in Fig. 3 and is sent from the layer 1-2 processing unit 302 to the control unit 312 through the signal line 311. The D channel information indicative of such a reception is transmitted to the main control unit 126 through the control bus 125, so that the call reception from the ISDN 104 is detected by the main control unit 126.When a call from the PSTN 102 is received, a check is first made in step S502 to see if a calling process to the ring assignment extension has been finished or not. When the calling process is not finished yet, the main control unit 126 searches the ring assignment extension in step S503. The process is branched in step S504 in accordance with the kind of extension.In the case where information indicating that the kind of ring assignment extension indicates the S point telephone has already been registered in the memory 126M, the main control unit 126 discriminates whether such as extension is a G4 facsimile or not by referring to the memory 128M in step S505. If YES, step S506 follows. If NO, step S507 follows to execute a ringing process.In step S506, the main control unit 126 discriminates whether such a G4 facsimile has the G3 function or not by referring to the memory 126M. If YES, step S507 follows. If NO, the ringing process is not performed and the processing routine is returned to step S502 to search the next ring assignment extension.The main control unit 126 requests a call setting through the ISDN-S point interfaces 113 and 116 to the terminals 130 and 132 connected to the S point in step S507 and waits for a call set acceptance display from the terminals 130 and 132. When it is determined in step S508 that the call set acceptance display has been transmitted, a check is made in step S509 to see if there are call notifications from the terminals 130 and 132 or not. When the call notification is recognized in step S509, the processing routine is returned to step S502.In the case where the kind of ring assignment extension has been registered as a special telephone in the memory 128M in step S504, the main control unit 128 progresses the processing routine to step S510. In step S510, a ringing tone is selected from the tone generation unit 111 shown in Fig. 1 and is connected to the ring assignment special telephone through the exchange unit 112. In step S511, a speaker of the special telephone is turned on. In step S512, a state indicative of the in-reception is displayed. For instance, when the special telephone has a display such as an LCD (liquid crystal display) or the like, the in-reception is displayed by the LCD. When the special telephone has an LED (light emitting diode) or the like in correspondence to an external line button or the like, the LED is allowed to flicker or the like.In step S504, when the ring assignment extension is an SLT (two-wire telephone) or a G3 facsimile, the ringer generation unit 127 in Fig. 1 is turned on in step S513 and an IR (call) signal is sent to the terminal. The processing routine is returned to step S502.In step S502, a check is made to see if all of the extensions to be allowed to ring have been searched or not. If YES, the processing routine advances to an incalling state and the apparatus waits for a response from the extension. If NO, the processes are repeated from step S503.In the case of ringing one extension such as in the case of a DIL (direct inline) or the like, the processes are also similarly executed.When the main control unit 126 detects that the extension such as a G3/G4 facsimile 130 has responded through the ISDN-5 point interface 118, the main control unit controls the exchange unit 112 so as to connect the external line 101 which has received and the extension 130 which has responded.On the contrary, in the case where there is a request for the G3 transmission from the G3/G4 facsimile 130 through the PSTN 102, the main control unit 126 recognizes the generation of such a request through the ISDN-S point interface 113 and controls the analog line interface 105 in accordance with dial information from the G3/G4 facsimile 130, thereby performing a call generation. The main control unit 126 controls the exchange unit 112 so as to connect the G3/G4 facsimile 130 with the external line which has generated the call in the PSTN 102.On the other hand, when the main control unit 126 detects the call reception by the ISDN-T point interface 108, in step S515, the received call set (set-up) information is stored into the memory 126M and a transmission ability information element in the call set information is extracted, in step S516, the process is branched by referring to the information transfer ability included in such information.Fig. 9 shows a schematic sequence of the call reception from the ISDN 104.When the transmission user executes the off-hook or the like and sends a call set message to the ISDN 104, the ISDN 104 transmite the call set message to the main apparatus 100. The ISDN 104 also sends a call set acceptance message to the transmission user in order to transmit the information indicating that the call set from the transmission user has been received.The main control unit 126 of the main apparatus 100 receives the call set and recognizes the reception call and executes a calling process and the like in step S516 and subsequent steps. The main control unit 126 detects the operation such as an off-hook or the like and transmits a response message to the ISDN 104. The ISDN 104 transmits a response recognition message to the main apparatus 100 and transmits a response message to the transmission user.For the reception of the ISDN 104, that is, the call set message, as shown in Fig. 10, the kinds of communication are shown in the transmisison ability information elements. The kinds of communication services are further finely specified in the optional high-order layer consistency information elements.Fig. 10 shows information formats when messages of a call generation, a reception call, a response, etc. in the ISDN are transmitted. The case of the call set message is shown as an example in Fig. 10.Reference numeral 20 denotes protocol identification data; 21 a call number; 22 a kind of message in which the value indicative of the call set is set; and 23 to 27 blocks in which necessary information can be added every message kind. The kind of information element is set into a head octet in each block.The transmission ability in the block 23 specifies the information transfer ability or the like of a voice, 3,1 kHz audio, and non-limited digital. The channel identification data in the block 24 specifies the interface type (fundamental or primary group) or specifies whether a change in channel of the fundamental interface is permitted or not.The reception number in the block 25 designates a communication partner and the telephone number of the reception user is set. The network is transparently transmitted to the high-order layer consistency in the block 26. The high-order layer consistency specifies the kind of communication service such as telephone, G2/G3, G4, teletex, or the like. The low-order layer consistency in the block 27 specifies an information transfer speed, each format (e.g., stop bit, parity) upon data communication, and the like.The case where the information transfer ability relates to the speech will now be described with reference to a flowchart of Fig. 6.In step S600, the main control unit 126 first checks to see if a calling process to the ring assignment extensions has been finished or not. If NO, the ring assignment extensions registered in the memory 126M are searched in step S601. The kinds of ring assignment extensions registered in the memory 126M are discriminated in step S602 and the processing routine is branched.When the main control unit 126 determines that the extension is an S-point telephone by referring to the memory 126M, a check is further made in step S603 to see if the extension is a G4 facsimile or not by referring to the memory 126M. When It is the G4 facsimile, the processing routine is returned to step S600 without executing the calling process. When it is not the G4 facsimile, the main control unit 126 sends a call set request to the S-point telephone in step S604 and waits for the call set acceptance display from the S-point telephone. When the main control unit 126 recognizes the call set acceptance display from the terminal in step S605, the call set acceptance display is sent to a T point, namely, the external line 103 which has received the call by the ISDN-T point interface 108 in step S806. When the call notification from the S-point telephone is subsequently recognized in step S607, a call request display is sent to the external line 103 in step S808. The processes in steps S808 and S808 are omitted so long as they have already been executed at least once by another route.When the ring assignment extension is the special telephone 134 in step S602, the call set acceptance display is sent to the T point, namely, the external line 103 in step S609. The call request display is transmitted in step S610. The processes in steps S609 and S610 are omitted so long as they have already been executed at least once by another route.A ringing tone is selected from the tone generation unit 111 shown in Fig. 1 in step S611. The ringing tone is connected to the ring assignment special telephone through the exchange unit 112. The speaker of the special telephone 134 is turned on in step S612. The in-reception display is executed in step S613 in a manner similar to step S512.When the ring assignment extension is an SLT or G3 facsimile in step S602, the call set acceptance display and the call request display are executed to the T point, namely, the external line 103 in steps S614 and S615. The processes in steps S614 and S615 are omitted so long as they have already been executed at least once by another route. In step S616, the ringer generation unit 127 in Fig. 1 is turned on and the IR signal is sent to the terminal. The calling process is finished.On the other hand, when the information transfer ability indicates 3.1 kHz audio in step S516 in Fig. 5, the main control unit 126 executes the processes shown in Fig. 7.The main control unit 128 discriminates whether the calling process has been finished or not in step S700. If NO, the ring assignment extension registered in the memory 126M is extracted in stop S701.The main control unit 126 discriminates the kind of ring assignment extension by referring to the memory 126M in step S702. When the ring assignment extension extracted in step S701 indicates the S-point telephone, a check is made in step S703 to see if the high-order layer characteristic identification data indicates the G3 facsimile or not by referring to the high-order layer constency information element which has been received from the external line 104 and stored in the memory 126M. When it is the G3 facsimile, step S704 follows. When it is not the G3 facsimile or when such information element is not transmitted, step S705 follows.In step S704, the main control unit 126 discriminates whether the S-point telephone terminal extracted in step S702 is the G3/G4 facsimile having the G3 function or not by referring to the memory 126M. When it is the G3/G4 facsimile, step S705 follows. If NO, the processing routine is returned to step S700.When the terminal is the G3/G4 facsimile which doesn't have the G3 function or the ISDN telephone having only the telephone function, the reception to the terminal registered in the memory 128M is inhibited. Therefore, it is possible to prevent that the call is received to the terminal which has been designated from the ISDN 104 and cannot perform the communication and a communicating efficiency deteriorates.In step S705, the call set request is sent to the S-point telephone and a check is made to see if the call set acceptance display is generated from the S-point telephone or not. When the main control unit 126 recognizes the call set acceptance display from the terminal. In step S706, the call set acceptance display is sent to the T point, namely, the external line 103 to which a reception call is performed by the ISDN-T point interface 108 in step S707. Subsequently, when the call notification from the S-point telephone is recognized in step S708, the cell request display is sent to the external line 103 in step S709. The processes in steps S707 and S709 are omitted so long as they have already been executed at least once by another route.When the ring assignment extension is the special telephone 134 in step S702, step S710 follows. The processes in steps S710 to S714 are similar to those in steps S609 to S613.When the ring assignment extension is the SLT or G3 facsimile in step S702, step S715 follows. The processes in steps S715 to S717 are similar to those in steps S614 to S616.When the information transfer ability indicates the non-limited digital in step S516 in Fig. 5, the main control unit 126 executes the processes shown in Fig. 8.The main control unit 126 checks to see if the calling process has been finished or not in step S800. If NO, the ring assignment extension registered in the memory 126M is extracted in step S801.When the main control unit 126 determines in step S802 that the ring assignment extension extracted in step S801 is the S-point telephone by referring to the memory 126M, a check is now made in step S803 that the high-order layer characteristic discrimination data indicates the G4 facsimile or not by referring to the high-order layer consistency information element which has been received from the external line and stored in the memory 126M. If YES, step S804 follows. If NO, or when such an information element is not transmitted, step S805 follows.In step S804, the main control unit 126 discriminates whether the S-point telephone terminal extracted in step S801 is the G4 facsimile (including the G4 facsimile having the G3 function) or not by referring to the memory 128M. If YES, step S806 follows. In step S805, the main control unit 126 checks to see if the S-point telephone terminal is a terminal which can handle only the voice or not by referring to the memory 128M. If yes, the processing routine is returned to step S800 without executing the calling process.In step S806, the call set request is sent to the S-point telephone and the apparatus waits for the generation of the call set acceptance display from the S-point telephone. When the main control unit 126 recognizes the call set acceptance display from the terminal in step S807, the call set acceptance display is sent to the T point, namely, the external line 103 to which a reception call is performed by the ISDN-T point interface 108 in step S808. Subsequently, when the main control unit recognizes the call notification from the S-point telephone in step S809, the call request display is sent to the external line 103 in step S810. The processes in steps S808 and S810 are omitted so long as they have already been executed at least once by another route.When it is decided in step S802 that the ring assignment extension is a special telephone, step S811 follows. The processes in steps S811 to S815 are similar to those in steps S609 to S613.When the ring assignment extension is the SLT or G3 facsimile in step S802, the processing routine is returned to step S800 without executing the processes.Although the embodiment has been described with respect to the facsimile communication, the invention can be also applied to the computer communication. That is, although the embodiment has been described with respect to the G3 and G4 facsimile apparatuses, the invention can be also applied to the analog computer communication and the digital computer communication.Although the invention has been described with respect to the preferred embodiment, the invention is not limited to the foregoing embodiments but many modifications and variations are possible within the scope of the appended claims of the invention.
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A private branch exchange comprising: detecting means (105, 108) for detecting an incoming call from an external line; andan extension digital interface (113) to connect a digital terminal corresponding to a digital procedure for a digital line,characterized in that said private branch exchange further comprises control means (126) for controlling said extension digital interface, when the incoming call for requesting communication using a G3 facsimile procedure for an analog line is detected by said detecting means, to transmit incoming call information to the digital terminal corresponding to the digital procedure in a case where the digital terminal is a G3/G4 facsimile terminal, and not to transmit the incoming call information to the digital terminal in a case where the digital terminal is not a G3/G4 facsimile terminal.A private branch exchange according to claim 1, wherein the digital procedure is an ISDN procedure.A private branch exchange according to claim 1, wherein the incoming call for requesting the communication using the analog procedure is received from an external analog line.A private branch exchange according to claim 1, wherein the incoming call for requesting the communication using the analog procedure is received from an external digital line.A private branch exchange according to claim 1, wherein said control means includes memory means (126M) for storing the kind of the digital terminal.A method for controlling a private branch exchange including an extension digital interface to connect a digital terminal corresponding to a digital procedure for a digital line, comprising the step of: detecting an incoming call from an external line,characterized in that said method is characterized by the step ofcontrolling (S506) the extension digital interface, when the incoming call for requesting communication using a G3 facsimile procedure for an analog line is detected in said detecting step, to transmit incoming call information to the digital terminal corresponding to the digital procedure in a case where the digital terminal is a G3/G4 facsimile terminal (S703), and not to transmit the incoming, call information to the digital terminal in a case where the digital terminal is not a G3/G4 facsimile terminal.A method according to claim 6, wherein the digital procedure is an ISDN procedure.A method according to claim 6, wherein the incoming call for requesting the communication using the analog procedure is received from an external analog line.A method according to claim 6, wherein the incoming call for requesting the communication using the analog procedure is received from an external digital line.A method according to claim 6, wherein whether the digital terminal corresponds to the analog procedure is judged based on a memory for storing the kind of the digital terminal.
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CANON KK; CANON KABUSHIKI KAISHA
|
SAKURAI SHIGEKI; TAKASHIMA SHOICHI; SAKURAI, SHIGEKI; TAKASHIMA, SHOICHI; SAKURAI, SHIGEKI, C/O CANON KABUSHIKI KAISHA; TAKASHIMA, SHOICHI, C/O CANON KABUSHIKI KAISHA
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EP-0489625-B1
| 489,625 |
EP
|
B1
|
EN
| 19,960,214 | 1,992 | 20,100,220 |
new
|
F16L37
|
E21B33
|
F16L23, E21B33, F16L37
|
E21B 33/03, F16L 37/00B
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Improved clamp and clamp supporting apparatus
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An improved clamp and clamp supporting apparatus includes a clamp (12) of semicircular arcuate segments (12a, 12b) with enlarged ear portions having bolt studs (40) positioned thereon in a staggered pattern. Through holes are drilled in the ear portions in a complementary pattern to receive the bolt studs (40) of adjacent clamp segments (12a, 12b) with nuts (42) threaded thereon to secure the clamps around abutting clamp hubs and maintain the hubs in sealed relationship. One of the clamp hubs has paired guide rods (16, 18) extending therefrom on opposite sides engaging mating holes in the clamp to allow positioning the clamp in a desired position without requiring additional support means.
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BackgroundThis invention concerns a device for supporting a connection apparatus of the type often used in the oilfield industry for connecting tubular members in sealed relationship. These connection apparatuses are referred to as clamps and are used in a variety of applications such as connecting valves to outlets of wellhead housings, connecting wellhead housings in series in vertical relationship and connecting large pressure control devices known as blowout preventers in end-to-end relationship. These clamps are preferred over conventional bolted flange connections in many situations as they require a fewer number of bolts to be tightened and are therefor usually quicker to install or remove. In the larger sizes however, these clamps are heavy and unwieldy and require some additional means for supporting them in a preferred position during installation. Previously, such means have included ad hoc methods as supporting the clamps with a fork truck or using various rigging arrangements with cables or straps supported by whatever hoisting equipment was available. These methods have proven unacceptable as the surrounding structure of the wellhead or blowout preventer interfered with the rigging arrangement or use of the fork truck. Additionally, these installations must often be done in hostile weather environments or underwater which impose even more problems in handling these large connecting structures. This invention is for an apparatus which supports a clamp on one hub of a clamp type connection to facilitate installation and removal of the clamp. The invention also has a unique configuration for the bolts used to hold the clamp in its clamped position which allows a greater number of smaller bolts to be used on a clamp -of conventional configuration. This use of smaller bolts allows lighter, easier to handle wrenching means to be used. Prior clamp connections include the J. D. Watts et al. U. S. Patent No. 2,766,829 which discloses a clamp of the type whose installation the present invention is intended to facilitate. A seal ring typically used with this type of connection is also disclosed. The R. L. Crain et al. U. S. Patent No. 3,403,931 shows a modification to the clamp of Watts whereby an axially extending shallow groove is cut in the clamp halves to allow flexure of the clamp body to better distribute the stresses developed in the clamp body during installation. Another form of clamp connection is disclosed by B. Saunders in pending U. S. Patent Application 07/458,957 filed December 29, 1989 and assigned to the same assignee as the present application. This clamp connection uses a plurality of collet segments urged into engagement with hubs configured to receive them by a pair of cam rings operated by axially disposed bolting means. No means for holding the segments or cam rings during installation or removal is disclosed. Such holding means are however known from GB-A-2208532, which shows a fluid conduit connection apparatus according to the preamble of claim 1. In this prior reference, the holding means are secured to a structure which is fixed relative to the hub but which is different therefrom, and remote from the clamping means, which renders difficult any coupling operation. An object of the present invention is therefore to provide an apparatus which facilitates the installation and removal of large clamps typically used in the oilfield industry. Another object of the invention is to provide a supporting apparatus for clamps which requires only minimal modification of existing clamp hub configurations and does not interfere with the normal operation of the clamp. A further object of the present invention is to provide a novel configuration for the bolting arrangement on a clamp required to maintain the clamp secured on the clamp hubs in order to reduce the size and weight of the wrenching means typically required to install these clamps. A still further object of the present invention is to provide a clamp hub connection wherein the clamp segments, studs and nuts are retained on one hub to eliminate any loose pieces. Accordingly, the fluid connection apparatus of the present invention is disclosed in claim 1. Brief Description of the DrawingsThese and other objects and advantages of the present invention are set forth below and further made clear by reference to the drawings wherein: FIGURE 1 is an elevation view, partly in section, of the clamp supporting apparatus supporting the clamp on the lower clamp hub of a blowout preventer which is suspended over a mating clamp hub on a wellhead connector. FIGURE 2 is an elevation view of the clamp supporting apparatus with the blowout preventer hub connected to the wellhead connector hub by the clamp. FIGURE 3 is a sectional view taken along lines 3-3 of FIGURE 1 of the clamp supporting apparatus and clamp in the fully open position. FIGURE 4 is a sectional view taken along lines 4-4 of FIGURE 2 of the clamp supporting apparatus and clamp in the fully closed position. FIGURE 5 is a sectional view taken along lines 5-5 of FIGURE 4 showing details of the bolt stud arrangement on the bolting lugs. Description of the Preferred EmbodimentWith reference to FIGURE 1, the improved clamp and supporting apparatus is denoted generally by numeral 10 and is composed of clamp assembly 12 and guide rods 14. Guide rods 14 have external thread 16 formed at their inner end and wrenching flats 18 at their outer end as seen in FIGURES 3 and 4. Guide rods 14 are disposed horizontally in tapped holes 20 in the enlarged portion 22 of clamp hub 24 to support clamp assembly 12 in its open position. Clamp hub 24 is disposed on the lower end of blowout preventer 26 with a similarly shaped clamp hub 28 on the upper end thereof. Wellhead connector 30 sealingly engages hub 32 of wellhead housing 34 in a manner well known to those skilled in the art. Clamp hub 36 is disposed on the upper portion of wellhead connector 30 and is of the same size as clamp hub 24 for engagement therewith. Seal ring 38 is placed within clamp hub 36 before hub 24 is lowered into position thereon. Clamp assembly 12 is composed of arcuate clamp halves 12a and 12b and suitable bolting means as studs 40 and nuts 42. Clamp halves 12a and 12b are semicircular in plan view as best seen in FIGURES 3 and 4 with bolting ears or lugs 44 disposed at each end. Clamp halves 12a and 12b are mirror images of one another differing only in the arrangement bolt studs 40 on bolting lugs 44. As best seen in FIGURE 5, clamp halves 12a and 12b have tapered internal profiles 46 and 48, respectively, which engage complementary profiles 24a and 36a of hubs 24 and 36. When nuts 42 are tightened on studs 40 to the position shown in FIGURE 4 the sealed connection shown is established. Seal ring 38 is held in position by the engagement of clamp hubs 24 and 36 in a manner well known to those skilled in the art. Studs 40 are arranged in a staggered pattern as best seen in FIGURE 5. Each bolting lug 44 has three studs 40 engaged in drilled and tapped holes 50 and three drilled through holes 52 as shown with the pattern in clamp half 12a being a mirror image of the pattern of clamp half 12b. The drilled holes 52 on a given bolting lug 44 of a clamp half as 12a receives the studs 40 of its mating clamp half 12b. This staggered arrangement of holes 52 and studs 40 allows a closer spacing of the bolting means, thereby allowing a larger number of smaller studs for a clamp of a given size. Each stud 40 has cross drilled holes 54a and 54b therein for purposes to be explained hereinafter. A typical sequence of operations for use of the improved clamp and supporting apparatus 10 would be as follows. Guide rods 14 are installed in hub 22 as seen in FIGURE 1 with clamp assembly 12 supported thereon. FIGURE 3 shows this assembly in plan view with clamp halves 12a and 12b in the fully open position to allow clearance for installation over mating hub 36. A cotter pin 56 or piece of welding rod (not shown) may be inserted in holes 54a and 54b to ensure nuts 42 are not removed from studs 40 and clamp halves 12a and 12b cannot be prematurely moved to a closed position. As previously noted, seal ring 38 is placed within the bore of mating hub 36. Blowout preventer 26 is lowered into position atop wellhead connector 30 with hubs 22 and 36 in face to face contact. Cotter pins 56 are removed from holes 54b thereby allowing clamps halves 12a and 12b to be manually positioned on guide rods 14 with internal profiles 46 and 48 contacting complementary profiles 24a and 36a of hubs 24 and 36. Nuts 42 can then be tightened on studs 40 to the position shown in FIGURES 2 and 4 by suitable wrenching means, not shown. If desired, guide rods 14 can be removed using wrenching flats 18. When removal of clamp assembly 12 is required, guide rods 14 can be reinstalled in tapped holes 20 of hub 22. Nuts 42 can then be loosened and unscrewed to a position adjacent holes 54a. Clamp halves 12a and 12b are then manually guided on guide rods 14 to a position as shown in FIGURE 3 and cotter pins 56 placed in holes 54b to maintain the clamp halves in the full open position while the blowout preventer 26 is lifted from wellhead connector 30. Reassembly is then accomplished as previously described. If an operator desires to use the improved clamp support appartus with a clamp of conventional configuration, i. e., without the improved staggered bolting means configuration, the following steps are required. The hub that is to support the clamp during installation must have holes drilled and tapped therein in the parallel configuration as shown in FIGURE 3 and 4. Guide rods can then be installed therein as on the preferred embodiment. The clamp halves to be installed can be drilled with holes in a parallel configuration through the clamp body complementary to the placement of the guide rods in the hub. The clamp halves can then be supported on the guide rods for installation in the manner described for the preferred embodiment. It should be noted the scope of the invention is not limited to the hubs and clamps lying in a horizontal plane as described for the preferred embodiment. The scope of the invention encompasses embodiments in which the hubs and clamps lie in a vertical plane as well as a horizontal plane or any position therebetween. Additionally, the scope of the invention includes embodiments in which there are more than two arcuate segments to the clamp body.
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A fluid conduit connection apparatus, in particular for use in the oilfield industry, comprising : a first hub (24), a second hub (36), a sealing means (38) disposed between said hubs, a clamping means (12) for retaining said hubs in abutting sealed relationship, and a support means (14) for maintaining said clamping means in a disengaged open position prior to installation and guiding said clamping means from said open position to a clamped position, characterized in that said support means includes a plurality of rods (14) positioned on either of said first and said second hubs and extending transversely from said hub, said rods being of sufficient length to support said clamping means (12) in said open position prior to installation. A fluid conduit connection apparatus according to claim 1, wherein said clamping means includes : a plurality of arcuate clamping segments (12a, 12b) surrounding said hubs, said clamping segments having an internal profile (46, 48) for mating with an external profile (24a, 36a) on said hubs (24, 36), said segments having a lug (44) at each end with bolting means (40) disposed thereon, and said bolting means cooperating with the lug of said adjacent segments (12a, 12b), to secure said hubs in abutting relationship. A fluid conduit connection apparatus according to claim 2, wherein : said guide rods (14) extend through openings in said arcuate clamping segments. A fluid conduit connection apparatus according to claim 3, wherein : said guide rods (14) threadedly engage said hub, and said guide rods are removable from said hub when said clamping segments are in clamping engagement with said first and said second hub profiles. A fluid conduit connection apparatus according to claim 4, wherein : the number of arcuate clamping segments (12a, 12b) is two, and said guide rods are parallel to said bolting means (40). A fluid conduit connection apparatus according to anyone of claims 1-5, wherein : said hubs comprise abutting tubular members having enlarged end portions with tapered backfaces ; said clamping means comprise a pair of clamp halves (12a, 12b), with a complementary internal profile (46, 48) which engages said backfaces ; said clamp halves (12a, 12b) have a lug at each end; a bolting means (40) disposed on each lug (44) cooperates with a lug of said opposite clamp half to secure said end portions in abutting relationship ; and said unclamped position of said clamp halves is a planar position. A fluid conduit connection apparatus according to claim 6, wherein said bolting means includes: a plurality of threaded studs (40) engaging threaded holes in said lugs, said studs (40) being disposed in staggered relationship on said lugs (44), to minimize spacing between adjacent studs, said lugs (44) having mating holes in complementary staggered relationship to the studs of a mating lug, said mating holes receiving said studs when said clamp halves (12a, 12b) are in clamping engagement with said enlarged end portions, and said clamp halves are retained in clamping engagement by threaded nuts (42) engaging said studs. A clamping apparatus according to claim 7, wherein : said studs (40) are of sufficient length to permit said clamp halves to be opened to a position allowing their installation over said enlarged portion while said studs are in engagement with said lugs, and said studs have means thereon for holding said clamp halves (12a, 12b) in their open position. A clamping apparatus according to claim 8, wherein : said guide rods extend through said clamp halves and threadedly engage said enlarged portion of said tubular members.
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COOPER CAMERON CORP; COOPER CAMERON CORPORATION
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HYNES JOSEPH H; HYNES, JOSEPH H.
|
EP-0489645-B1
| 489,645 |
EP
|
B1
|
EN
| 19,980,812 | 1,992 | 20,100,220 |
new
|
H04M11
|
H03G3, H04B3
|
H03G1, H04M3, H04M1, H03G3, H04Q11
|
H04M 3/40, H03G 3/00D, H03G 3/20B8, H04M 1/253, H04Q 11/04S1T, H03G 1/00B8, H04M 3/22S, T04Q213:096, T04M3:56, T04Q213:190
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Voice level controller
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A voice level controller comprises a discriminator for determining whether speech is done through an analog line or not, and a control circuit (16) for controlling a speech level in accordance with the output of the discriminator.
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BACKGROUND OF THE INVENTIONField of the InventionThe present invention relates to an apparatus for controlling a level of voice received from a digital network.Related Background ArtPresent days, there are a PSTN network which is an analog network and an ISDN network which is a digital network, and they interwork. In the PSTN network which is the analog network, a sending signal and a received signal are in the same voice band and the PSTN network which accommodates a subscriber uses a 2-4 line converter to separate the sending signal and the received signal.However, since it is difficult to completely separate the sending signal and the received signal by the 2-4 line converter, a howling sound is generated unless a loss is inserted to lower a voice level.SUMMARY OF THE INVENTIONIt is an object of the present invention to enable hearing of a received voice at a preferred voice level without regard to the type of network connecting a calling station.It is another object of the present invention to enable hearing of the received voice at the preferred voice level whether an analog network connecting the calling station is present or not.Other objects of the present invention will be apparent from the following description of the embodiments of the present invention. To this end, the present invention proposes a voice lever controller, as claimed in claim 1, and a method for controlling a level of speech signals exchanged with a communication partner, as claimed in claim 6. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a circuit diagram of a telephone set having a speech level controller in accordance with the present invention;Fig. 2 shows a configuration of a network;Fig. 3 shows a flow chart of an operation of the apparatus of Fig. 1;Fig. 4 shows a format of a progress identifier information element; and Fig. 5 shows an assignment of progress content . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSAn embodiment of the present invention is now explained with reference to the drawings.Fig. 2 shows a network configuration in which a PSTN network and an ISDN network interwork. Numeral 1 denotes an analog telephone set, numeral 2 denotes a subscriber line, numeral 3 denotes a PSTN network, numeral 4 denotes a 2-4 line converter, numeral 5 denotes an internetwork base transmission line, numeral 6 denotes an ISDN network, numerals 7 and 70 denote ISDN lines, and numerals 8 and 80 denote digital telephone sets having speech level controllers in accordance with the present invention.An operation of the network of Fig. 2 is now explained. The telephone set 8 is connected to the telephone set 80 through the ISDN network 6 and the ISDN lines 7 and 70 so that the telephone sets 8 and 80 communicate by a digital signal. In this case, a digital 1 link is formed and a loss of voice does not take place on the network 6 or the lines 7 and 70.The PSTN network 3 which is the analog network and the ISDN network 6 interwork by a digital signal through the internetwork base transmission line 5. The analog telephone set 1 is connected to the PSTN network 3 through the subscriber line 2 and the 2-4 line converter 4. Because the analog telephone set 1 is accommodated in the PSTN network 3, a level loss L1 on the subscriber line 2 and a level loss L2 on the 2-4 line converter 4 take place. L1 is in the range of 0 to 7 dB, and 3 to 4 dB in average while L2 is approximately 8 dB. Thus, L1 + L2 is 14 to 16 dB in average. The telephone set 8 accommodated in the ISDN network 6 may communicate with both the telephone set 80 accommodated in the ISDN network 6 and the telephone set connected to the PSTN network 3. There is a voice level difference of 14 to 16 dB between the telephone sets 8 and 80 and between the telephone sets 8 and 1. In the present embodiment, the voice level difference between the telephone sets 8 and 1 is eliminated in the telephone set 8.Fig. 1 shows a circuit diagram of a digital telephone set having a speech level controller in accordance with the present invention. Numeral 11 denotes an ISDN line, and numeral 12 denotes a line interface which is an interface to the ISDN line 11. The line interface 12 sends and receives a D channel control signal through a signal line 13, sends a B channel signal through a signal line 14 and receives a B channel signal through a signal line 15. Numeral 16 denotes a control unit which controls the overall system. It is connected to the line interface 12 through the signal line 13 through which a call control signal (D channel control signal) is exchanged. Numeral 17 denotes a codec for converting an analog signal to a digital signal, and numeral 18 denotes a codec for converting a digital signal to an analog signal. Numerals 19 and 20 denote amplifiers, numerals 21 to 24 denote signal lines, numeral 25 denotes a hand set, numeral 26 denotes a receiver of the hand set 25, and numeral 27 denotes a transmitter of the hand set 25.A signal a from the codec 18 is supplied to the amplifier 20 through the signal line 22, and a signal b from the amplifier 20 is sent to the receiver 26 of the hand set 25 so that the receiver 26 reproduces the voice. On the other hand, a signal c inputted from the transmitter 27 of the hand set 25 is sent to the amplifier 19, and a signal d from the amplifier 19 is supplied to the codec 17 through the signal line 21. The amplification factors of the amplifiers 19 and 20 are controlled by signals e and f supplied from the control unit 16 through the signal lines 23 and 24.The operation of the telephone set of Fig. 1 is now explained with reference to Figs. 3 to 5. Fig. 3 shows a flow chart of a send process of the digital telephone set. When an operator dials to request a call (step S1), the line interface 12 (Fig. 1) sends to the ISDN line 7 (Fig. 2) an SETUP message as the D channel information in accordance with a command from the control unit 16 (Fig. 1) (step S2). In response thereto, the ISDN network 6 sends back a CALL PROC message (step S3). The control unit 16 controls the two amplifiers 19 and 20 to connect the speech path in accordance with a progress identifier information element contained in the CALL PROC message. A format of the progress identifier is shown in Fig. 4. Horizontal numerals 1 to 8 indicate bits. The progress content in octet 4 has an assignment as shown in Fig. 5, in which non-ISDN network is assigned to #1 - #3. Thus, when the progress content of the progress identifier is #1, #2 or #3, the control unit 16 increases the amplification factor (step S5), and when it is #4 or #8 which indicates the end-end of the digital network, the control unit 16 sets the amplification factor to a normal level (step S6). Alternatively, when the progress identifier is #1, #2 or #3, the amplification factor may be set to the normal level, and when it is #4 or #8, the amplification factor may be lowered. Further, the digital signal before the conversion to the analog signal may be level-shifted in accordance with the progress identifier . When a called station is later connected, an ALERT message is sent from the network 6 (step S7), and when the called station responds, a CONNECT message is sent from the network 6 (step S8) so that the speech status is established (step S9).In case that the progress identifier is not contained in the CALL PROC message, it is contained in the ALERT or CONNECT message. Thus, the decision of the step S4 is made each time the message is received.In the receiving mode, the progress identifier is contained in the ALERT message.In the present embodiment, the speech level controller in the telephone set has been described. Alternatively, the speech level may be controlled in a key telephone set or a PBX which accommodates the ISDN line.When the present invention is applied to the PBX, the speech level control may be used to automatically set a constant speech level when a call from an external line is transferred to another external line or when a conference speech with two external lines and one internal line is made.While preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment but various modifications thereof may be made without departing from the scope of claim.
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A voice level controller comprising: connecting means (12, 17, 18) for connecting a receiver (26) and a transmitter (27) for exchanging speech signals with a communication partner to a digital communication line (11), andcontrol means (16, 19, 20) for controlling a level of the speech signals exchanged with the communication partner, characterized in thatsaid control means is adapted to control the level of the speech signals in accordance with a progress identifier information signal received from the communication line, the progress identifier indicating whether or not the communication partner is connected to an analog network.A controller according to claim 1, wherein said control means raises the level in a case where the communication partner is connected to the analog network (3).A controller according to claim 1, wherein the communication line is connected to a digital network (6).A controller according to claim 1, wherein said control means further comprises conversion means (18) for converting a digital speech signal supplied from the communication line into an analog speech signal and controlling the speech level of the analog speech signal.A controller according to claim 1, wherein the communication line is connected to an ISDN.A method for controlling a level of speech signals exchanged with a communication partner, characterized by the steps of: analyzing (S4) a progress identifier information signal supplied from a digital communication line, the progress identifier indicating wherher or not a communication partner is connected to an analog network; andcontrolling (S5, S6) the level of the speech signals exchanged with the communication partner in accordance with the analysis in said analysis step.A method according to claim 6, wherein, in said controlling step (S5), the speech level is raised in a case where the communication partner is connected to the analog network.A method according to claim 6, wherein, in said controlling step (S6), the level of the speech signal supplied from a digital network is controlled.A method according to claim 6, wherein said controlling step further comprises a step of converting a digital speech signal from a digital network into an analog speech signal, and a step of controlling the speech level of the analog speech signal.A method according to claim 6, wherein, in said controlling step, the level of the speech signal supplied from an ISDN is controlled.
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CANON KK; CANON KABUSHIKI KAISHA
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HIRATA OSAMU; HIRATA, OSAMU; Hirata, Osamu, c/o Canon Kabushiki Kaisha
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EP-0489657-B1
| 489,657 |
EP
|
B1
|
EN
| 19,950,802 | 1,992 | 20,100,220 |
new
|
C09C3
|
C09C1
|
A61Q1, C04B14, A61K8, C09C1, C09C3
|
C09C 1/00F, A61K 8/11C, M01P4:61, M01P6:90, A61K 8/44, A61Q 1/10, C09C 3/08, K61K201:021, M01P4:82, M01P4:84, M01P4:20, C09C 1/00F2, C09C 1/00F10, M09C200:40D8B
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Improved platy pigments
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Platy pigments with good tactile characteristics are obtained by treating such pigments with a compound of the general formula: where m is an even number from 8 to 18 and n is 3 or 4 under defined conditions. Nε-lauroyl lysine is preferred. The pigments are especially useful in cosmetic compositions such as eye shadow.
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BACKGROUND OF THE INVENTIONDuring the past decade, attempts have been made to improve the tactile or feel characteristics of powders and of solid compacts intended for cosmetic makeup purposes in the eye region and on the face. The general approach has been to treat the surfaces of the major pigments in these formulations. Treatment also was intended to improve the dispersion or the compatibility of the pigment in the compact formulation. Compact formulations containing largely platy pigments or extenders such as mica already had reasonably smooth and soft tactile properties, due to the flat or platy shape of the pigment particles. However, it was recognized that these pigments could also be improved by treatment. Talc, a platy extender frequently used in compact formulations, showed several disadvantages. The softness of talc contributed to its ease of breaking up physically so that the platy character would be substantially decreased or lost. The softness of the talc also contributed to its hard compaction when subjected to pressure, so that pay-off of the formulation in use became low. Mica, as an extender in these compact formulations, was found to overcome some of the disadvantages of the talc. Mica, as a harder material but still platy in shape, resists being broken up physically. It also has some resistance to compaction, so that by adjusting the binder formulation of the compact, a reasonably soft compact is attainable along with good pay-off. The outer structure of human skin is a mosaic of hydrophilic and hydrophobic areas. The best tactile effects, or the best smoothness and softness, are attained with the coating of pigment surfaces with compounds that have a hydrophile-hydrophobe balance similar to human skin, and with compounds that have some chemical relationship to skin. Mica, as well as some of the metal oxide coated mica pigments used as pearlescent and color interference type pigments in compact and powder formulations, may have more surface hydrophilic character than is desirable for good tactile qualities on the skin. This means that the surface of the mica or of the platy pigment may have some drag in being applied to the skin. The hydrophile-hydrophobe balance of the pigment surface should be shifted. This is done with appropriate treatment of the pigment surfaces. The treatment consists of coating the surfaces of the pigment with a suitable compound. In many cases, the compounds or agents used have shifted the hydrophile-hydrophobe balance very strongly toward hydrophobic. This is neither desirable nor necessary. Compounds that have been used for pigment surface treatment include silicones, silanes, siloxanes, fatty acids, chemically modified polyolefins, and fatty acid triglycerides (fats). These generally cause a large shift towards hydrophobic character and therefore, less than desirable tactile qualities. Others have been used that are substantial improvements over the above group. They include amino acid derivatives, lecithin, sarcosine derivatives, and others based on derivatives of natural products. The hydrophile-hydrophobe shift is modest towards hydrophobic and desirable. The tactile qualities are improved. However, in some cases, rancidity may result from the oxidation of some unsaturated fatty acid components. The solubilities of some of these compounds in components of the binder formulation may be substantial, leading to removal of some of the compound from the pigment surface. Mechanical treatment in the course of preparing the formulation for compaction may result in mechanically removing some of the treatment compound from the pigment surface. Finally, the adherence or adsorption of the treatment compound to the pigment surface is questionable, so that migration of the compound away from the pigment surface may take place with time. European Patent Publication No. 139,481 of May 2, 1985 discloses methods for treating inorganic pigments with N-mono-acylated basic amino acids containing long chain acyl groups, e.g., Nε-lauroyl-L-lysine. The publication states that any dry or wet procedure may be used. The dry procedure involves dry blending of the components. A wet procedure involves dissolving the treatment compound in an organic solvent, using calcium chloride as a solubilizing agent, bringing the inorganic pigment into contact with the solution and then washing the mixture with water to remove calcium chloride. An alternative wet procedure involves dissolving the treatment compound in an aqueous alkali or an aqueous solvent, bringing the inorganic pigment into contact with the solution, neutralizing the mixture, precipitating and adhering the treatment compound to the pigment surface, washing with water and drying. It is implied that the alternative methods yield equivalent products. Of the three methods disclosed, the dry blending method is shown in Example X, infra, not to yield a satisfactory product; the only solvent mentioned in connection with a wet method is calcium ethylate, the use of which is expensive and impractical; and the alternative wet method suggested is not disclosed with sufficient particularity to enable it to be successfully practiced. It is an object of the invention to provide an improved method for producing a treated platy pigment with improved tactile characteristics and with good adherence of the treatment material to the pigment surface. Other objects of the invention will become apparent from the following description. SUMMARY OF THE INVENTIONWe have found that the objects of the invention may be achieved by precipitating a compound of the general formula where m is an even number from 8 to 18 and n is 3 or 4, onto the surface of a platy pigment. The precipitation is accomplished by adding an acid or alkaline solution of the compound of that formula to an aqueous dispersion of the platy pigment, the amount of the solution being such as to supply that compound in an amount of about 0.5-5.0% by weight of the pigment, at a rate within the range of about 0.10-1.50 mg. per gram of pigment per minute, adding alkali or acid as required to bring the pH of the resulting mixture to between 1 and 8, and recovering the platy pigment coated with said compound, as by allowing it to settle, washing it, concentrating it by centrifuging or filtration and then drying it. Although racemic mixtures of the D and L forms of the compound can be used, the stereoisomeric forms wherein the structure is entirely D or L are greatly preferred for better crystallinity and greater insolubility. The treatment is preferably carried out at a temperature between about 15° and 80° and the pH of the resulting mixture is preferably brought to about 2.5 to 5.0. It is further preferred that the treatment be carried out in the presence of a calcium salt, e.g., calcium chloride, which is suitably present in the range of about 0.25-1.0 mole per mole of treatment compound. The preferred treatment compound is Nε-lauroyl-L-lysine and the compound which is entirely either the D or L isomer is most preferred. The coated platy pigment is preferably recovered by allowing it to settle, washing it, concentrating it by centrifugation or filtration and then drying it. The resultant treated pigment is markedly improved in its tactile (or feel) characteristics, which is particularly advantageous for cosmetic formulations, especially for powder or pressed compact types in the eye region in particular, and on the skin in general. The treatment, with some variations, is applicable to platy pigments in general, including mica, talc, titanium dioxide coated mica, iron oxide coated mica and chromium oxide coated mica. It also can be used for the more complex interference type colorants based on titanium dioxide coated mica such as those containing carmine or iron blue, as well as those containing laked forms of D&C or FD&C colorants disclosed in US-A-4,968,351. However, the treatment would seme little purpose applied to platy pigments which already have good tactile properties and disperse well in hydrophobic systems. An example of such pigment is bismuth oxychloride. In the case of certain coated pigments, e.g,, mica coated with iron oxide, titanium dioxide or chromium (III) oxide, the pigment is treated with a polyvalent metal compound, e.g., such as a hydroxide or a compound hydrolyzable to a hydroxide, aluminum chloride for titanium dioxide coated mica, ferric chloride for iron oxide coated mica and chromium III chloride or sulfate for chromium oxide coated mica before or during the addition of the treatment compound. A preferred platy pigment product of this invention, which has improved tactile, dispersion and stability properties, comprises a Nε-lauroyl-L-lysine substrate of platelets of mica, talc or metal oxide coated mica, the platelets having a particle size in the range of about 2-80 microns, and an average particle size of about 5-40 microns, the Nε-lauroyl-L-lysine coating being present on the surface of the platelets in the range of about 0.5% to 5.0% by weight of the platelets, and at least 80% of the coating remaining adhered to the substrates after four centrifugations, each centrifugation being carried out on a dispersion of 1.00 g. of the platy pigment in 75 ml. of distilled water. The substrate may be talc, wet ground Indian mica, iron oxide coated mica, titanium dioxide coated mica, or chromium oxide coated mica. The titanium oxide coated mica may be further coated with a dye or pigment, e.g., carmine, a laked dye or ferric ferrocyanide. Where an organic colorant is used, it may be deposited concurrently with Nε-lauroyl-L-lysine. Another feature of the invention is cosmetic compositions containing the improved platy pigments in combination with cosmetically acceptable ingredients, especially powders and compacts intended for cosmetic makeup purposes in the eye region or the face, such as pressed powder eye shadow compositions. DETAILED DESCRIPTION OF THE INVENTIONFor a number of reasons, treatment with the compounds of the above given general formula, Nε-lauroyl-L-lysine in particular, overcomes the various shortcomings of the prior art surface treatments. The following properties of Nε-lauroyl-L-lysine are significant in distinguishing this compound from others hitherto used for pigment surface treatment: (1) It is a pure compound chemically. (2) It is stereochemically a pure compound. (3) It is very insoluble in nearly all solvents. (4) It is a distinctly crystalline compound stable up to high temperatures (∼300°C). A discussion of the unique character of this compound is in order. Nε-lauroyl-L-lysine is synthesized from lauric acid and L-lysine; both raw materials are very pure compounds. L-lysine is the result of a biological reaction, so the compound is entirely in the L-stereoisomeric form. L-lysine has 2 amino groups, one in the α-position and the other in the ε-position. The reaction to form Nε-lauroyl-L-lysine is carried out so that both the reaction to form the peptide linkage is entirely with the ε-amino group, and the stereoisomeric structure of the lysine portion is maintained. Thus, the Nε-lauroyl-L-lysine is obtained, a compound of specific stereostructure, high crystallinity, great stability even up to 300°C, and insoluble in nearly all solvents. The chemical structure is such that both hydrophilic and hydrophobic groups are evident. The hydrophilic groups may serve in part to assist the adsorption and crystal growth of the compound on to the mica platelet surface. The insolubility and inertness of Nε-lauroyl-L-lysine limits its potential for use by precipitation from solution. It is virtually insoluble in all common organic solvents. It is soluble in mineral acids. It can be dissolved in 1.0 N HCl at elevated temperature and in concentrated HCl at room temperature. Solutions in alkali are more convenient as the solubility is greater; 1.0% solutions in 0.5 N NaOH are easily attainable. Since the Nε-lauroyl-L-lysine is insoluble in aqueous solution except under the strongly acid or alkaline conditions, the precipitation of the compound on a platy pigment can be carried out by adding either an acidic or alkaline solution of the compound to an aqueous reservoir with stirring, in which the platy pigment is dispersed. Alkali or acid is then added to bring the pH into the range of 1-8 and preferably near about 2.5-5.0. The reaction can be carried out at ambient temperature. The compound precipitates out of solution and, under the conditions of the reaction medium, on to the platy pigment surfaces. The pigment is allowed to settle, is washed several times, concentrated by centrifuging or filtration, and finally dried by any of a number of methods. In some cases, the precipitation of the compounds is carried out with a calcium salt in the stirred aqueous reservoir. Calcium chloride is the convenient salt, present in the reservoir within the range of about 0.25-1.0 mole, preferably at about 0.5 mole, for each mole of Nε-lauroyl-L-lysine added. A salt with the compound is essentially not formed. The effect of the calcium chloride is a salting out effect. That is, the salting out may speed up or facilitate the precipitation, and it beneficially affects the character of the precipitate and the treated pigment. The compound is deposited, at concentrations in the range of about 0.5% - 5.0%, on the pigment, preferably in the concentration range of about 2.0% - 4.0%. Variables in the several procedures include pH, temperature, concentrations, and addition rates. The mica substrate is usually a wet ground mica with particle size in the range of about 2-100 microns. Usually, for cosmetic ingredient purposes the mica is fractionated into relatively tight ranges of particle size distribution. Common ranges are 5-25 microns with 10 micron average, 1-45 microns with 20 micron average, 20-70 microns with 45 micron average, and 15-90 microns with 50 micron average. All are suitable substrates, but in terms of tactile smoothness, the larger particles within these ranges are less desirable. The pH of the solution during lauroyl lysine addition can be varied or held constant over the range of 1-8. The preferred pH range is about 2.5-5.0, both for constant pH procedures and for procedures of variable pH starting low and ending up at pH 2.5-5.0. Temperature is essentially not critical in that any temperature from about 15°C to 80°C can be used. Since there are usually no advantages at high temperatures, it is more convenient to use ambient temperatures, or about 15° - 35°C, preferably about 20° - 30°C. Mica as a substrate is generally dispersed in the aqueous medium at about 20% wt./wt., before the start of the treatment reaction. The mica cannot form a good dispersion and cannot be stirred adequately if the concentration is much higher. 24% wt./wt. can be taken as about the upper limit of concentration. On the other hand, the mica can be as dilute as 4% wt./wt. There is no product quality advantage and the yield of product, based on total batch size, would be quite small. Mica concentration can therefore be in the range of about 4% - 24% wt./wt., and preferably about 10% - 20% wt./wt. These concentration ranges are also applicable to laked dye coated titanium dioxide coated mica. Iron oxide, titanium dioxide or chromium (III) oxide coated mica concentration can be in the range of about 5-15%, preferably about 7-12% wt./wt. Other substrates, such as talc, are more sensitive to substrate concentration and are generally in the range of about 7.5% - 10.0% wt./wt. However, any concentration within the range of about 5% - 15% wt./wt. may be employed, preferably the range of about 7% - 12% wt./wt. The critical rate in all procedures is that of the lauroyl lysine solid addition rate per weight of substrate in the reservoir. These rates can be within the range of about 0.10 - 1.50 mg. lauroyl lysine per g. substrate per minute. However, the extremes are inconvenient in that the times and/or concentrations become too high or too low for convenience. The preferred rate range is about 0.15 - 1.0 mg. lauroyl lysine per g. substrate per minute. Rates are not varied in general during the treatment procedure, so that lauroyl lysine concentration (wt. per wt. substrate) is not a factor. The final treated powders are evaluated in three ways: tactile properties, adhesion to substrate, and dispersion properties. Most important is tactile quality, which is determined by comparison testing on the skin, using control samples as well as the untreated pigment. Substantial improvement in smoothness and softness on the skin is to be expected, comparable to the untreated platy pigment and as good as, or slightly better than other platy pigment samples that received treatments with other compounds. The treated platy pigment is more hydrophobic than the untreated pigment. The dispersion is improved in going to more hydrophobic solvents, i.e., butanol to butyl acetate to toluene. The improvement in tactile character and the increased hydrophobicity depend largely on the chemical structure of the treating compound and how it is oriented on the surface of the platy pigment. While the Nε-lauroyl-L-lysine can easily be made very insoluble, nevertheless, the compound must precipitate, and adhere to the substrate pigment surface. The process of the present invention results in a high degree of adherence of the compound to the pigment surface. It has been found that different pigment surfaces vary widely in the extent of acceptance of the treating compound to the pigment surface. Coating and adhesion to the substrate pigment surfaces can be improved by adjusting the treatment condition variables such as pH profile, salt content, rates of addition of reactants, and temperature. In some cases, the substrate pigment surface remains unreceptive to the treating compound and appears to reject it totally. In such cases, the platy pigment requires a pretreatment with an unrelated agent to render the surfaces more receptive. There is another category of platy pigments that would benefit from treatment with the described compound. These are the more complex interference type pigments that contain absorption colorants deposited on the platy pigment surface through a laking process. The latter involves the insolubilization of the absorption colorant and adherence to the substrate platy pigment by means of aluminum hydroxide alone, or replaced by or in conjunction with other polyvalent hydroxides of barium, calcium, zirconium, and others. These products are sensitive to variable pH conditions in solution, and the laked color may be altered, partially removed, or otherwise damaged by the later procedure involving the deposition of Nε-lauroyl lysine or a homologue thereof. It has been found that the treatment with such compounds can be included in the laking process for the absorption colorant. These include absorption colorants such as carmine, ferric ferrocyanide, D&C colors and FD&C colors. While the pigment treatment is limited to those of platy shape or structure, the invention is not limited to only those pigments given in the examples. While Nε-lauroyl-L-lysine is here exemplified as the treating compound, the invention is not limited to this compound, and those of related chemical structure, such as Nε-lauroyl-L-ornithine, can be used as well. The compounds which are contemplated are those of the general formula appearing above. The process of this invention is illustrated by the following examples. EXAMPLE IWet Ground Indian Mica Coated with 4.0% Nε-Lauroyl-L-LysineIndian mica is wet ground, followed by extensive classification by settling in water to remove fine and coarse particles. The resultant fraction has an average platelet particle size of 10 microns, and 95% of the platelets are within the range of 4-32 microns (in length). 150 g. of this mica is slurried in 600 ml. of distilled water in a 2.0 liter beaker. 25 ml. of concentrated HCl are added and the suspension is stirred with power from a small motor, for 10 minutes. 1.68 g. of CaCl₂.2H₂O are added as a solid and the suspension is stirred for 10 minutes to allow for dissolution. A solution of 6.0 g. of Nε-lauroyl-L-lysine in 579 ml. of 0.50 Normal NaOH is prepared. This solution is added to the mica slurry at the rate of 4.8 ml. per minute until it is used up, ambient temperatures being maintained. This requires 2.0 hours in time. The final pH is 4.0, or adjusted to this pH, if necessary. The product is filtered on a Buchner funnel, and the filtrate is washed 4 times each with 400 ml. of distilled water. The filter cake is dried in an air oven overnight at 95°C. The dried cake is screened through a 200 mesh screen. Analyses show that practically all of the Nε-lauroyl-L-lysine has been precipitated on the mica surfaces, at 4.0%. The calcium chloride was used at 0.63 moles per mole of the Nε-lauroyl-L-lysine, yet very little calcium is found by analysis of the coated product. Thus, the calcium salt acts to reduce further the solubility of the compound used for treatment. Settling tests in a set of organic solutions carried out with the treated mica, as well as the original untreated mica separately, shows that the treated mica displays a more hydrophobic behavior compared to the original untreated mica. The treated mica sample, the untreated mica, and a sample of lecithin treated mica were each evaluated and compared for tactile properties. The untreated mica showed less smoothness and softness when spread on the skin, as well as a slight drag during spreading, compared to the two other samples. The Nε-lauroyl-L-lysine treatment of the mica yielded slightly better softness and smoothness compared to the lecithin treated mica. The treated sample was subjected to an evaluation for the adhesion of the compound to the mica substrate. 100 ml. of distilled water were added to 3.0 g. of the treated mica, dispersed, centrifuged, and the supernatant liquid separated. Washing of the settled solid in this way was repeated three more times. The sample was then analyzed for the remaining treatment compound. It was found that 92% of the treatment compound remained adhering to the mica. Analysis of the treated mica for calcium shows that very little calcium is co-precipitated with the treatment compound, so that the calcium chloride is effecting a salting out effect on the Nε-lauroyl-L-lysine. EXAMPLE IIUpscaled Coating of Wet Ground Indian Mica with 4.0% Nε-Lauroyl-L-LysineIndian wet ground mica is prepared and classified as in Example I. The Nε-lauroyl-L-lysine, 6.0 lbs., is added and dissolved in 260 lbs. of 3.50% NaOH solution. This is a 2.30% treatment solution in 3.50% NaOH. 10% HCl solution, for pH control, is prepared by adding 8.4 lbs. of 31% HCl to 17.1 lbs. of demineralized water. 800 lbs. of demineralized water are added to a 500 gallon reactor fitted with a stirrer and 2.25 lbs. of CaCl₂.2H₂O are added and dissolved. 200 lbs. of the above-prepared mica are dispersed in this solution. The temperature is adjusted to 30° ± 1°C and maintained at that temperature. The 3.50% NaOH solution, containing the treatment compound, is added at a rate of 4.7 lb. per minute, and the 10% HCl solution is added at about the same rate, or adjusted so as to maintain the pH at 6.0±0.1. 200 lbs. of the 3.50% NaOH solution containing 2.30% of the treatment compound are added in about 60 minutes. The treated mica is allowed to settle, is decanted, and the liquid is replaced with an equal volume of demineralized water. After settling, the washing process is repeated. The settled paste of treated mica is dried. The product is tested in the same way as in Example I, yielding similar results. EXAMPLE IIIWet Ground Indian Mica Coated at Constant pH to 2.0% Nε-Lauroyl-L-Lysine225 g. of mica, prepared and classified as in Example I are dispersed in 900 ml. of distilled water. The pH is adjusted to 6.0. 5.85 g. of Nε-lauroyl-L-lysine are dissolved in 562 ml, of 0.50 Normal NaOH. This solution is added to the mica suspension, with stirring, at a rate of 6.0 ml. per minute. The pH is maintained constant at 6.0±0.1 by simultaneous addition of 0.50 Normal HCl solution at such a rate so as to maintain the pH at 3.0, ambient temperatures being maintained. When 432 ml. of the 0.50 Normal NaOH solution has been added, the additions are halted. The slurry is filtered, washed 3 times with 400 ml. of distilled water, and dried overnight at 95°C. The product is tested in the same way as in Example I, yielding similar results. EXAMPLE IVTalc Treated with 3.0% Nε-Lauroyl-L-Lysine681 g. of talc (Suprafino A, Cyrus Industrial Minerals Co.) were added to 7900 ml. of distilled water and stirred vigorously to disperse well. This dispersion was carried out in a 5 gallon polycarbonate tank, fitted with baffles, a pH electrode, and a stainless steel turbine stirrer. Ambient temperature was employed. To this dispersion with vigorous stirring were added at 21 ml. per minute, a solution of 1.04% Nε-lauroyl-L-lysine in 1965 ml. of 0.50 Normal NaOH. The pH was maintained at 6.4±0.2 by the simultaneous addition of a solution of 0.28% CaCl₂.2H₂O in 2120 ml. of 0.50 Normal HCl. Upon completion of the addition, the slurry was stirred an additional 10 minutes and allowed to stand overnight. The next day a very small amount of material was floating on the top of the liquid, which was skimmed off. The bulk of the treated talc had settled, and this material after decantation, was filtered, washed with demineralized water and dried at 95°C for 4 hours. The product was sieved through a 60 mesh screen. The tactile properties were tested and found to be improved over those of the original untreated talc. Dispersion tests also showed that the treated product displayed increased hydrophobicity. Examples I to IV, above, illustrate methods useful for treating uncomplicated substrates, such as mica, kaolin, and talc. Certain more complicated pigments such as titanium dioxide coated mica with a carmine coating may also be treated in a similar way, as shown in Example V. EXAMPLE VCarmine Coated Titanium Dioxide Coated Mica Additionally Coated with 3.0% Nε-Lauroyl-L-LysineBefore carrying out the coating reaction, the solutions needed were prepared. 21.0 g. of Nε-lauroyl-L-lysine were dissolved in 2.0 liters of 0.50 Normal NaOH. 6.72 g. of CaCl₂.2H₂O were dissolved in 2400 ml. of distilled water to which had previously been added 100 ml. of concentrated HCl solution. A 5.0 gallon polycarbonate tank was fitted with baffles and a stainless steel turbine stirrer fitted with a motor drive. To this reactor were added 7.90 liters of distilled water, and 681 g. of the pigment were added and slurried in with vigorous mixing. The pigment was Cloisonne Red of The Mearl Corporation, titanium dioxide coated mica with a carmine treatment (2.0% carmine, 39% TiO₂, and 59% mica). The pigment has a red interference reflection color enhanced further by the red color of the carmine colorant treatment. At ambient temperature, the alkaline treatment solution was added at a rate of 25 ml. per minute while simultaneously maintaining the pH at 7.1±0.2 by the addition of the acidic calcium chloride solution. When the first solution was used up, the slurry was stirred an additional 15 minutes, filtered, washed three times with small volumes of distilled water, and dried overnight at 55-60°C. The product was screened through a 60 mesh sieve. The testing was done as in Example I, and the tactile properties in particular were significantly improved over the original untreated pigment. Dispersion also displayed improved color intensity and luster, compared to the original untreated pigment. Titanium dioxide coated mica, iron oxide coated mica and chromium oxide coated mica all require treatment with another compound, either before or during the lauroyl lysine addition, to effect improved adhesion to the substrate pigment surface by the lauroyl lysine. In general, a polyvalent metal hydroxide or a salt which hydrolyzes to a hydroxide during the treatment process is suitable, and the particular one selected must meet specific requirements concerning refractive index, color, and solubility. For titanium dioxide coated mica, aluminum chloride is suitable; for iron oxide coated mica, ferric chloride; and for chromium oxide coated mica, chromium (III) chloride or chromium (III) sulfate. Examples VI and VII illustrate such methods. EXAMPLE VIIron Oxide Coated Mica Treated with 3.0% Nε-Lauroyl-L-Lysine100 g. of iron oxide coated mica pigment (Matte Orange of The Mearl Corporation, 9% Fe₂O₃ and 91% mica) were dispersed in 1.0 liter distilled water in a 2.0 liter beaker fitted with an appropriate mixing device. With stirring, this solution was raised to 74°C and the pH adjusted down to 3.0 by the addition of a small amount of an acidic ferric chloride solution (2.66 g. 38% FeCl₃ and 97.34 g. 37% HCl solution). Then an alkaline solution of Nε-lauroyl-L-lysine (3.0 g. in 100 ml. of 3.5% NaOH solution) was added at 2.5 ml. per minute while maintaining the pH at 3.0±0.1 by the addition of the above acidic ferric chloride solution. After all the Nε-lauroyl-L-lysine solution had been added, the slurry was allowed to cool, was filtered, and washed with distilled water until the filtrate tested free of chloride. The product was dried at 80°C overnight and sieved through a 100 mesh screen. The ferric chloride addition results in hydrolysis to form a small amount of iron hydroxide which aids in the adhesion of the Nε-lauroyl-L-lysine to the pigment surface. Testing of this product for tactile properties and for dispersibility showed substantial improvements over the initial untreated pigment, Matte Orange. EXAMPLE VIITitanium Dioxide Coated Mica Treated with 3.0% Nε-Lauroyl-L-Lysine100 g. of titanium dioxide coated mica pigment (Flamenco Blue of The Mearl Corporation, 46% TiO₂ and 54% mica) were dispersed in 1.0 liter distilled water in a 2.0 liter vessel. With stirring, the pH was adjusted to 5.0 with O.10 Normal HCl solution. An alkaline solution of Nε-lauroyl-L-lysine (3.0 g. in 100 ml. of 3.5% NaOH solution) were added at 2.5 ml. per minute while simultaneously adding a 20% solution of AlCl₃.6H₂O at a rate so as to maintain the pH at 5.2±0.1. When the Nε-lauroyl-L-lysine solution has been used up, the slurry is filtered, washed with distilled water until the filtrate tested free of chloride, and dried at 95°C for 4 hours. The product was sieved through a 60 mesh screen. The product was evaluated as in Example I and, compared to the original untreated titanium dioxide coated mica product, showed improved tactile and dispersion properties. In addition, the product has a blue interference reflection color which appears somewhat brighter and more lustrous than the original untreated product. The small amount of aluminum hydroxide formed aids in the adhesion of the treatment compound. Titanium dioxide coated mica pigments showing interference reflection colors, due to the thickness of the TiO₂ layers on the mica, can be further enhanced in color effects by laking dyes to the TiO₂ surfaces. Such products are described in Patent No. 4,968,351, above referred to. These products have interesting and excellent color properties, but the tactile properties are poor. The treatment with Nε-lauroyl-L-lysine can affect tactile properties, but the post-treatment may cause other undesired effects such as dye bleeding or some loss of color intensity. Therefore, it is preferable to carry out the treatment during the actual laking process for fixing the dye to the TiO₂ surface. Many different dyes can be used for this type product, as disclosed-in Patent No. 4,968,351, and the laking process can be basically the same for all. Colorants, e.g., pigments or dyes other than laked dyes, such as carmine, may also be employed. Treatment of a complex nacreous pigment which is to contain an absorption colorant may require the use of a method which involves the addition of the lauroyl lysine during the process of precipitating the colorant, such as an organic colorant, on the base pigment, as by a laking process of an organic dye. This method may also be advantageous in some cases with other post-coatings of colors, such as carmine or iron blue. EXAMPLE VIIILaked Dye Coated Titanium Dioxide Coated Mica Additionally Coated with 3.0% Nε-Lauroyl-L-LysineFor this example, a titanium dioxide coated mica sample with gold interference reflection color was used (35% TiO₂ and 65% mica). The dye for laking selected was FD&C Yellow 5 (Tartrazine). The FD&C Yellow 5 (supplied by Kohnstamm) was prepared as a 0.5 solution by dissolving 10.0 g, of the dye in 2.0 liters of distilled water. The Nε-lauroyl-L-lysine solution was prepared by dissolving 16.5 g. Nε-lauroyl-L-lysine in 550 ml. 3.5% NaOH solution. The laking solution consisted of 20% AlCl₃.6H₂O in distilled water. 500 g. of the substrate pigment described above (Flamenco Gold of The Mearl Corporation) were dispersed in the dye solution described above, at ambient temperature in a 5 liter Morton flask fitted with a stirrer which was rotated at 270 rpm. 200 ml. of the 20% AlCl₃.6H₂O solution were added at 2.0 ml. per minute, maintaining the pH at 5.0 ± 0.1 by the simultaneous addition of the alkaline treatment solution described above. The total addition time was about 100 minutes. The slurry was then filtered on a 24 cm. diameter Buchner Funnel fitted with No. 2 Whatman filter paper. The filtrate was washed two times, each with 500 ml. portions of distilled water. The washing of the filter cake was continued with 500 ml. portions of distilled water until the filtrate was essentially free of chloride. The filter cake was dried at 80°C for 4 hours, and it was then sieved through a 100 mesh screen. Testing was done as in Example I, and in particular it was noted that the tactile properties were quite smooth and soft and far superior to the same product laked with the same dye, but lacking the treatment with Nε-lauroyl-L-lysine. EXAMPLE IXIron Blue Coated Titanium Dioxide Coated Mica Additionally Treated with 3.0% Nε-Lauroyl-L-LysineA titanium dioxide coated mica pigment, characterized by an average platelet size of 10 microns, a mica content of 29%, a titanium dioxide coating on the mica consisting of 63% of the pigment, and a post-coating on the titanium dioxide of ferric ferrocyanide, 8% of the total pigment by analysis, was employed. 125 g. of this pigment (Mattina Blue of The Mearl Corporation) are dispersed in 1450 ml. of distilled water in a 3-liter flask fitted with a stirrer and a pH electrode. 360 ml. of an 0.5 normal sodium hydroxide solution containing 1,06% of Nε-lauroyl-L-lysine are added to the stirred dispersion of the pigment at a rate of 5.0 ml. per minute, at ambient temperature. Concurrently, a solution of 0.50 normal hydrochloric acid solution containing 0.28% CaCl₂.2H₂O is added at such a rate so as to maintain the pH of the pigment dispersion constant at 3.5± 0.1, the addition time being 72 minutes. The stirring was continued another 10 minutes, and then the product was filtered, washed with distilled water, dried at 50°C overnight, and sieved through a 60 mesh screen. The tactile properties of this treated product were tested and compared with others, including the untreated original product, Mattina Blue. The treated product was distinctly better than the original untreated material. Dispersion tests, using several different solvents, were carried out. The treated product showed greater hydrophobicity over the untreated product. The determination of the adhesion of the Nε-lauroyl-L-lysine to the substrate pigment was also carried out. The adhesion of the lauroyl lysine treated product was 82%. In Examples V and IX, above, the colorants (carmine in Example V and ferric ferrocyanide in Example IX) are deposited on the titanium dioxide coated mica pigments prior to the treatment with lauroyl lysine. Alternatively, however, the colorant and the lauroyl lysine can be deposited on the pigments concurrently, e.g., as in Example VIII. The differences in the properties of the final products are minor. The post-treatment method is simpler and more direct. However, in the case of Example VIII, which employs an organic colorant, post treatment with the lauroyl lysine results in an unsatisfactory final product. The data in Examples I to IX may be summarized as follows: Rates of Addition of Solid Nε-Lauroyl-L Lysine (LL) per Unit Weight of Substrate Example Substrate LL Addn. Time (min) LL Concn. % Rate (mg./g./min.) I150 g.6.0 g.12040.33 II200 lb.6 lb.603 0.50 III225 g.4.5 g. 72 2 0.28 IV681 g.20.4 g.93.530.32 V681 g.21.0 g.8030.38 VI100 g.3.0 g.4030.75 VII100 g.3.0 g.4030.75 VIII500 g.16.5 g.10030.33 IX125 g.3.8 g.7230.42 EXAMPLE XComparison Example: Blend of Mica and 3.0% Nε-Lauroyl-L-Lysine, Compared to Coating on Mica4.00 g. of wet ground Indian mica, average platelet size of 10 microns (same as used in Example II) were placed in a 2 oz. glass jar. 0.12 g. of Nε-lauroyl-L-lysine powder were added along with 4 steel shots, the jar capped and placed on a roller for 30 minutes. The jar was then removed from the roller, and the 4 steel shots were separated from the pigment. The tactile properties were determined in comparison with other samples. The product of this experiment was much poorer than that of Example II, and it was only somewhat better than that of the untreated mica. The determination of adhesion of the treatment compound to the substrate pigment was carried out, and it was found to be 21%. This is quite unsatisfactory compared to treatment procedures of this invention, yielding adhesions of at least 80% in most cases, and not less than 60%. EXAMPLE XIVariation of Addition Rates of Nε-Lauroyl-L-Lysine to Mica Substrate100 g. of wet ground Indian mica, average platelet size of 10 microns, were dispersed in 400 ml of distilled water at room temperature. 300 ml of 0.5 normal sodium hydroxide solution were prepared containing 1.0% Nε-lauroyl-L-lysine. This solution was added at a particular rate to the mica dispersion in each of the following experiments, holding the pH constant at 3.0±0.1 by the concurrent addition of 0.50 normal HCl solution. The rates of addition of the NaOH solution containing 1.0% Nε-lauroyl-L-lysine, and the results are given in the following table: Expt. Addn. Rate of NaOH Soln. (ml/min) Addn. Time (min) Addn. Rate, Mg. Lauroyl Lysine/g mica/min Tactile Rank Tactile Rating Pct.of Cmpd. Adhered A4.0251.23Good-97 B3.0330.91Good93 C2.0500.62Good96 D (Std at pH 6)2.2--4-- E (Mica)---5-- Room temperature was used. The addition rate is that of the 0.5 normal NaOH solution containing 1.0% Nε-lauroyl-L-lysine to the mica slurry. The actual addition rates of the treatment compared to the substrate are 0.4, 0.3, and 0.2 mg/g/min. EXAMPLE XIIVariation of Addition Rates of Nε-Lauroyl-L-Lysine to Titanium Dioxide Coated Mica Pigment SubstrateTitanium dioxide coated mica characterized by an average platelet size of 18 microns, an analysis of 46% TiO₂ and 56% mica, and an interference reflection color of blue, was used. 100 g. of this pigment (Flamenco Blue of The Mearl Corporation) were dispersed in 600 ml. of distilled water. 100 ml. of 3.5% NaOH solution containing 3.0% Nε-lauroyl-L-lysine were added, at different rates in each experiment. The pH was maintained at 6.0±0.1 by the concurrent addition of 0.5 normal HCl solution. The particular rates used in the several procedures are given in the following table, along with the results. Room temperature was used. Expt. Addn. Rate of NaOH Soln. (ml/min) Addn. Time (min) Addn. Rate, Mg. Lauroyl Lysine/g mica/min Tactile Rank Tactile Rating Pct.of Cmpd. Adhered A0.52000.152Good93 B1.01000.303Good96 C4.0251.21Good87 D(Std )---1-- E (Un-Treated Pigment)---4-- The addition rate is that of the 0.5 normal NaOH solution containing 1.0% Nε-lauroyl-L-lysine to the pigment slurry. The actual rates of addition of the treatment with respect to the substrate are 0.15, 0.30, and 1.20 mg./g./min. The limitations on the particular post-treatment method are predicated upon attaining a final platy pigment product that has improved tactile properties, shows evidence of good adhesion of the lauroyl lysine to the pigment surface substrate, and demonstrates improved dispersion behavior of the treated pigment compared to the untreated pigment. This improvement is generally in the direction of greater hydrophobic character. The lauroyl lysine crystalline solid surface has both hydrophilic and hydrophobic character, and in a sense the lauroyl lysine partially replaces the substrate surface hydrophile-hydrophobe character for its own. Thus, treated mica is more hydrophobic than untreated mica. The tactile properties are evaluated by spreading the powder on the skin and judging the smoothness and lack of drag, compared to standard materials. These evaluations are commonly carried out by experienced people in laboratories of cosmetic formulating firms. As indicated above, in determining the adhesion of the coating to the substrate, four successive centrifugations are carried out. The conditions of the centrifugation are not critical so long as effective separation of the solid (settled) and liquid (supernatant) phases are achieved. The following procedure may suitably be employed: To 75 ml. of distilled water is added 1.00 g. of the powder sample and dispersed in a 150 ml Corex centrifuge tube, No. 1265 (Catalog No. 21025-065 of VWR Scientific). Care must be taken to thoroughly disperse the sample, which can be done by vibratory or ultrasonic techniques usually available in laboratories. Centrifugation is carried out for 20 minutes, using a Servall refrigerated centrifuge fitted with the large head. The effective radius is 5.75 inches, and for a speed of 7200 rpm, the force field is about 8440 x g (g = gravitational constant). A high force field is desirable so as to obtain a clean separation of the liquid floating the non-adherent lauroyl lysine from the pigment particles, and the latter preferably should pack hard on the bottom of the tube, which facilitates the separation of the solid powder and liquid phases by decanting the latter. Lesser force fields can be used, so long as they enable effective separation of the solid settled and liquid supernatant phases. The supernatant liquid is decanted and saved, and the settled solid is redispersed in an equal volume of distilled water, and centrifugation is repeated. After four centrifugations are carried out in this way, the supernatant liquids are combined and analyzed for the treatment compound that was removed. Alternatively, the settled paste of the powder can be analyzed. Generally, the amount of treatment compound that adheres to a mica substrate in the products of this invention is at least 80% and often over 90%. For other pigment substrates at least 80% adhesion is desired, Evaluation of the dispersion properties is done so as to determine the shift in hydrophilic-hydrophobic character with the added treatment of the pigment. 2.0 g. of treated or untreated mica (1.50 g. of other substrates) are dispersed in 100 ml of each solvent in a graduated centrifuge tube, shaken, and allowed to settle. The tubes are observed at 30 min., 60 min., and 120 min. The centrifuge tube is Corning 8160 (Thomas Scientific 2622-D40) of 100 ml with graduations on a red glass layer, and measures about 7-3/4 inch in length and about 1-1/2-inch in outside diameter at the midpoint in height. The solvents usually used are distilled water, isopropanol, butyl acetate, and toluene. After two hours, two observations are recorded for each tube, settled volume of the powder, and appearance (clarity or haziness) of the supernatant liquid. The tests are done with the untreated pigments for comparison. Hydrophobic behavior is shown by high volume of the powder and clarity of the supernatant liquid in water along with low volume of powder and haziness of the supernatant liquid in toluene. For hydrophilic behavior the two solvents are reversed; the behavior in the two other solvents is intermediate. In general, but not necessarily always, the hydrophilic-hydrophobic is shifted towards the latter. The extent of the shift towards hydrophobicity varies with the substrate pigments. This test is generally significant because it indicates whether or not the substrate pigment has been adequately treated by the lauroyl lysine. The platy pigments of this invention may be advantageously employed in eye shadow compositions, such as pressed powder eye shadow in a wide range of proportions. Useful ranges of proportions of componenets in such compositions are listed in the following table, the pigments exemplified being treated before formulation with a compound of the general formula shown above: Component Proportions, weight % Matte Comp. (Low Luster) Frosted Comp. (High Luster) Talc5-705-70 Zinc Stearate2-102-10 Iron Oxides3-10-- Mica, wet ground, 10 microns avg. size5-70Flamenco Blue titanium dioxidecoated mica--25-70 Mineral Oil2-72-7 Isopropyl Myristate2-7-- 2-Ethyl-Hexyl Palmitate--2-7 The following are examples of eye shadow compositions of this invention: EXAMPLE XIIIMatte (Low Lustre) Pressed Powder Eye Shadow Component Weight % Talc30 Zinc Stearate3 Iron Oxides5 Mica, wet ground, 10 microns avg. size50 Mineral Oil6 Isopropyl Myristate6 The talc and the mica were treated before formulation with Nε-lauroyl-L-lysine. This formulation has superior tactile properties on the skin compared to the same formulation containing untreated talc and untreated mica. EXAMPLE XIVFrosted (high luster) Pressed Powder Eye Shadow Component Weight % Talc25 Zinc Stearate8 Flamenco Blue titanium dioxide coated mica60 Mineral Oil3 2-Ethyl-Hexyl Palmitate4 The talc and titanium dioxide coated mica pigment were treated before formulation with Nε-lauroyl-L-lysine. This formulation has superior tactile properties in testing compared to the same formulation containing untreated talc and untreated platy pigment.
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A process for improving the tactile characteristics of a platy pigment comprising precipitating a compound of the general formula where m is an even number from 8 to 18 and n is 3 or 4, onto the surface of said platy pigment, said precipitation being accomplished by adding an acid or alkaline solution of said compound to an aqueous dispersion of said platy pigment, the amount of said solution being such as to supply said compound in an amount of about 0.5.5.0% by weight of said platy pigment, while maintaining the temperature between about 15° and 80°C, said acid or alkaline solution being added at a rate within the range of about 0.10 - 1.50 mg of said compound per gram of platy pigment per minute, adding alkali or acid as required to bring the pH of the resulting mixture to between 1 and 8, and recovering said platy pigment coated with said compound. A process as defined in claim 1, wherein the compound of said general formula is entirely either the D or L isomer. A process as defined in claim 2 wherein said pH of the resulting mixture is brought to about 2.5-5.0. A process as defined in claim 2 wherein the compound of said general formula is Nε-lauroyl-L-lysine. A process as defined in claim 2 wherein the compound of said general formula is precipitated onto the surface of said platy pigment in the presence of a calcium salt. A process as defined in claim 2 wherein said platy pigment is titanium dioxide coated mica and said titanium dioxide coated mica is treated with a polyvalent metal compound before or during the addition of the compound of said general formula, said polyvalent metal compound being a hydroxide or a compound hydrolyzable to a hydroxide. A platy pigment having improved tactile, dispersion, and stability properties, said pigment comprising a substrate of platelets of mica, talc, or a metal oxide coated mica, said substrate being coated with Nε-lauroyl-L-lysine, said platelets having a particle size in the range of about 2 - 80 microns, with the average particle size in the range of about 5 - 40 microns, the Nε-lauroyl-L-lysine coating being present on the surface of said platelets in the range of about 0.5% to 5.0% by weight of the platelets, and at least 80% of said coating remaining adhered to said substrate after four centrifugations in the distilled water, each centrifugation being carried out on a dispersion of 1.00 g. of said platy pigment in 75 ml. of distilled water. A cosmetic composition containing a platy pigment product produced by the process defined in claim 1 in combination with cosmetically acceptable ingredients. An eye shadow composition containing a platy pigment produced by the process defined in claim 1 in combination with cosmetically acceptable ingredients. An eyeshadow composition containing a platy pigment produced by the process defined in claim 4 in combination with cosmetically acceptable ingredients.
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MEARL CORP; THE MEARL CORPORATION
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AHMED WASI; BLUM ADOLPH; GREENBERG PHILIP; MILLER HAROLD A; AHMED, WASI; BLUM, ADOLPH; GREENBERG, PHILIP; MILLER, HAROLD A.
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EP-0489678-B1
| 489,678 |
EP
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B1
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EN
| 20,020,417 | 1,992 | 20,100,220 |
new
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B08B3
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F16K5
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B08B3, F16K5
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B08B 3/02H, F16K 5/06B
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Cleaning equipment
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A cleaning equipment, switchable between washing operation for washing with sanitary water and foam application with cleaning agent mixed with the water via an injector (8), and having interchangeable nozzles for the various operations connected to the equipment by a hose, one can switch between the various operation modes from the handset, as the equipment comprises a pressure or flow sensor (42), which registers pressure or flow difference at interchange between washing nozzle and foam applicator and having a connection to the injector (8). Accordingly the equipment switches automatically between the various operation modes dependent on the different nozzles. The function is based on a specially designed change-over valve, which partly functions as injector and partly allows free liquid flow without injector effect.
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The invention relates to a cleaning equipment, switchable between washing operation for washing with tap water and foam application with cleaning agent mixed with the water via an injector system, and having interchangeable nozzles for the various operations connected to the equipment by a hose. Such equipment is generally known. There is known low-pressure cleaning equipment in the nature of mobile and stationary equipment, e.g. for cleaning walls and floors in factories, production equipment, and their transport systems such as transport carriages, transport boxes, containers, moulds etc. and which also can be used for internal and external cleaning of vehicles. The equipment is remarkable for operating at low-pressure, e.g. in the range of 22 bar compared with high-pressure equipment.The stationary installations comprise a master station and a number of satellite stations, or only a master station. The master station receives its water supply from the sanitary installation and comprises a centrifugal pump to increase the water pressure. From the master station the water is distributed to the satellite stations via a pipe installation. The individual stations including the master station are supplied with compressed-air from an existing compressed-air equipment or a compressor to the specific purpose.The master station and the satellite stations comprise a three-way valve for changing between washing operation and foam operation or disinfection. During washing operation a large flow of water under high pressure is led directly to the hose connection of the station. During foam operation the three-way valve is set, such that the water is led to an injector having a hose connection for a suction hose, which is slipped into a container containing a cleaning agent. The injector sucks some cleaning agent from the container for mixing with the water, and to the mixture is added compressed-air for foaming purposes. Disinfection is carried out in a similar manner by suction of disinfectant from a container, but without the adding of compressed-air afterwards.Cleaning is initiated by turning on the water by a valve next to the station, likewise the three-way valve is changed from the closed position to the washing position. In advance the hose has been connected to the station and the gun equipped with a washing nozzle. Washing is carried out moving away from the station. At changing to foam operation one must go back to the station for setting the three-way valve in position for foam operation. The route back to the station can be inconvenient as the way leads through production equipment and pipe installations. Thus the same distance is covered twice, whereas once would suffice, if an optional change between washing operation and foam operation independently of the position in relation to the station could be performed.According to the present invention it is recognized that the valve arrangement can be simplified to a great extent and at the same time providing possibility for changing between washing operation and foam operation or vice versa independently of the position in relation to the station. This is achieved by a simple injector system, consisting of a change-over valve with a rotary-symmetrical valve body in the flow passage of the valve housing, said valve body having two crossing channels, one having a relatively large cross section, and constitutes the washing channel, while the other has a minor cross section, and constitutes the injector channel, and the valve body being rotatable between a position where the washing channel is in alignment with the flow passage of the valve housing for delivering water without additives, and a transverse position, where the washing channel is in connection with an adding intake in the side of the valve housing for intake of adding agents, and where the injector channel is in alignment with the flow passage of the valve housing for procuring of an injection for suction of adding agents and mixing thereof into the water.When the washing channel is in its washing operation position, the velocity of the water flow will be relatively low, such that it does not cause any injection effect, while such effect will occur in the other position, where the narrower injection channel cooperates with the valve inlet. As the water pressure remains the same, the velocity of the water flow through the narrower channel will increase remarkably, namely sufficiently to create a low pressure in the washing channel, which is in its transverse position, and through which additives can now be sucked from the side inlet.According to the invention a three-way valve and a special injection unit can be replaced by a simple tap-valve with an extra inlet in the side; this is a very appreciable simplification.To prevent water from running out through the additive inlet during washing operation, there can be placed a check valve therein, preferably unified with the valve. The injection effect is optimum when the injection channel at one side of the washing channel has a larger cross section than the part of the injection channel at the other side of the washing channel. The wider part of the injection channel constitutes the injector outlet and the narrower part the injector inlet. The injector outlet is adapted to the increased liquid flow in consequence of the addition of cleaning agent/disinfectant to the water flow. The larger outlet area also results in a self cleaning effect, in case any residue is left in the opening after completing the foam application/disinfection. At restart the residue will be washed away.It is noticed that the valve body can be ball shaped, cylindrical, truncated or have a similar rotary symmetrical shape.As previously indicated the simplification of the valve arrangement allows the optional switch-over at the hose end from washing operation to foam application or vice versa irrespective of the operator's position in relation to the master station. This is achieved according to the invention by a pressure or flow sensor, which senses the pressure or flow difference at interchange between washing nozzle and foam applicator and having a connection to the change-over valve. Hereby one can freely switch between washing operation and foam application just by interchange between the washing nozzle and the foam applicator. When switching to disinfection it is necessary anyway to return to the station to change to a container containing disinfectant, thus compressed air admission can manually be turned off at the station panel.The invention is explained in further detail in the following, with reference to the accompanying drawing, in which:- Fig. 1 is a vertical longitudinal section of a valve according to the invention, shown in its washing position;Fig. 2 is a horizontal longitudinal section of the valve shown in its washing position;Fig. 3 is also a horizontal longitudinal section, but with the valve member shown in its disinfection position and with a hose connector;Fig. 4 is a schematical view of a first embodiment for automatic changes between the various modes of the cleaning equipment;Fig. 5 is a schematical view of the principle of a specially designed limiter valve for limiting the liquid flow;Fig. 6 is a more detailed view of a second embodiment for automatic change between the various modes;Fig. 7 is a view of a specific embodiment of the limiting valve in connection with the changing valve in Figs. 1-3;Fig. 8 is an enlarged longitudinal section of the limiting valve in Fig. 7;Fig. 9 is a view of a second embodiment of the limiting valve in connection with the changing valve in Figs. 1-3;Fig. 10 is a view of third embodiment for automatic change between the various modes;Fig. 11 is a view of a fourth and different embodiment for automatic change between the various modes of the equipment.The valve shown can be of the ball-valve type, having a valve housing 2 with an inlet 4 and an outlet 6. In the side of the valve housing there is a hose connection 8, having an incorporated check valve 10. Further the valve has an operating handle 12, which can be set in two different operative positions, namely in alignment with and transversely to the flow direction between the inlet and outlet 4,6 respectively.The valve element 14 is designed with a wide washing channel 16, which is the primary flow passage of the valve, through which the valve is fully open for flow during washing operation, and with a secondary injector channel 18 transversely thereto and having a narrow channel part 20 at one side of the washing channel 16 and a wider channel part 22 at the other side of the washing channel. In Figs. 1 and 2 the valve element 14 is shown in dotted lines in the position, where the channel 16 is in alignment with the inlet 4 and the outlet 6. In this position the injector channel 18 is open towards the side inlet 8, but as the water flow is relatively low through the wide washing channel 14, no injection effect will be generated, and besides at the injector side a check valve 10 is incorporated, such that no outpressing of the flow water through the hose connector 8 occurs neither.In Fig. 3 the valve element 14 is shown in its transverse position, where the narrow channel part 20 is situated in front of the valve inlet 4, whereas the broader part 22 is facing the valve outlet 6. The broad washing channel 16 is now in its transverse position and is open towards the narrow side spout 8. At the inlet 4 the water will flow through the narrow channel part 20 with highly increased velocity, which results in a low pressure at the spout of this channel part in the washing channel 16, and this results in suction from the injector side via the hose connection 8. The water and the injected liquid are spouted out through the broader channel part 20 to the valve outlet 6, and the valve now operates as an injector unit.It is realized that the unit shown is remarkable not only by a very simple mechanical construction, but also operational with a very effective mixing of the injection medium, and thus it appears to be an operational advantage, that the injection takes place through a relatively large space at the spout of the narrower channel part 20.During use of the washing channel 16 it is insignificant whether it is the narrower or the broader part of the injection channel 18, which is facing the side spout 8.In the following examples of stationary low-pressure cleaning installations will be described having a master station and satellite stations based on the above described valve, and with utilization of the possibility of the valve to change between washing operation and foam operation from the outer end of the hose, regardless of the position in relation to the relevant station.With reference to Fig. 4 of the drawing sanitary water is led through the pipe line 24 to the valve 26, as next to the station a valve is placed. For mounting and repair purposes said valve will be present anyway, such that the station can be mounted and serviced without having to shut down the entire installation.The valve 26 is connected to two cylinders 28,30, more explicitly the valve element is connected to the piston rods 34,36 of said two cylinders by means of a connecting rod 32. The front end of the cylinder chamber of the cylinder 28 is connected to the valve by a pipe line 38 via an opening in the side of the valve house placed opposite the suction opening. The front end of the cylinder chamber of the other cylinder 30 is connected to the pipe line downstream the valve by a pipe 40, while the rear end of the chamber is connected to the pipe line upstream the valve by a pipe 52.Just after, i.e. downstream the valve 26, but before the pipe connection 40 of the cylinder, a specially designed limiting valve 42 is inserted in the pipe line, and which can limit the liquid flow. The valve 42 comprises a conical valve seat 44, cf. Fig. 5 and a belonging valve element 46 spring loaded 48 to its opening position towards the liquid flow. In the valve element there are two passage holes 50, through which a limited liquid flow can pass when the valve element is in its closing position.In washing operation the arrangement is in the position as shown in Fig. 4. At change to foam operation the washing nozzle is interchanged with a foam applicator and by activating the pistol/valve a large water flow is sent through the change valve 26, which is still in its washing position. The large water flow causes the limiting valve 42 to close, such that only the limited water flow remains through the passage in the valve member. This causes a large pressure drop from the inlet of the change valve 26 to the outlet of the limiting valve, which causes the cylinder 30 to switch, i.e. the piston is pressed to the top due to the pressure difference in the pipe lines 40,52 over the valves. The rod connection 32 will turn the valve member of the change valve to the suction position. The resulting reduced water flow through the valve 26 will cause the limiting valve 42 to reopen. At the end of the movement curve of the piston rod of the other hudraulic cylinder 28 there is a valve 54, which is activated by the rod for opening of compressed air to the pipe line. The station is thereby switched to its foam position. This position is indicated by a dotted line in Fig. 4.One of the advantages of the equipment is that it automatically returns to its washing position when the foam operation is switched off. The pressure which is built up in the system when the pistol is shut off will influence on the cylinder 28 via the pipe line 38 and switch the valve to its washing position. The other cylinder 30 will act as a slave cylinder, as it is pressure neutral. There is the same pressure at either side of the piston. The foam operator is interchanged with a washing nozzle, and the equipment is switched to its washing position.At temporary interruption of the foam operation the equipment will automatically change to the washing position, but by activating the pistol/valve, the equipment will automatically re-switch to the foam position as the foam applicator is applied. During foam operation one will not notice the temporary switches to the washing position, as it only occurs when the foam operation is temporarily interrupted.The third operation mode is disinfection, where the change valve 26 also is used for suction, namely of disinfectant. The operation mode however presents one difficulty, as a disinfection nozzle with only a small water flow is applied. At the first start one can open the pistol/valve without the nozzle applied, thereby causing a large water flow, switching the equipment to the suction position, and after this the nozzle is mounted. In case the disinfection is interrupted, the equipment will automatically change to the washing position, but as the disinfection nozzle is applied, a large water flow is not present at restart as is the case in foam operation, which can switch the equipment to suction position. Instead of dismounting the valve each time, it can be designed with a side outlet for a large water flow, which can be activated at the start situation.Constructionally the two cylinders can be placed at the same side or replaced by only one cylinder. An embodiment is shown in Fig. 6 of the drawing. The cylinder 56 is a differential cylinder having a suitable difference between the areas at either side of the piston, such that the pressure difference, taken from the area, is sufficient to cause the shifting of the valve 26. On the smallest area side of the piston, the cylinder is connected by a hose 58 to the pipe line 24 upstream the valve 26, and the other side of the cylinder is connected downstream the valve 26 and the limiting valve 42. The piston rod 60 of the cylinder is connected by a rod 32 to the valve member of the valve. In washing operation the piston is in its projected position. The admixing of air is controlled by an air valve 62, which is spring loaded to its shut off position, such that the compressed air is shut off during washing. In foam and disinfection positions the piston is in its retracted position. At interchanging from washing nozzle to foam applicator the limiting valve 42 will close. The pressure upstream the limiting valve 42, which is considerable higher than the pressure difference on the piston from the area, will urge the piston into its retracted position, and thereby shifting the valve 26 to its foam operation position.At the same time the end of the connection rod 32 activates the pneumatic cylinder 62 for a flow of compressed air through a reduction valve 64, a counter valve 66 and finally through a nozzle 68 for mixing with the liquid flow for foaming of same. The reduction valve is also connected to a manometer. At reswitch to washing operation the pressure difference on the-piston displaces this to its projected position, and the air valve 62 will shut off the compressed air flow. It is realized that the equipment automatically will revert to washing position, which is start position. Disinfection is carried out as previously described by cheating the equipment with a valve at the disinfection nozzle.The limiter valve 42 is shown schematically in Fig. 5 of the drawing. An embodiment of the valve is shown in detail in Fig. 7 of the drawing unified with a change valve by means of a body, such that the valves appear as a unit. The limiter valve, which is shown separately in Fig. 8 , comprises an outer mantel 70 with inserts 72,74 at both ends and having internal threads. In the outlet end there is a sleeve 76 with a groove for an O-ring which constitutes the valve seat 44. Between the sleeve and the end of the other insert there is embedded a finned grid 78, bearing the valve body 46 which is springloaded to its open position. The valve body having a central pin 80 fixed in the grid, around which is placed a helical spring 48 resting between the grid and the inwards facing side of a nut 82 on the end of the threaded pin 80. In the valve body there are holes 50 permitting passage of a minor liquid flow when the valve is in its closed position, i.e. when the valve body is resting on the valve seat, the body being guided in the grid structure. In case the valve body comprises a pair of discs with holes, which could be rotated in respect to each other, the flow passage could readily be adapted to the current situation.In special circumstances it appears that a throttle valve may be used as a limiter valve. In Fig. 9 of the drawing is shown an embodiment also unified with a change-over valve in the same manner as shown in Fig. 7. However the intensive constriction causes a severe pressure drop across the valve, which is undesirable during washing operation. The function is the same as previously described. At interchange of the washing nozzle with the foam applicator, the liquid flow is increased considerably and the resulting pressure drop across the valve activates the cylinder which switches the change-over valve to its foam position.Though the required force for rotating the valve body 26 of the change-over valve is relatively small, a relatively large cylinder or cylinders are required due to the minor power in a low pressure cleaning equipment. Further, differental cylinders are relatively expensive. As compressed air always will be present, this could be utilized to activate the change-over valve, e.g. by means of a pneumatic cylinder and control this by the liquid flow/liquid pressure. An embodiment is shown in Fig. 10 of the drawing, where 88 indicates the inlet for sanitary water, while 90 indicates the liquid outlet having a snap coupling. Besides, 26 indicates the change-over valve and 42 the limiter valve as shown in Figs. 7 and 8. The hose connection of the change-over valve for inlet of cleaning detergent/disinfectant is indicated by 8. Liquid connections are indicated by intermitting lines, while compressed air connections are indicated by dot and dash lines. The valve body of the change-over valve is by a short arm linked to the piston rod of the pneumatic cylinder 94. Said cylinder 94 is controlled by a set of air switches 96, which is activated by a small hydraulic cylinder 98 connected to the pipe line 24 upstream the change-over valve and downstream the limiter valve 42 respectively, in the same manner as in the embodiment shown in Fig. 6. At the end of the hydraulic cylinders 98 piston rods there is a plate 100, which activates the air switches 96, of which the two topmost usually are shut off, while the two lowermost are open. The normal position of the station is its washing position. At change-over to foam application the liquid part acts as previously described, i.e. that the piston rod of the hydraulic cylinder 98 goes into its retracted position, activating the air switches. The upper air switch set opens, while the lower shuts off. Compressed air from the reduction valve 102 via a manifold 104 and the switches is led to a branch pipe 106, where the air is led to the cylinder 94 at 108 and presses the piston to its retracted position, whereby the change-over valve is rotated to its injection position. From the other branch of the branch pipe compressed air is led to a valve 110, from which compressed air is fed to the liquid through the counter valve 66 and nozzle 68 as previously. At reswitch to washing position or temporary shut off of foam application the liquid part acts as previously, i.e. the cylinder 98 returns to its initial projected position and activates the air switches, such that the upper set shuts off, while the lower opens. Compressed air will thus flow from the regulator via the manifold and the lower switches to the other end of the pneumatic cylinder at 112, whereby the piston is pushed out and the change-over valve rotates to washing position. As the air pressure at the same time is released from the compressed air activated air valve 110 the supply of compressed air to the liquid flow is disconnected. Disinfection takes place as previously described. The system functions as before, only a pneumatic cylinder is added as auxiliary for activating the change-over valve. An electrical linear actuator could as well be added.A variant of the embodiment described above is shown in Fig. 11 of the drawing. Instead of the change-over valve there is a by-pass 114 across the limiter valve 42, of which the valve body by the way is without flow passage, i.e. the liquid flow is completly shut off when activated, such that the liquid flow is led through the by-pass, in which is placed a common injector 116 with a hose connection 8 for the suction hose. Across the limiter valve 42 is as previously placed a small hydraulic cylinder 98 with a plate 100 at the end of the piston rod, and which activates an air switch 98, which opens and shuts off the supply of compressed air 118. The station is shown in washing operation, where the supply of compressed air is shut off, and the water flows straight through the limiter valve 42. At shift to foam application the limiter valve reacts on the pressure build up and shuts off, whereby the water is led through the by-pass. The small hydraulic cylinder responds likewise on the pressure build up and the piston goes to its retracted position, whereby the air switches are activated by the plate to their open position, and compressed air is added to the liquid via the reduction valve 64, the counter valve 66 and the air nozzle 68. At reswitch to washing position the pressure drops across the limiter valve 42, and this opens, likewise the cylinder 98 returns to its normal position, the supply of compressed air is shut off. At temporary interruption of foam application the station will automatically return to its washing position. Disinfection takes place as previously described.Thus according to the invention there is provided a cleaning equipment, where from the end of the hose one is able to switch between washing and foam operation. Furthermore the equipment offers the advantage that it automatically returns to its washing position. Another obvious advantage is the simple constructive design. Although the invention is described especially in connection with a stationary low pressure cleaning installation, it is obvious that the utilization of the invention is not limited thereto.
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A cleaning equipment, switchable between washing operation for washing with tap water and foam application with a cleaning agent mixed with the water via an injector system, and having interchangeable nozzles for the various operations connected to the equipment by a hose, characterized in that the injector system is constituted by a change-over valve with a rotary-symmetrical valve body (14) in a flow passage (4,6) of a valve housing (2), said valve body having two crossing channels, one having a relatively large cross section, and constitutes the washing channel (16), while the other has a minor cross section, and constitutes the injection channel (20,22), and the valve body (14) being rotatable between a position where the washing channel (16) is in alignment with the flow passage (4,6) of the valve housing for delivering water without addings, and a transverse position, where the washing channel is in connection with an adding intake (8) in the side of the valve housing for intake of adding agents, and where the injection channel (20,22) is in alignment with the flow passage (4,6) of the valve housing for procuring of an injection effect for suction of adding agents and mixing thereof into the water.Cleaning equipment according to claim 1, characterized in that there is a check valve (10) in the adding agent inlet (8), for shutting off the inlet, when the change-over valve is in its washing operation position.Cleaning equipment according to claim 2, characterized in that the part of the injection channel, which is at one side of the flow passage channel, and which constitutes the injector outlet (22) has a larger cross section than the part of the injection channel, which is at the other side of the flow passage channel, and which constitutes the injection inlet (20).Cleaning equipment according to claims 1, 2 or 3, characterized in that it comprises a pressure or flow sensor (42), which senses the pressure or flow difference at interchange between washing nozzle and foam applicator and having a connection to the change-over valve, and where the valve body (14) is connected with pressure or flow actuating means (28,30,56,94) for switch between the two operation modes.Cleaning equipment according to claim 4, characterized in that the pressure sensor comprises a flow limiter valve (42) in continuation of the change-over valve (26).Cleaning equipment according to claim 5, characterized in that the valve body (46) of the limiter valve (42) is springloaded (48) for opening against the flow direction, and that in the valve body (46) there is a minor flow passage (50).Cleaning equipment according to claim 4, characterized in that the actuating means (28,30,56,94), comprises two cylinders (28,30), one of which (30) by the bottom end is conntected to the pipe line upstream the valves (26,42) and the top end being connected to the pipe line downstream the valves, and that the top end of the other cylinder (28) is connected to the valve housing (2) opposite the suction opening.Cleaning equipment according to claim 4, characterized in that the actuating means comprises one cylinder (56) (a differential cylinder), where the under side of the piston is larger than the upperside, and that the top end of the cylinder is connected to the pipe line upstream the valves (26,42) and the bottom end downstream said valves.Cleaning equipment according to claims 7 or 8, characterized in that the cylinders during foam operation activate a valve for admixing compressed air to the liquid flow. Cleaning equipment according to claim 8, characterized in that the valve body (14) of the change-over valve (26) is activated by a pneumatic cylinder (94), controlled by hydraulic cylinders (94) via control devices such as air switches and air valves.
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SCANIO FLOW EQUIP; SCANIO FLOW-EQUIPMENT A/S
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GULSTAD FRANK RONFELDT; PEDERSEN VILLY LEENHARDT; GULSTAD, FRANK RONFELDT; PEDERSEN, VILLY LEENHARDT
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EP-0489680-B1
| 489,680 |
EP
|
B1
|
EN
| 19,950,215 | 1,992 | 20,100,220 |
new
|
B05B1
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B05B3
|
B05B1
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B05B 1/32, B05B 1/26A
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Static sector-type water sprinkler
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The static, sector-type water sprinkler produces a variable-sector water-distribution pattern and includes an outlet opening (6) having an effective length around the circumference of its housing (2) which may be manually varied for preselecting the sector angle of the water distribution around the sprinkler. The outlet opening (6) is defined by a slot of fixed length extending around the circumference of the housing (2), and its effective length is varied by a blocking member (8) which is manually movable with respect to the slot to preselect the portion thereof to be unblocked, and thereby the sector angle of the water to be distributed around the sprinkler.
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The present invention relates to water sprinklers, and particularly to a static, sector-type water sprinkler producing a variable-sector water-distribution pattern around the sprinkler. Variable-sector water sprinklers of this type are known. Generally, they include a housing formed with an inlet opening at one end connectible to a supply of pressurized water, and an outlet opening having an effective length around the circumference of the housing which may be manually varied for preselecting the sector angle of the water distribution around the sprinkler. Examples of a known sprinkler of this type are illustrated in US-A-4,184,239 and US-A-4,579,285. US-A-4,184,239 discloses a static, sector-type water sprinkler producing a variable-sector water-distribution pattern, including a housing formed with an inlet opening at one end connectible to a supply of pressurized water, and an outlet opening having an effective length around the circumference of the housing which may be manually varied for preselecting the sector angle of the water distribution around the sprinkler; and a blocking member manually adjustable with respect to the outlet opening for preselecting the sector angle. In the water sprinkler therein disclosed, the outlet opening is in the form of a plurality of spaced apertures arranged in a closed elliptical array defining a plane which extends in an angle to the axis of the sprinkler. According to the present invention, there is provided a static, sector-type water sprinkler as described in the preamble of claim 1, but characterized in that the outlet opening is defined by a slot extending helically around the circumference of the housing; the blocking member being manually movable with respect to the slot to preselect the portion thereof to be unblocked by the blocking member, and thereby the sector angle of the water distribution around the sprinkler. Such a construction provides a uniform distribution of the water since it produces a continuous arcuate discharge. In addition, the preslection of the sector angle is simple. According to further features in the preferred embodiment of the invention described below, the blocking member is disposed within a cylindrical bore extending axially of the housing and rotatable therein to preselect the portion of the slot to be unblocked, and thereby the sector angle of the water distribution around the housing. More particularly, in the described preferred embodiment, the outer face of the blocking member is formed with a helical rib receivable in the helical slot to preselect the portion of the slot to be unblocked according to the rotated position of the blocking member and its helical rib. According to a further feature of the invention, the portion of the housing defining the upper surface of the helical slot is formed with a plurality of radially-extending ribs. Such ribs direct the water radially outwardly, thereby increasing the range and producing a more uniform water distribution. According to further features in the described preferred embodiment, the blocking member is formed with a non-circular (e.g., a hexagonal) bore extending axially of the blocking member, and the sprinkler includes a corresponding non-circular stem extending through the bore and having an externally-accessible finger-gripping element to facilitate manual rotation of the blocking member in order to preselect the sector angle of the water distribution around the sprinkler. According to a further feature in the described preferred embodiment, the stem carries a flow control element adjacent the inlet opening of the housing and presettable towards and away therefrom to preset the size of the inlet opening, and thereby the rate of flow of the water therethrough. Water sprinklers constructed in accordance with the foregoing features may be manufactured and assembled in volume and at low cost. Further features and advantages of the invention will be apparent from the description below. The invention is herein described, by way of example only, with reference to the accompanying drawings, wherein: Fig. 1 is an exploded view illustrating the main elements of one form of sprinkler constructed in accordance with the present invention; Fig. 2 is a side elevational view illustrating the sprinkler of Fig. 1 in assembled condition; Fig. 3 is a longitudinal sectional view of the sprinkler of Fig. 2; Fig. 4 is an enlarged fragmentary view of a portion of the sprinkler of Figs. 1-3; and Fig. 5 is an exploded view illustrating a modification in the construction of the sprinkler of Figs. 1-4. The sprinkler illustrated in Figs. 1-4 is a static, sector-type water sprinkler producing a water-distribution pattern which may be manually varied both with respect to the sector, and the rate of water distribution, around the sprinkler. The illustrated sprinkler comprises a housing, generally designated 2, formed with an inlet opening 4 (Fig. 3) at one end connectible to a supply of pressurized water, and a helical slot 6 (Fig. 2) extending helically around the circumference of the housing and serving as an outlet opening for discharging the water around the sprinkler. While helical slot 6 is a fixed length, the effective size of the slot discharging the water may be varied by a blocking member, generally designated 8 (Fig. 1), manually movable with respect to the slot to preselect the portion thereof to be unblocked by the blocking member, and thereby the sector angle of the water distribution around the sprinkler. Presetting the sector is effected by a manually-rotatable stem assembly, generally designated 10, which may be rotated to thereby rotate the blocking member 8. Housing 2 is formed with an axially-extending bore 11 for receiving the stem assembly 10. More particularly, housing 2 is constituted of three sections 2a, 2b and 2c. Housing section 2a is formed with the upper surface 6a of the helical slot 6, whereas housing section 2b is formed with the lower surface 6b of the helical slot. The two sections 2a, 2b, with the blocking member 8 in between, are secured together by a plurality of posts 12 formed in the lower surface of housing section 2a received within blind bores 14 in housing section 2b. Housing section 2c is integrally formed with inlet opening 4 and is secured to housing section 2b by a friction fit, wherein the smooth outer surface 16 in housing section 2c is frictionally received within the smooth inner surface in the lower end of housing section 2b. Housing section 2b is formed with recesses 17 on its inner surface which define flow passageways from the inlet 4 to the blocking member 8. Blocking member 8 is of generally cylindrical configuration to be snugly received within the two housing sections 2a, 2b when secured together. The blocking member is formed with a central axially-extending bore 18 of non-circular (e.g., hexagonal) configuration, and an outer rib 20 extending helically around its circumference. Helical rib 20 is of a configuration corresponding to that of helical slot 6, and is of a height equal to the height of that slot, so as to be snugly receivable and movable within that slot. Stem assembly 10 includes a stem 22 of the same cross-section (e.g., hexagonal) as axial bore 18 formed in blocking member 8 so as to be non-rotatably receivable within the blocking member. Assembly 10 further includes a circular collar 24 at one end of stem 22, and a plurality of lugs 26 at the opposite end of the stem. The outer end of collar 24 forms an externally-accessible finger-gripping element permitting stem 22, as well as blocking member 8 received thereon, to be rotated in order to move the helical rib 20 of blocking member 8 within the helical slot 6 of the housing 2. Lugs 26 form an annular abutment engageable with an annular shoulder 27 (Fig. 3) in the housing adjacent the inlet opening 4. These lugs permit rotational movement, but not axial movement, of stem 22 within the housing. As shown particularly in Fig. 3, lugs 26 are formed with outer tapered surfaces permitting the stem to be inserted with a snap-fit into the axial bore 11 defined by the housing 2. Stem assembly is further fomred with a threaded, axially-extending bore 30 for receiving an externally-threaded pin 32. As shown particularly in Fig. 3, the inner end of pin 32 is formed with an enlarged head 36 to be located adjacent to the throat 4a of the sprinkler inlet 4. The opposite (outer) end of pin 32 is formed with a screwdriver slot 38. Head 36 of pin 32 thus serves as a flow-control element which is movable, upon rotation of pin 32, towards or away the inlet throat 4a for presetting the size of the inlet opening, and thereby the rate of flow of the water therethrough to the sprinkler and the range of the sprinkler. As particularly seen in Fig. 4, both the upper surface 6a and the lower surface 6b of the helical slot 6 are tapered outwardly to produce a spray-pattern of the water discharged through the helical slot. In addition, the upper surface 6a of the helical slot is formed with a plurality of radially-extending ribs 40 which tend to direct the discharged water to the radial direction, thereby increasing the range of water discharge, and also to move the water discharge more uniform over the preselected sector. The lower end of housing section 2b is internally threaded, as shown at 50 (Fig. 1) for attaching the sprinkler to a vertical riser. The sprinkler is assembled as follows: Blocking member 8 is inserted between the two housing sections 2a, 2b, and then the two housing sections are secured together by inserting posts 12 of section 2a into openings 14 of section 2b. The two sections may be secured removably by a friction fit, or permanently by adhesive or heat-welding. Stem assembly 10 is then inserted through bore 11 of the housing, and through bore 18 of the blocking member 8. This insertion is facilitated by the flexible lugs 26 and by their outer tapered surfaces, which permit the assembly to be inserted with a snap-fit with the lugs engaging annular surface 27 (Fig. 3) of the housing. Pin 32 is then threaded into stem 22 from its bottom. The assembled two housing sections 2a, 2b, with the blocking member 8, stem assembly 10 and pin 32 in between, are then assembled to the lower housing section 2c by press-fitting the outer smooth surface 16 in the latter section within the internal smooth surface of section 2b. The sprinkler may then be preset to provide the desired sector of water-distribution, and also the desired rate of water distribution, as follows: To preset the sector, collar 24 is rotated, which thereby moves helical rib 20 of blocking member 8 more or less within helical slot 6 of the housing, such that the portion of the helical slot not blocked by the helical rib determines the sector angle of the water distribution around the sprinkler. The rate of water distribution may be preset externally, e.g., by inserting a screwdriver or other tool into slot 38 of pin 32, and rotating the pin, which will thereby move head 36 at the opposite end of the stem assembly 10 towards or away from throat 4a of the inlet opening 4. It will be seen that in the Figs. 1-4 embodiment, the helical slot 6 is not continuous, but rather is interrupted by the three posts 12 connecting housing section 2a to housing section 2b. The posts may be of an oblong cross-section to minimize this interference. In most cases, they will not substantially interfere with the water distribution pattern around the sprinkler, since the angular length of all the posts together is at least an order of magnitude smaller than the angular length of the helical slot (e.g., the circumference of the housing). Fig. 5 illustrates a variation wherein the helical slot, therein designated 106, is not interrupted, but rather is continuous for its complete length around the circumference of the housing. The two housing sections 102a, 102b are integrally joined together as one part, e.g., by injection molding. In this construction, the opposite ends of the helical slot 106 overlap and are interconnected by a web portion 107. In all other respects, the construction, presetting, and operation of the sprinkler illustrated in the modification of Fig. 5 are otherwise the same as described above with respect to Figs. 1-4, and therefore the corresponding parts are identified by the same reference numbers.
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A static, sector-type water sprinkler producing a variable-sector water-distribution pattern, including a housing (2) formed with an inlet opening (4) at one end connectible to a supply of pressurized water, and an outlet opening (6, 106) having an effective length around the circumference of the housing which may be manually varied for preselecting the sector angle of the water distribution around the sprinkler; and a blocking member (8) manually adjustable with respect to said outlet opening for preselecting said sector angle; characterized in that said outlet opening (6) is defined by a slot extending helically around the circumference of the housing; said blocking member (8) being manually movable with respect to said slot to preselect the portion thereof to be unblocked by said blocking member, and thereby the sector angle of the water distribution around the sprinkler. The sprinkler according to Claim 1, wherein said blocking member (8) is disposed within a cylindrical bore (11) extending axially of the housing (2) and is rotatable therein to preselect the portion of said slot (6, 106) to be unblocked, and thereby the sector angle of the water distribution around the sprinkler. The sprinkler according to Claim 2, wherein the outer face of said blocking member is formed with a helical rib (20) receivable in said helical slot (6, 106) to preselect the portion of said slot to be unblocked according to the rotated position of the blocking member (8) and its helical rib (20). The sprinkler according to Claim 3, wherein said blocking member (8) is formed with a non-circular bore (18) extending axially thereof, and said sprinkler includes a non-circular stem (22) extending through said non-circular bore and having an externally-accessible finger-gripping element (24) to facilitate manual rotation of said blocking member in order to preselect the sector angle of the water distribution around the sprinkler. The sprinkler according to Claim 4, wherein said externally-accessible finger-gripping element (24) is a circular collar fixed to one end of said stem, the opposite end of the stem being formed with an annular abutment (26) engageable with an annular shoulder (27) formed on the housing adjacent to said inlet opening, permitting rotational movement, but not axial movement, of said stem within said housing. The sprinkler according to Claim 5, wherein said opposite end of the stem carries a flow control element (36) adjacent the inlet opening (4) of the housing and presettable towards and away therefrom to preset the size of the inlet opening and thereby the rate of flow of the water therethrough. The sprinkler according to Claim 6, wherein said flow control element (36) is carried by an externally-threaded pin (32) received in an internally threaded bore (30) formed in said stem (22) and accessible from said one end of the stem for presetting the position of the flow control element. The sprinkler according to any one of Claims 2-7, wherein the portion of said housing formed with said helical slot (6, 106) includes a first section (6a, 106a) formed with one surface of said slot, and a second section (6b, 106b) formed with the other surface of said slot; said first section being further formed with a plurality of circumferentially-spaced posts (12) fixed within bores formed in said second section. The sprinkler according to any one of Claims 1-8, wherein the portion of the housing defining the upper surface of said helical slot is formed with a plurality of radially-extending ribs (40).
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LEGO LEMELSTRICH LTD; LEGO M. LEMELSHTRICH LTD.
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HADAR YORAM; HADAR, YORAM
|
EP-0489693-B1
| 489,693 |
EP
|
B1
|
EN
| 19,951,011 | 1,992 | 20,100,220 |
new
|
B01D69
|
B01D69
|
B01D71, B01D61, B01D67, B01D69
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B01D 69/02, B01D 67/00R18, B01D 67/00F10, B01D 69/14B
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Charged asymmetric mosaic membranes
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The present invention relates to semipermeable mosaic polymer membranes of asymmetric structure and with a macroscopic distribution of the mosaic-forming anionic and cationic charges (sites). The membranes can be prepared by casting a polymer solution of an optionally charged matrix-forming polymer and at least one precursor polymer, incompatible with the matrix-forming polymer, in a selected solvent, into a film, forming a skin on one side of the film, precipitating the skinned film to form the asymmetric membrane and charging it by chemical reactions to introduce or complete their mosaic structure. These membranes have good permeability for electrolytes, such as salts of mono- or polyvalent inorganic acids, while retaining low molecular weight organic solutes.
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The present invention relates to semipermeable charge-mosaic organic polymer membranes of asymmetric structure and with a macroscopic distribution of the mosaic-forming anionic and cationic charges (sites). These membranes have good permeability for electrolytes, such as salts of mono- or polyvalent inorganic acids, while retaining low molecular weight organic solutes. The separation of mono-, di- or polyvalent salts, such as sodium chloride, or sodium sulfate or sodium triphosphate, from low molecular weight (MW < 1000) organic compounds in (aqueous) solutions, via membranes is an important industrial separation problem which has not been economically solved. Membranes have been shown to offer an economical solution to many separation problems because of their ability to concentrate without a phase change, and to separate different solutes. The traditional membrane process of reverse osmosis (RO) rejects all salts and organics. The relatively newer membranes of selective reverse osmosis cannot efficiently achieve the above separations even though they are designed to pass salt and retain the organic solutes. The mode of separation in selective RO is based on size and electrostatic discrimination, and the proper choice of materials has not been found to give e.g. a sulfate passage. However, membrane structures containing separated macroscopic domains (0.05 to 100 micrometers) of anionic and cationic ion exchange materials connecting the opposite faces of the rejecting layer (called a charge-mosaic membrane) have a built-in salt transport mechanism. They have been postulated and shown to give separation between organic solutes and salts. Under a pressure gradient the membranes preferential transport salt across the charge-mosaic while retaining the organic solute [H. Kowatoh et al., Macromolecules 21, 625-628, 1988]. Charge-mosaic membranes have also been shown to give high water flux, while, at the same time, giving a permeate enriched in salt [F. B. Leitz, J. Shore, Office of Saline Water, Res. Developm. Program Report No. 775 (1972)]. Charge-mosaic membranes are membranes with a macroscopic distribution of cationic and anionic sites. Typically, though not exclusively, they are arranged as particles, such as cationic and/or anionic particles distributed in a neutral matrix, or particles of one charge distributed in a matrix of the other charge. In this case, particles may be defined as regular or irregular approaching such shapes as spheres, multisided, fibers, cones, and others. See for instance FR-A-2 166 382 and DE-A-2 524 870. The different approaches to achieve the structures of charge-mosaic membranes comprise such methods as the introduction of preformed particles in a matrix via resin suspension in a casting solution of the matrix, block or random copolymerisations, or phase separation in a common solvent (material incompatibility). Charge-mosaic membranes have not yet become commercially important in separation processes because of the difficulty in upscaling a reproduceable process for making mosaics. Of all the above approaches, one of the simplest with a good upscaling and fabrication potential is the said material incompatibility, or phase separation in a common solvent. However, it is also the most difficult to make without imperfections which destroy membrane properties. Further, the known mosaic membranes do not have high enough rejection to low (less than 400) molecular weight solutes, or if they have high enough rejection their water fluxes are too low. Surprisingly, it was found that if the wet film coating of polymers is such that it can be made into an asymmetric membrane by a process of coating, partial evaporation and then immersing in a gelling solvent, such as water, charge-mosaic structures are formed without leaks or imperfections with good rejection to organic solutes and salt passage. It is, therefore, a principal object of the present invention to provide asymmetric semipermeable charge-mosaic membranes. Other objects of the present invention are processes for the manufacture of the inventive membranes, as well as their use in separating organic, low molecular weight solutes from inorganic salts of mono- or polyvalent inorganic acids. These and other objects of the present invention will become apparent from the following detailed description. The present invention accordingly provides in its main aspect a semipermeable charge-mosaic organic polymer membrane with macroscopic distribution of the mosaic-forming anionic and cationic charges which comprises an asymmetric structure of at least one charged polymer dispersed in a matrix-forming polymer of opposite charge, or of polymers of both charges dispersed in a neutral matrix-forming polymer or in a matrix-forming polymer of one or both charges. Asymmetric membranes are characterized by a thin dense upper layer (usually less than 5.0 micrometers but preferably less than 1.0 micrometer thick), which is the selective barrier extending continuously from a thicker (10 to 1000 micrometers) porous structure. The asymmetric structure is made simultaneously in the casting of a polymeric solution and gelling. The membranes of the present invention have the aforementioned asymmetric structure, but in addition contain a mosaic structure of ionic materials distributed within the upper discriminating layer. This mosaic structure confers upon the membrane the ability to pass salts by the mosaic mechanism of salt/water flow coupling. Preferably, the inventive membranes comprise the matrix-forming polymer as major component and the polymers dispersed therein as minor component. Essential embodiments of these membranes - as mentioned - comprise at least one charged polymer dispersed in a matrix-forming polymer of opposite charge; or polymers of both charges that are dispersed in a neutral matrix-forming polymer or in a matrix-forming polymer of one or both charges. The term charges means that negative (anionic) or positive (cationic) charges, or both, are present in the polymers, such as in a preferred embodiment, which comprises a membrane with a dispersed polymer containing the cationic charges and a matrix-forming polymer containing the anionic charges. As a rule, the dispersed polymers are present as regular or irregular particles of one or both charges within the matrix of opposite charge or of one or both charges. Ideally, the size of the particle is such that it is large enough to penetrate from the uppermost surface through the active rejecting layer of the asymmetric layer, which is from about 0.01 to 5 micrometers thick. Polymeric materials for the matrix can be chosen from materials which are film formers and/or can be cast into asymmetric membranes. Such materials can be chosen from cellulosics, polysulfones, polyethersulfones, polyetherketones, polyether-etherketones, polyether imides, polyphenylene oxides, polyphenylene sulfides, polyamides, polyimides, polyamide-imides, polycarbonates, polyacrylonitriles, polyethers, polybenzamidazole, and their derivatives, such as derivatives containing sulfonic or phosphoric acid groups. Of special interest are polymeric materials that can be cast into asymmetric membranes with cutoffs in the range of small organic molecules of a molecular weight less than 1000, and preferably between 150 and 700. Preferred polymeric materials for achieving such performance are cellulose acetates, sulfonated polysulfones and polyether sulfones, or polyetherimides, polyamides, polyimides, polycarbonates, and sulfonated 2,6-dimethylphenylene oxides. Especially applicable because of their membrane forming properties, chemical stability, anionic charge and availability are sulfonated polysulfones and polyethersulfones. Polymeric materials for the dispersed particles may be chosen from a broader range of materials than that which goes into making the matrix. The choice of materials is in part determined by how the minor component which forms the particles is introduced. The polymers that go into forming the particles can be chosen from those that may in another case form the matrix, with the condition that the polymers of the particle forming material are incompatible with the polymer which forms the matrix. Polymer compatibility/incompatibility is a well studied field [The Handbook of Solubility Parameters and other Cohesion Parameters by Allan F.M. Barton, CRC Press 1983] and the method is preferred because, by this approach, fine particles of the range of 0.05 to 10 micrometers are easily achieved. Suitable charged polymers for the dispersed particles in the matrix structure can be inorganic or organic polymers that show the desired incompatibility with the matrix-forming polymers. Preferred are halomethylated polyphenylene oxides, polyether sulfones, polysulfone or polystyrenes, each quaternated with tertiary amines; sulfonated and/or carboxylated polystyrenes, polysulfones or polyether sulfones, especially sulfonated polysulfones with ion-exchange capacities suffiently different from the matrix materials to make the two incompatible (such as sulfonated polysulfones of 0.6 meq/g and 1.2 meq/g are incompatible). Further suitable polymers are such on the basis of polydialkyl(dimethyl)siloxanes, such as polydimethyl-siloxanes containing in addition e.g. groups that can be charged with amino or halogen compounds, such as vinyl methyl, (acyloxypropyl)methyl, (aminopropyl)methyl, (chloromethylphenethyl)methyl, chloropropyl(methyl), (epoxycyclohexylethyl)methyl, or (mercaptopropyl)methyl pendants attached to the silicone atoms, as homo- or copolymers with polydimethyl siloxanes. Especially preferred are halomethylated 2,6-polyphenylene oxides, polysulfones or polyether sulfones, quaternated with tertiary amines. The inventive semipermeable asymmetric charge-mosaic organic polymer membranes can be prepared by a process which comprises (a) forming a polymer phase of charged or non-charged matrix-forming polymer and at least one precursor polymer, incompatible with the matrix-forming polymer, by mixing solutions of the two polymers in a common solvent or solvent mixture or different solvents or their mixtures to get a casting solution, (b) casting a film of said solution, (c) forming on one side of said film a skin, (d) effecting precipitation of the skinned film to form asymmetric membranes, (e) charging them by chemical reactions to introduce or complete their charge-mosaic structure, and (f) optionally crosslinking either the matrix and/or the precursor polymer. The inventive process for preparing the asymmetric charge-mosaic membranes may comprise such embodiments wherein in step (a) the matrix-forming polymer is the major polymer component and the precursor polymer is the minor polymer component to be mixed from their corresponding solutions in a common or different solvent or solvent mixtures to get a casting solution; the matrix-forming polymer and the precursor polymers are neutral or of the same charges; the matrix-forming polymer is neutral or of one or both charges and the precursor polymers are neutral; the matrix-forming polymer and one precursor polymer are of the same charge and incompatible or compatible with each other, and a second precursor polymer is neutral. A further embodiment of the inventive process comprises forming a polymer phase of a neutral matrix-forming polymer and two different precursor polymers which are incompatible with the matrix-forming polymer and each other by mixing solutions of the polymers in a common solvent or solvent mixture or different solvents or solvent mixtures to get a casting solution, casting a film of said solution, forming on one side of said film a skin, effecting precipitation of the skinned film to form asymmetric membranes, and charging them by chemical reactions to introduce anionic and cationic charges. More particularly, for making the inventive membranes and introducing the precursor polymers as the particles into the membrane, these polymers can be dissolved in the solvents (solvent mixtures) common or different to the matrix polymers. After the membranes are formed with the said particles, the particles are quaternized with tertiary amines. In this case, the matrix material is chosen to be anionic, such as sulfonated polysulfones. Then the halomethylated polymer solution is added to the solution of the sulfonates polysulfone, the large difference in the physico-chemical properties of the polymers causes the minor component (halomethylated polymer) to precipitate. If the quaternized polymers were added instead of its halomethylated precursor, then the cationic and anionic sulfonated polymer would precipitate together and a membrane could not be formed. As described, the incompatibility may manifest itself in the casting solution; in effect, when the solution of one of-the minor polymer components are mixed in the presence of another polymer, the minor polymer precipitates out in the casting solution as separated particles. Alternatively, this incompatibility may occur during the evaporation stage when the top surface of the wet film is densified prior to coagulation in the process of making asymmetric membranes. The particles may also be formed during the coagulation step. Surfactants, emulsifiers, and stability/compatibility agents may be added to the casting solution in order to improve the stability between the particles and the matrix being incompatible to each other. The basic principles for making asymmetric membranes are known in the literature. Membrane casting may be performed by casting procedures cited in the patent literature, for example in US-A-4,029,582, GB-A-2,000,720, US-A-3,556,305, US-A-3,615,024, US-A-3,567,810, or CA-A-1,234,461; further in Desalination 36, 39-62 (1981). Thus, the polymer or its derivatives may be dissolved in a suitable solvent or mixture of solvents (for example N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphortriamide, N,N-dimethylacetamide (DMCA), dioxane), which may or may not contain co-solvents, partial tetrahydrofuran solvents, non-solvents, salts, surfactants or electrolytes for altering or modifying the membrane morphology and its flux and rejection properties (i.e. acetone, ethanol, methanol, formamide, water, methylethylketone, triethyl phosphate; sulfuric acid, hydrochloric acid; organic acids, preferably of low molecular weight such as formic, acetic or lactic acid; surfactants and emulsifiers of the group of e.g. partial esters of fatty acids and sugar alcohols or their ethylene oxide adducts, e.g. polyoxyalkylated fatty acid partial esters of polyhydric alcohols, such as polyoxyethylene sorbitan tristearates or polyoxyethylene sorbitan trioleates; polyhydric alcohol fatty acid esters such as sorbitan monolaurate, -monpalmitate, -monostearate, -monooleate, -tristearate or -trioleate; sodium dodecyl sulfate; fatty acid amides, such as coconut fatty acid diethanol amine adducts; or alkylphenol polyglykolethers, sodium dodecyl sulfate (SDS), or sodium dodecylbenzene sulfonate; sodium hydroxide, potassium chloride, zinc chloride, calcium chloride, lithium nitrate, lithium chloride, magnesium perchlorate, etc. The casting solution may be filtered by any of the known processes (i.e., pressure filtration through microporous filters or by centrifugation), and cast on a support, such as e.g. glass, metal, paper or plastic, from which it may then be removed. It is preferred, however, to cast on a porous support material from which the membrane is not removed. Such porous suports may be non-woven or woven clothes, such as cellulosic derivatives, polyethylenes, polypropylenes, polyamides (nylon), polyvinyl chlorides and its copolymers, polystyrenes, polyethylene terephthalates (polyesters), polyvinylidene fluorides, polytetrafluoroethylenes, polyether ketones, glass fibers, porous carbon, graphite, inorganic membranes based on alumina and/or silica, optionally coated with zirconium oxide or other oxides, or ceramics. The membrane may alternatively be formed as flat sheet or as a hollow fiber or tubelet. The concentration of polymer in the casting solution may vary as a function of its molecular weight and of the further additives between 5 to 80%, but preferably between 10 and 50% and most preferred between 15 to 30%. The temperature of casting may vary from -20 to 100°C, but the preferred range is between 0 and 60°C, varying as a function of the polymer, its molecular weight and the cosolvents and additives in the casting solutions. The polymer casting solution may be applied to the above mentioned supports by any of the well known techniques, known to those skilled in the art (step b). The wet film thickness may vary between 15 micrometers to 5 mm, the preferred range being 50 to 800 micrometers and the most preferred 50 to 400 micrometers, especially for flat membranes; tubelets may, of course, have thicker walls. The wet film and support may then be immersed immediately or, after a partial evaporation step (from 5 seconds to 48 hours), at ambient conditions or elevated temperatures, or vacuum or any combination thereof (step c) into a gelling bath of a non-solvent (step d). The partial evaporation of the solvent or solvent mixture may be carried out by exposing one side of the wet film to gas or air at temperatures in the range of from -10°C to 130°C, preferably 0°C to 100°C. It appears that the process of evaporation of the top layer followed by a rapid immersion into a gelling bath gives an asymmetric structure wherein particles of the minor polymer are dispersed in the membrane matrix. In some cases, asymmetric membranes may be formed without the evaporation step. Such baths are usually water or water with a small percentage of a solvent (for example DMF or NMP) and/or a surfactant (for example sodium dodecyl sulfate and/or (watersoluble) salts such as sodium chloride, sodium nitrate, calcium chloride and others) at a temperature of 0 to 70°C. An example of a commonly used gelling bath is water with 0.5% SDS at 40°C. In another mode of forming membranes, a polymer solution containing a component that may be leached out in water or another solvent is cast and dried before immersion. After immersion, leachable material is removed, resulting in a porous membrane. In a third variation, a polymer solution without any leachable materials is cast and taken to dryness, resulting in a porous membrane by virtue of the physicochemical properties of polymeric material - solvent combination or by a subsequent chemical reaction that creates pores. While the above procedures are general, the asymmetric membrane should be cast in such a way that it has the desired molecular weight cut-off. Ultrafiltration (UF) membranes with cutoffs of 1500 Daltons or more are easily prepared by state of the art methods. Such UF-membranes may be made into mosaics as described above, but are of limited value because these membranes pass salt without the need for a mosaic pathway. Most mosaic membranes will be needed with membranes that reject organic solutes with molecular weights of less than about 500, because such membranes begin to reject mono- and divalent salts. Asymmetric membranes with cutoffs of less than 1000 and especially between 150 und 700 are difficult to make, and very few materials have been cast with cutoffs in this range. The preferred polymers for achieving said performance have been mentioned hereinbefore. The sulfonated polysulfones and polyethersulfones give particularly good results. In the case of sulfonated polysulfones, solvent mixtures of THF, water, DMAC, DMF, NMP, DMSO, dioxane can give good asymmetric membranes with molecular weight cutoffs below 500. These solvent mixtures are also suitable because they allow the formation of particles of the minor component in the asymmetric membrane matrix. After membrane formation chemical treatments are established in order to introduce charges into the dispersed particles and/or the matrix for forming or completing the mosaic structure within the asymmetric membrane (step e). In optional step (f) of the process for preparing the inventive mosaic membranes either the matrix and/or the precursor polymers (particles) may be cross-linked. Such a cross-linking step is useful to decrease swelling of the inventive membranes, and, thus, improves the rejection to organic solvents. Crosslinking of the halomethylated polymers, for example, can be brought about with di- or poly-primary, secondary or tertiary amines on alkyl or aromatic moieties. Di-tertiary amines can be used to both charge and crosslink. In all cases, the di- or polyamines can be added together with the mono tertiary amines, or before or after the quaternization step. Polyamines may be monomers with more than two amino groups, or they may be polymers, such as polyethyleneimines or polyallylamines. Cationic and anionic polymers cannot be mixed together without special precautions in a solution because they interact and precipitate and the resultant gelatinous mass cannot be cast into a membrane. Since the final membrane must contain both cationic and anionic areas, one or both of the charges must be formed after the membrane has been formed. Preferred precursors are haloalkylated polymers. Where the alkyl may be chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl and further alkyls up to 12 carbon atoms, straight chained or branched, the halogen may be Cl, Br or J. From the point of view of ease of preparation, bromomethylated polymers are preferred. The polymers that are preferred are halomethylated 2,6-dimethyl polyphenylene oxide or halomethylated polysulfone. After the membrane is formed, the halomethylated groups are converted into quaternary phosphonium, sulfonium or preferably ammonium groups, the latter by reaction with solutions containing tertiary alkyl amines, whereas the alkyl groups may contain 1 to 12, preferably 1 to 4 carbon atoms. Most preferred are methyl and ethyl. The conditions of reaction are known from the state of the art. Other precursor polymers which finally form amino or quaternary ammonium salts are polyvinyl halides when reacted with amines; or amino group-containing polyolefins or polyaromatics which are converted to amides or exist as phthalimides and are then hydrolyzed back to the amines after the membrane is formed. Other amino-blocking groups may be used similarly. Precursor anionic polymers may be carboxyl or/and sulfonic acid groups containing olefinic or aromatic backbones, which are in their ester form. Once the membranes are formed, the esters are hydrolyzed to give the fixed anionic group. The precursor polymers may be used for forming either the particles or the membrane matrix, but if they are used as the major component to form the membrane, they must be a film former and be able to be cast into an asymmetric membrane with the desired cutoff. In addition, the chosen precursor should be incompatible with the other polymer. As preferred combinations to prepare the inventive asymmetric membranes sulfonated polysulfone as the matrix-forming polymer, in which the sulfonic content is betweeen 0.05 to 1.2 meq/g of polymer, preferably 0.6 to 0.8 meq/g can be used. The particle forming polymers are bromomethylated polyphenylene oxide with an active bromo content of 0.5 to 5.0 meq/g, but preferably 2.5 to 3.5 meq/g, The sulfonated polysulfone is dissolved in a solvent such as dioxane, or tetrahydrofuran (THF) at a level of 5 to 50%, but preferably 15 to 30%. To this solution other components which may be added are water, NMP, DMA, DMF, DMSO, sulfolane, methanol, ethanol mono- and divalent salts, surfactants and/or emulsifiers in concentrations from 0.05 to 200% of the polymer, preferably from 1.0 to 50% of the polymer. Other preferred combinations are e.g. sulfonated polyether sulfones and bromomethylated polyphenylene oxides; and sulfonated polysulfones or polyethersulfones together with bromo- or chloromethylated polysulfones. Further, matrix-forming polymer containing a relatively low quantity of sulfonic groups, as, for example, 0.5 to 0.7 meq/g with a smaller quantity of a sulfonated polymer containing a relatively high concentration of sulfonic groups (1.2 meq/g), such that the two different polymers are incompatible even though they both contain sulfonic groups, can be used. Both sulfonated polymers would also be incompatible with the bromomethylated polymer. The resultant asymmetric membrane would thus contain particles of the highly sulfonated polymer and cationic particles made from the bromomethylated polymer in a matrix of the sulfonated polysulfone of lower ion exchange capacity (IEC). The inventive membranes are useful for separating organic compounds of low molecular weight from aqueous inorganic salts containing solutions. The corresponding method for separating these compounds from said aqueous media, which comprises disposing the solutions on one side of a semipermeable composite membrane and filtering them through the membrane by applying a hydraulic pressure against said solutions and said membrane being greater than the osmotic pressure of said solutions, is a further object of the present invention. The molecular weight range of the organic compounds to be separated (cut-off level of the inventive membranes) may be less than about 1000, preferably between about 150 and 700. The inorganic salts present in the solutions, which are subjected to the membrane treatment (reverse osmosis), are preferably alkali metal salts of mono- or polyvalent inorganic acids, such as alkali metal halides or sulfates, e.g. sodium chloride and sodium sulfate. The inventive membranes are very suitable for membrane separating processes, especially reverse osmosis processes. They can be prepared and used as flat in plate and frame devices or spiral wound elements, hollow fibers or tubular membranes in corresponding separation devices, such as modules. They have superior rejection to organic compounds of low molecular weight, good flux properties, superior flexibility, to chemical and/or biological degradation. These membranes are especially useful for recovering organic compounds of low molecular weight from chemical reaction solutions or from waste water. These compounds can then be reused or disposed if toxic or dangerous. The separation effect (the rejection) of the inventive membranes can be measured as follows: a circular membrane with a surface area of 13 cm², resting on a sintered stainless steel disc, is used in a cylindrical cell made of stainless steel. 150 ml of the solution (to be tested), which contains the substance to be tested in the concentration C₁ (g of substance per g of solution), are introduced onto the membrane in the steel cylinder and, using nitrogen, subjected to pressure of 40 bars. The solution is stirred magnetically. The liquid which collects on the outlet side of the membrane is examined to determine its content (concentration) C₂ of the substance to be tested, 3 samples of 5 ml each being taken from the start of the experiment. In general, the amount which flows through the membrane and the composition of the 3 samples are constant. The rejection can be calculated from the values obtained, using the equation: The amount of the material passed through the membrane per surface and time is found to be: F = V.S⁻¹.t⁻¹ V :Volume S :membrane surface area t :time F is approximately expressed in m³/m².d, i.e. the number of cubic meters per square meter surface area of the membrane and per day, or in l/m².h, i.e. liters per square meter surface area of the membrane per hour. In addition to the measurements on flat membranes, measurements on tubular membranes 60 cm long and with an outer diameter of 1.4 cm are also carried out. For this purpose, these tubular membranes are placed in a perforated tube made of stainless steel. The whole is placed in a tube made of polycarbonate. The outflow from the membrane is between this outer polycarbonate tube and the steel tube. The liquid is added as a stream of the solution in turbulent or laminar flow under pressure. The flow rate is kept constant at 10 to 15 liters per minute. The rejection (R) and the flux (F) are calculated in the same way as for the flat membranes. In the following examples parts and percentages are by weight, if not otherwise indicated. The temperatures are in degrees Centigrade. Example 18 g of sulfonated polysulfone (PSU-SO₃H) (0.9 meq/g sulfonic acid groups in free acid form, ion exchange capacity - IEC)) is dissolved in 22 ml of dioxane and 3.2 ml of water. Separately 3.4 g of bromomethylated polyphenylene oxide (PPO-Br) (Br content 4 meq/g) is dissolved in 12 ml of dioxane. Both solutions are mixed and stirred well with a mechanical stirrer. From the above solution a wet film is cast on glass 0.4 mm thick, evaporated for 9 minutes at RT (23°C) and gelled in water. The obtained asymmetric membrane is charged in a 10% aqueous solution of trimethylamine (TMA) for 24 hours. The membrane's flux is 1000 l/m².d at 30 bar for a 5% Na₂SO₄ solution, with a sulfate rejection of 21% and a rejection to dinitrostilbene sulfonic acid (DNS) (using a 1% DNS solution) of 99.8%. If not otherwise indicated the testing solutions used hereinafter contain 2 to 5% of sodium sulfate or 1% of DNS. When using mixed solutions, they contain 0.5% of DNS and 2% of sodium sulfate. The tests are carried out at room temperature and at 30 to 40 bar. Example 2Solutions of 8 g PSU-SO₃H (0.9 meq/g) in 24 ml of dioxane, and 2.5 g of PPO-Br (4 meq/g) in 12 ml of dimethylacetamide are prepared. The two solutions are mixed, and 0.1 ml of an octyl alcohol ethylene oxide adduct is added to the casting solution and stirred well. After casting a 0.4 mm wet film, this is heated for 5 minutes at 90°C to evaporate some solvent, gelled and quaternized in TMA according to Example 1. The membrane has a water flux of 136 l/m².d, a sulfate rejection of 10.4% and a rejection to DNS of 99.2%. Example 3Example 2 is repeated with 5.3 g of PSU-SO₃H (0.65 meq/g) and 2.5 g of PPO-Br (4 meq/g). The wet cast membrane film is heated for 3 minutes at 90°C for partial solvent evaporation. The membrane has a water flux of 1120 l/m².d, a sulfate rejection of 33% and a rejection to DNS of 99.5%. Example 4Example 3 is repeated with 5.3 g of PSU-SO₃H (0.65 meq/g) and 5 g of PPO-Br (8 meq/g). The wet cast membrane film is heated for 5 minutes at 90°C for partial solvent evaporation. The membrane has a water flux of 166 l/m².d, a sulfate rejection of 15% and a rejection to DNS of 98.7%. Example 58 g of PSU-SO₃H (0.71 meq/g) are dissolved in 24 ml of dioxane, 1 g of PPU-SO₃H (1.2 meq/g) is dissolved in 5 ml of dimethylacetamide (DMCA) and 3.4 g of PPO-Br are dissolved in 10 ml of DMCA. All three solutions are mixed and stirred well with a mechanical stirrer. From the obtained solution a 0.4 mm wet film is cast on glass, evaporated for 9 minutes at room temperature, and then gelled in water to form an asymmetric membrane. The membrane is charged in a 10% aqueous solution of TMA for 24 hours. The membrane has a water flux of 373 l/m².d, a sulfate rejection of 43%, and a rejection to DNS of 99.3%. Example 64 g of PPU-SO₃H are dissolved in 24 ml of DMAC and 2 g PPO-Br are dissolved in 12 ml of dioxane. Both solutions are mixed and stirred well with a mechanical stirrer. From the obtained solutions a 0.4 mm wet film is cast on glass, dried for 12 minutes at 90°C and gelled in water to form an asymmetric membrane. This membrane is then charged in a 10% aqueous solution of TMA for 24 hours. The membrane has a water flux of 1300 l/m².d, a sulfate rejection of 17%, and a rejection to DNS of 92%. Example 78 g of PSU-SO₃H are dissolved in 29 ml of dioxane and 2 g of PSU-CH₂Br are dissolved in 10 ml of DMAC. Both solutions are mixed and stirred well with a mechanical stirrer. From the obtained solution a 0.4 mm wet film is cast on glass, dried for 4 minutes at 90°C, and gelled in water to form an asymmetric membrane. This membrane is then charged in a 10% aqueous solution of TMA for 24 hours. The membrane has a water flux of 120 l/m².d, a sulfate rejection of 45%, and a rejection to DNS of 98%. Example 8Example 7 is repeated by using 3 g of a brominated polyvinyltoluene instead of PSU-CH₂Br. The results obtained are: a water flux of 950 l/m².d, a sulfate rejection of 20% and a rejection to DNS of 82%. Example 9Example 2 is repeated with other neutral surfactants: Flux (l/m².d) Rejection (%) sulfate DNS (a) polyoxyethylene sorbitanmonooleate6004099.5 (b) nonylphenol polyglakolether9003399.5 (c) coconut fatty acid-diethanolamine adduct80027.598.6 Example 10 Example 1 is repeated by using tetrahydrofuran (THF) instead of dioxane as solvent. The cast wet film is evaporated for 5 minutes at room temperature. The resultant membrane has a water flux of 1200 l/m².d, a sulfate rejection of 10%, and a rejection to DNS of 99%. Example 11 Example 1 is repeated by using THF instead of dioxane as solvent. To the combined solutions 2 ml of DMCA is added. From the casting solution a wet film is bobcast on a tubular polyester support. After an evaporation time of 7 minutes at room temperature, the film is gelled in water and the obtained asymmetric membrane is then charged with TMA as in Example 1. The resultant membrane has a water flux of 800 l/m².d, a sulfate rejection of 5%, and a rejection to DNS of 99%. A scanning electron microscope picture of the membrane surface and cross-section shows uniformly dispersed particles. When a mixture of an aqueous solution containing 5% of the dye of the formula 0.5% of sodium sulfate and 0.5% of sodium chloride are measured with the membrane of this example, the rejection to the dye is 99%, while the rejections to sulfate are 5% and chloride less than 10%, respectively. Example 12A THF/DMAC/H₂O (36/3/4/v/v/v) solution containing 10 g of PSO-SO₃H (0.8 meq/g), 4.25 g of PPO-Br (3.5 meq/g) and 0.2 ml of a coconut fatty acid-diethanolamine adduct as surfactant is cast on a glass and further prepared into an asymmetric membrane according to Example 1. The resultant membrane has a water flux of 750 l/m².d, a sulfate rejection of 0% and a rejection to DNS of 97%. Example 13Example 12 is repeated. When the wet film is cast on glass, evaporated and gelled in water, the asymmetric membrane is charged in an aqueous solution containing 10% of TMA and 2% of diaminopropane for 24 hours. Thus, in one step, the PPO-Br areas are quaternized and cross-linked. The resultant membrane has a rejection to DNS of 99% and 8% rejection to sulfate, with a flux of 630 l/m².d. Example 14A casting solution formulation comprising 6.0 g PSU-SO₃H (IEC 0.8 meq/g), 2.55 g PPO-Br (4 meq/g), 14.5 ml THF, 2.5 ml NMP and 0.1% surfactant is prepared with different quantities of water, and bob cast as in Example 11. The results are given in Table 1 for single solutes and solute mixtures. (Effect of water content in casting solution on mosaic membrane performance in separate and mixed solutions.) Water (ml) Evap.time (min) separate solutions mixed solution %Rej (SO₄--) %Rej (DNS) Flux (l/m².d) %Rej (SO₄--) %Rej (DNS) Flux (l/m².d) 0.51.017.599.332026.799.0290 1.01.010.399.16558.645.1670 Example 15Example 14 is repeated with the addition of 0.2 g lactic acid to the casting solution formulation. The results for different water and evaporation times are given in Table 2. The results show the importance to adjust casting solution composition to get the maximum selectivity. Water (ml) Evap.time (min) separate solutions mixed solution %Rej (SO₄--) %Rej (DNS) Flux (l/m².d) %Rej (SO₄--) %Rej (DNS) Flux (l/m².d) 0.52.029.899.62308.197.0225 1.01.06.799.348013.397.8490 Example 16In Example 5, 8 g PSU-SO₃H is the matrix material with 0.7 meq/g, while the 1.0 g of PSU-SO₃H has an IEC of 1.2 meq/g, and forms particles in the matrix. The total system is thus composed of low IEC-PSU-SO₃H, with particles of relatively high IEC-PSU-SO₃H and PPOBr. In this example a different matrix is used based on polyetherimide (Ultem 100/GE®), instead of the low 0.7 meq/g IEC sulfonated polysulfone. Example 5 is repeated using 5 g Ultem 100 instead of 8 g PSU-SO₃H, and the solvent mixture used contains 15 g NMP and 30 g THF. The resultant tubular membrane gives 94% rejection to DNS and 15% to sodium sulfate. Example 17Example 12 is repeated using chloromethylated polyslfone instead of PPOBr. The rejection to DNS is 98% and 10% to sodium sulfate.
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A semipermeable charge-mosaic organic polymer membrane with macroscopic distribution of the mosaic-forming anionic and cationic charges which comprises an asymmetric structure of at least one charged polymer dispersed in a matrix-forming polymer of opposite charge, or of polymers of both charges dispersed in a neutral matrix-forming polymer or in a matrix-forming polymer of one or both charges. A membrane according to claim 1 which comprises the matrix-forming polymer as major component and the polymers dispersed therein as minor component. A membrane according to any one of claims 1 or 2, wherein the dispersed polymer contains cationic charges and the matrix-forming polymer contains anionic charges. A membrane according to any one of claims 1 to 3, wherein the charged polymers are in the form of distinct particles in the matrix structure. A membrane according to any one of claims 1 to 4, wherein the matrix-forming polymers are polysulfones, polyether sulfones, polyetherketones, polyether-etherketones, polyether imides, polyphenylene oxides, polyphenylene sulfides, polyamides, polyimides, polyamide-imides, polycarbonates, polyacrylonitriles, polyethers, polybenzimidaxoles, cellulosics, or their derivatives. A membrane according to claim 5, wherein the matrix-forming polymers are cellulose acetates, sulfonated polysulfones and polyether sulfones, or polyether imides, polyamides, polyimides, polycarbonates, or sulfonated 2,6-dimethylphenylene oxides. A membrane according to any one of claims 1 to 6, wherein the charged polymers dispersed in the maxtrix-structure are organic or inorganic polymers incompatible with the matrix-forming polymers. A membrane according to claim 7, wherein the charged polymers are halomethylated polyphenylene oxides, polyether sulfones, polysulfones or polystyrenes, each quaternated with tertiary amines; sulfonated and/or carboxylated polystyrenes, polysulfones or polyether sulfones; or homo- or copolymers on the basis of polydimethyl siloxanes, containing groups that can be charged with amino or halogen compounds. A membrane according to claim 8, wherein the polymers are halomethylated 2,6-polyphenylene oxides, polysulfones or polyethersulfones, quaternated with tertiary amines. A membrane according to any one of claims 5 to 9, wherein the matrix-forming polymer is a sulfonated polysulfone and the polymer dispersed therein is a halomethylated 2,6-polyphenylene oxide, quaternated with a tertiary amine. A membrane according to any one of claims 1 to 10 in flat or tubular form. A process for the preparation of semipermeable asymmetric charge-mosaic organic polymer membranes according to claim 1, which comprises (a) forming a polymer phase of a charged or non-charged matrix-forming polymer and at least one precursor polymer, incompatible with the matrix-forming polymer, by mixing solutions of the two polymers in a common solvent or solvent mixture or different solvents or their mixtures to get a casting solution, (b) casting a film of said solution, (c) forming on one side of said film a skin, (d) effecting precipitation of the skinned film to form asymmetric membranes, (e) charging them by chemical reactions to introduce or complete their mosaic structure. A process according to claim 12 which comprises as additional step (f) cross-linking the matrix and/or the precursor polymer. A process according to claim 12, wherein in step (a) the matrix-forming polymer is the major polymer component and the precursor polymer is the minor polymer component to be mixed from their corresponding solutions in a common or different solvent or solvent mixtures to get a casting solution. A process according to any one of claims 12 to 14, wherein in step (a) the matrix-forming polymer and the precursor polymers are neutral or of the same charges. A process according to claim 15, wherein in step (a) the matrix-forming polymer is neutral or of one or both charges and the precursor polymers are neutral. A process according to claim 15, wherein in step (a) the matrix-forming polymer and one precursor polymer are of the same charge and incompatible or compatible with each other, and a second precursor polymer is neutral. A process according to any one of claims 12 to 17, wherein the polymer concentration of the casting solution is in the range of from 5 to 80 % by weight. A process according to claim 18, wherein the polymer concentration of the casting solution is in the range of 10 to 40 % by weight. A process according to any one of claims 12 to 19, wherein in step (c) the skinned film is formed by physical or chemical treatments. A process according to claim 20, wherein in step (c) a portion of the solvent or solvent mixture is evaporated by exposing said one side of the film to gas or air at a temperature in the range of from -10 to 130°C. A process according to any one of claims 12 to 21, wherein in step (d) precipitation is effected by immersing the film in a non-solvent coagulating bath. A process according to any one of claims 12 to 22, wherein in step (e) the matrix-forming polymers and the precursor polymers within the membrane are treated to charge them with opposite charges. A process according to claim 23, wherein in step (e) the matrix-forming polymers within the membrane are sulfonated to charge them with anionic charges and the precursor polymers within the membrane are quaternated and/or sulfonated to charge them with cationic and/or anionic charges. A process according to any one of claims 12 to 22, wherein in step (e) the charge-mosaic structure is completed by quaternating the precursor polymers which are dispersed in an anionically charged matrix-forming polymer within the membrane. A process according to any one of claims 13 to 25, wherein in step (f) either the matrix and/or the precursor polymer is cross-linked. A process according to claim 12, which comprises forming a polymer phase of a neutral matrix-forming polymer and two different precursor polymers which are incompatible with the matrix-forming polymer and each other by mixing solutions of the polymers in a common solvent or solvent mixture or different solvents or solvent mixtures to get a casting solution, casting a film of said solution, forming on one side of said film a skin, effecting precipitation of the skinned film to form asymmetric membranes, and charging them by chemical reactions to introduce anionic and cationic charges. A method for separating organic compounds of molecular weight of less than 1000 from aqueous, inorganic salt containing solutions which comprises disposing the solutions on one side of a semipermeable membrane according to any one of claims 1 to 11 or obtainable according to the process of any one of claims 12 to 27 and filtering them through the membrane by applying a hydraulic pressure against said membrane being greater than the osmotic pressure of said solution.
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ALIGENA AG
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KETRARO REUVEN; LINDER CHARLES DR; NEMAS MARA; PERRY MORDECHAI DR; KETRARO, REUVEN; LINDER, CHARLES, DR.; NEMAS, MARA; PERRY, MORDECHAI, DR.
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EP-0489697-B1
| 489,697 |
EP
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B1
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EN
| 19,960,522 | 1,992 | 20,100,220 |
new
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H01H51
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H01H1
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H01H51, F02N11, H01H1, H01H50
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H01H 1/50, H01H 51/06B
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An electrical switch, particularly for controlling the supply of current to the electric starter motor of an internal combusion engine
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An electrical switch, particularly for controlling the supply of current to the electric starter motor of an internal combustion engine, in which the movable device (17; 22; 24) and/or its control means (13; 15) are formed in such a way that, in its operating position, the movable contact (22) oscillates after it has struck the fixed contacts (5) and assumes successive configurations (Figure 5) in which its deformation or deflection (X) always keeps the same sign.
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The present invention relates to an electrical switch usable in particular for controlling the supply of current to the electric starter motor of an internal combustion engine. More specifically, the invention concerns an electrical switch of the type including: a support structure carrying two fixed contacts, a device which carries a movable contact and is movable relative to the support structure between a rest position in which the movable contact is separated from the fixed contacts and an operating position in which the movable contact is brought to bear against the fixed contacts, is deformed resiliently like a beam, and is subject to damped oscillations, and control means for moving the movable device between its rest position and its operating position, in which the movable device and/or the control means are formed in such a way that, in the operating position, the movable contact oscillates after it has struck the fixed contacts and assumes successive configurations in which its deformation or deflection always keeps the same sign. In known devices, the control means typically comprise an electromagnet including an excitation coil or solenoid and an associated movable core which, when the solenoid is energised, can urge the movable device into the operating position defined above. In devices produced up to now, the movable contact is usually constituted by a metal (copper) plate and the fixed contacts are usually arranged symmetrically of the axis of the movable device. In these devices, when the control solenoid is energized, the movable contact is urged against the fixed contacts and may then bounce several times before it stops firmly against them. This bouncing results in the striking of arcs and the material of the fixed contacts and the movable contact may fuse locally, with the danger that one or both ends of the movable contact may be welded ( stuck ) to the fixed contacts. When this happens, the means for returning the movable device to its rest position (usually a spring) cannot detach the movable contact from the fixed contacts and, in this event, the electric starter motor of the internal combustion engine remains activated even after the control solenoid has been de-energised. European patent application EP-A-0 324 262 relates to a switch for an electric starter motor of the type specified, in which the movable contact comprises a main bridging contact to carry the entire current of the starting motor and which is subject to bounce and a bridging element which is overlapped to the bridging contact. The bridging element is so shaped that during the movement of the bridging contact the element engages the fixed contacts before the bridging contact and thereafter flexes variably during the bounces of the bridging contact but remaining engaged with the fixed contacts. A movable contact of this structure results quite expensive. German patent application DE-A-1104024 relates to a contact device comprising a movable contact constituted by a main mass subject to a given static force and a stationary contact, carried at one end of a leaf spring. The static force on the main mass will provide a static deflection on the leaf spring. This reference gives elements to determine the elastic constant of the leaf spring as function of various parameters to avoid the bounces between the contacts. However the above elements cannot be transferred to the structure of switch of the aforesaid type. The object of the present invention is to provide a device of the type specified above, which does not have the disadvantages described above. According to the invention, this object is achieved by means of an electrical switch of the aforesaid type, the main characteristic of which lies in the fact that after it has struck the fixed contacts, the movable contact is subject to the combined effect of a static load and damped vibrations which cause a resilient deflection of the movable contact having a substantially constant static deflection component and a damped oscillating component which, during successive time intervals, alternately has a sign the same as and the opposite of that of the static component, and the dimensions of the device are such that the static component of the deflection of the movable contact is greater than or at least equal to the maximum value assumed by the dynamic component whose sign is the opposite of that of the static component. As will become clearer from the following, in the device according to the invention, it is impossible for the movable contact to move away from the fixed contacts during its damped oscillation after it has struck them so that the striking of arcs and the related damaging consequences are effectively prevented. Further characteristics and advantages of an embodiment of the invention will now be made clear by the detailed description which follows, with reference to the appended drawings, provided purely by way of non-limiting example, in which: Figure 1 is a partially-sectioned view of an electrical switch embodying the invention, Figures 2 to 5 are schematic diagrams relating to theoretical considerations upon which the present invention is based, and Figure 6 is a graph showing the deflection of the movable contact of the switch embodying the invention plotted against the time t shown on the absicssa. In Figure 1, an electrical switch usable, in particular, for controlling the supply of current to the electric starter motor (not shown) of an internal combustion engine, is generally indicated 1. It includes, in known manner, a substantially cup-shaped support 2 to the top of which an electromagnet, generally indicated 3, is fixed. The support 2 has a recess 4 in its side which faces the electromagnet 3. Screws of electrically-conductive material, preferably copper, indicated 5, extend through holes 7 in the base wall of the support 2. In the embodiment illustrated, the screws 5 have respective hexagonal heads 5a which act as fixed contacts, as will become clear from the following. The screws 5 are fixed to the support 2 by washers 11 force-fitted onto their respective threaded shanks. The base wall of the recess 4 in the support 2 has a substantially cylindrical recess 12. In known manner, the electromagnet 3 includes a tubular housing 14 in which a coil or solenoid 10 carried by a spool 9 is mounted. A stop and guide element 8 with an axial hole 8a is inserted in the spool 9 at its end facing the support element 2. The movable core of the electromagnet 3 is indicated 15. The core is movable in the axial hole in the spool 9. A movable device, generally indicated 17, is movable axially in the axial hole 8a in the stop and guide element 8. The device comprises a rod 18 with a head 19 at its end facing the support element 2. A helical spring, indicated 20, is disposed in the recess 12 in the support element 2 between the base wall of the recess and the head 19 of the rod 18. A sleeve 21 is fixed to the other end of the rod 18 and is guided slidably in the hole 8a in the element 8. A movable contact 22 in the form of a substantially rectangular conductor plate is fitted on the rod 18, between the guide sleeve 21 and the head 19 of the rod. The plate has a central hole 22a through which the rod 18 extends with the interposition of a washer 23. A fairly stiff helical spring 24 is disposed around the rod 18 between the guide sleeve 21 and the washer 23. The spring is preloaded under compression and urges the movable contact 22 towards the position shown, that is, against the head 19 of the rod 18, with a force F. The arms of the movable contact 22 face the fixed contacts constituted by the heads 5a of the screws 5. As in prior-art devices, the energisation of the control solenoid 13 in operation causes the core 15 to be moved towards the movable device 17. The core 15thus reaches the rod 18 of the device and urges it towards the fixed contacts 5a. Immediately after the movable contact 22 strikes the fixed contacts, the rod 18 still continues towards the base wall of the support element 2, further loading the helical spring 24. In the device embodying the invention, the bouncing or jumping of the movable contact on the fixed contacts after its initial impact is conveniently prevented by virtue of measures which will be described below after the explanation of some theoretical considerations or premises upon which the invention is based and which will now be explained with reference to Figures 2 to 6. The movable contact 22 bearing on the fixed contacts 5a may be considered essentially as a resiliently deformable beam according to the simplified diagram of Figure 2. The fixed contacts 5a represent the supports of the beam. In the following description with reference to Figures 2 to 5, each time the term beam is used it actually means the movable contact and each time the term supports is used it means the fixed contacts. In Figure 2, the resultant of the forces acting on the movable contact 22 which bears on the fixed contacts 5a, due to the preloading of the spring 24 is indicated F. The force F is represented as a concentrated load but is actually the resultant of distributed forces. The beam 22 bends under the force F in the manner shown qualitatively in Figure 3. In this drawing, the static deflection of the beam 22 from its undeformed condition (measured at the centre of the beam 22) when beam 22 is subject to the static load represented by the force F and to the reactions of the fixed contacts 5a is indicated xst. The ratio k between the force F and the static deflection xst is a characteristic of the beam 22 and will be defined below as the elastic constant of the beam. As stated above, after it has struck the fixed contacts 5a, the movable contact 22 is resiliently deformed and is subject to damped dynamic vibrations. Since the elastic constant of the helical spring 24 is typically much lower than that of the movable contact 22, the mode of the vibration of the system may be considered to be due only to the movable contact itself. If f₁ indicates the basic frequency of the flexural vibration of the movable contact 22, the dynamic deflection or displacement at the centre of the movable contact 22 during vibration can be expressed as follows: xt=Vowe-µtsin wt in which Vo is the speed of the movable contact 22 when its resilient reaction equals the preloading F of the spring 24, w is the angular frequency corresponding to the frequency f₁ (w=2pi.f₁), µ is a damping coefficient, and t is the time. The speed of the displacement of the centre of the movable contact is derived from the equation (1) above and can thus be expressed as follows: xt = Vow[-µe-µtsinwt + we-µtcoswt] During the vibration, the speed of the centre of the movable contact becomes zero at successive moments which can be calculated as follows: xt = 0 µe-µtsin(wt) = we-µtcos(wt) t = 1w[tan-1(wµ) + npi] n=0,1,2,... The speed of the centre of the movable contact will therefore first become zero at a moment t = t1 = 1w[tan-1(wµ)] n=0 With reference to Figure 4, at the time t₁, the beam 22 will assume, for example, the configuration indicated 22 (t₁). This configuration corresponds to the maximum dynamic deflection of the beam. The speed of the movable contact/beam 22 subsequently becomes zero at a moment t = t2 = 1w[tan-1(wµ) + pi] n=1The configuration generally assumed by the beam 22 at the moment t₂ is indicated (qualitatively) 22 (t₂) in Figure 4. The speed of the movable contact/beam 22 then becomes zero again at the moment t = t3 = 1w[tan-1(wµ) + 2pi] n=2 and the configuration assumed by the movable contact/beam is correspondingly indicated 22 (t₃) in Figure 4. The movable contact/beam 22 has a smaller dynamic deflection at the moment t₃ than at the moment t₁. At the moments t₁ and t₃, therefore, the curvatures of the movable contact/beam 22 are different but have the same sign. In general, the sign of the curvature of the movable contact/beam 22 at the moment t₂ (and at subsequent moments t2n), resulting solely from its dynamic oscillation (and hence taking no account of the static load represented by the force F) is the opposite of that of its curvature at the moments t1 and t3 (and at subsequent moments t2n+1). If an electric switch of the type described above with reference to Figure 1 is formed in such a way that its static deflection xst as defined above is greater than or at least equal to its dynamic deflection x(t₂) at the moment t₂, then the overall deflection X(t) = xst + x(t) will always have the same sign. In other words, if this condition occurs in a real situation, after it strikes the fixed contacts 5a, the movable contact 22 is subject to damped vibrations as a result of which it assumes successive configurations in which its curvature always has the same sign, as shown in Figure 5. The fact that the movable contact 22 vibrates but remains deflected to the same side, that is, towards the fixed contacts, means that it is not raised from the contacts as could occur if it were able alternately to assume opposite curvatures during its vibration. In view of the foregoing, the condition necessary for the movable contact/beam 22 always to bend to the same side can be expressed analytically as follows: In a simplified (but nevertheless conservative) hypothesis in which the damping factor µ is zero, the foregoing condition is further simplified as follows: FK≥Vow and this can be rewritten as follows: K≤wFVo The equation (9) immediately provides a design criterion usable to ensure that the movable contact 22 does not bounce. Thus, in designing a device of the type of Figure 1, one can, for example, take the movements of a similar existing device and simply alter solely the dimensions of the movable contact member 22. The dimensions of this member should be such that it conforms to the equation (9) given above. Figure 6 of the appended drawings shows, by way of example, a curve of the overall deflection X(t) of the movable contact/beam of a device for which the equation (7) or (more conservatively) the equation (9) given above is satisfied. In the graph of Figure 6, the static deflection xst has been considered to be constant and equal to the ratio between the force F and the elastic constant k of the movable contact/beam 22. Strictly, in a device of the type shown in Figure 1, the action of the spring 24, which is further (though slightly) loaded after the movable contact 22 has struck the fixed contacts 5a, also contributes to the definition of the static deflection xst. It should be noted, however, that the contribution to the static deflection due to this further loading of the spring 24 is extremely small if one takes account of the fact that it involves an extremely slow increase in the static deflection (as indicated, for example, by the broken line in Figure 6), whilst the oscillations of the dynamic component take place at a very high frequency. In general, in order to comply with the conditions expressed by the equation (7) or the equation (9), the designer can alter the mass of the movable contact 22 (on which its basic vibration frequency f₁ and hence its angular frequency w=2πf₁ depends), the flexural elastic constant k of the movable contact, the elastic constant of the spring 24, the preloading of the spring and the speed of the movable contact when it strikes the fixed contacts. This last parameter in turn depends on a series of factors such as the size of the control solenoid, the mass of the core 15, etc..
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An electrical switch, particularly for controlling the supply of current to the electric starter motor of an internal combustion engine, including: a support structure (2) carrying two fixed contacts (5), a device (17) which carries a movable contact (22) and is movable relative to the support structure (2) between a rest position in which the movable contact (22) is separated from the fixed contacts (5) and an operating position in which the movable contact (22) is brought to bear against the fixed contacts (5), is deformed resiliently like a beam, and is subject to damped oscillations, and control means (13, 15) for moving the movable device (17) between its rest position and its operating position, in which the movable device (17; 22; 24) and/or the control means (13; 15) are formed in such a way that, in the operating position, the movable contact (22) oscillates after it has struck the fixed contacts (5) and assumes successive configurations in which its deformation or deflection (x) always keeps the same sign, characterised in that, after it has struck the fixed contacts (5), the movable contact (22) is subject to the combined effect of a static load (F) and damped vibrations which cause a resilient deflection (X(t)) of the movable contact (22) having a substantially constant static deflection component (xst) and a damped oscillating component (x(t)) which, during successive time intervals, alternately has a sign the same as and the opposite of that of the static component (xst), and the dimensions of the device are such that the static component (xst) of the deflection of the movable contact (22) is greater than or at least equal to the maximum value (x(t₂)) assumed by the dynamic component (x(t)) whose sign is the opposite of that of the static component (xst). An electrical switch according to Claim 1, characterised in that the movable contact (22) comprises a single deformable member for bridging the fixed contacts (5). An electrical switch according to Claim 1, or Claim 2, characterised in that the dimensions of the movable contact (22) are such that its elastic constant (k) is less than or at least equal to w.F/Vo, in which w is the angular frequency corresponding to the basic frequency of the flexural vibration of the movable contact (w=2πF1), F is the static load and Vo is the speed of the movable contact when its resilient reaction equals the static load.
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MAGNETI MARELLI SPA; INDUSTRIE MAGNETI MARELLI S.P.A.
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CERIZZA GIOVANNI; FASOLA GIANCARLO; HYDER WILLIAM THOMAS; CERIZZA, GIOVANNI; FASOLA, GIANCARLO; HYDER, WILLIAM THOMAS; Fasola, Giancarlo, c/o Industrie Magneti
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EP-0489700-B1
| 489,700 |
EP
|
B1
|
EN
| 19,940,622 | 1,992 | 20,100,220 |
new
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E21D20
| null |
E21D20
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E21D 20/00G
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Rock bolting device
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Rock bolting device comprising a swingable bolting unit (2) which carries a conduit (4) for transport of hardenable mass to a drill hole (3). The conduit is surrounded by a tube (5) in which a thickened part (6) of the conduit is movable to-and-fro under sealing cooperation with the tube. Through this the conduit (4) can be fed towards or away from the mouth (7) of the drill hole (3).
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The present invention relates to a rock bolting device in which a hardenable mass is entered into a drill hole in the rock. In a prior art device of the above mentioned kind, see US-A-4 215 953, a hydraulic cylinder is used in order to feed a tube, for supply of hardenable mass, to or from the drill hole in the rock. The present invention, which is defined in the subsequent claims, aims at achieving a device where the above mentioned hydraulic cylinder can be avoided. Through this two advantages are achieved, lower costs and lower weight of the bolting unit which is situated far away from the carrier. A further advantage which is obtained if the conduit for feeding hardenable mass to the drill hole is made of plastic or rubber is that the device becomes comparatively insensitive to side loads or other loads caused by caving or similar. An embodiment of the invention is described below with reference to the accompanying drawings in which fig 1 shows a rock bolting device according to the invention. Fig 2 shows a part of the device according to fig 1 during drilling of a hole in the rock. Fig 3 shows the device with the conduit for feeding in of hardenable mass in line with the drill hole. Fig 4 shows the device during feeding forward of the conduit towards the drill hole mouth. Fig 5 shows the device with the conduit at the drill hole mouth. Fig 6 shows a circuit diagram for the feeding of the conduit towards or from the rock. The device shown in the drawings comprises a carrier 1 and a bolting unit 2 arranged on a boom 8 on the carrier. The bolting unit comprises a feed beam 9 along which a rock drilling machine 10 is movable to-and-fro. The feed beam is at its front end provided with a support 11 for contact with the rock 12. This contact defines an axis about which the bolting unit is turnable between a drilling position and a position for introduction of hardenable mass into the bore hole. The bolting unit comprises furthermore a magazine 13 for rock bolts. The device comprises a, not shown, storage for hardenable mass on the carrier. Hardenable mass is fed from the carrier 1 via conduit 4 to a nozzle 14 on the bolting unit 2. The bolting unit is provided with a swingable drill guide 15 which guides a drill string 16 connected to the rock drilling machine 10 and carries the nozzle 14. The conduit 4 shown in the drawings comprises at its front end two tube pieces 17,18 which are interconected by means of a thickened part in form of a piston 6. This piston cooperates sealingly with a tube 5 surrounding conduit 4. Tube 5 is provided with two connections 19,20 for supply of pressure fluid, preferably water, to drive the piston 6 in one or the other direction in tube 5. Conduit 4, including tube pieces 17,18, is suitably made in some suitable plastic or rubber material. Conduit 4 can alternatively be a through conduit provided with a thickened part in form of a ring which is fastened by means of glueing, welding or in another suitable way. Conduit 4 is provided with a loading tube 23 where cartridges 29 with hardenable material, e.g. plastic with hardener, can be supplied to conduit 4. Other materials can be used as hardenable material, e.g. a cement mixture, whereby the supply to conduit 4 is performed in another way. Conduit 4 is via a valve 22 connected to a compressed air source 21. Connections 19,20 are via valves 25,27 connected to a pressure fluid source 24, in the shown example a pressure liquid source. The connections are furthermore via valves 26,28 connected to low pressure. The device shown in the drawings works in the following way. Support 11 is applied against the rock 12 after which the bolting unit 2 is turned to the position shown in fig 2. Hole 3 is drilled. Then the drill string 16 is returned and the bolting unit 2 is swung to the position shown in fig 3. Valves 25 and 28 are opened so that nozzle 14 is displaced towards the drill hole mouth 7 via the position in fig 4 to the position in fig 5. One or more cartridges 29 with hardenaable mass is introduced into loading tube 23 after which valve 22 is opened so that the cartridges are introduced into bore hole 3. Then valves 22, 25 and 28 are closed. Valves 27 and 26 are opened so that conduit 4 is returned. The bolting unit 2 is swung away so that a rock bolt can be entered into bore hole 3. On doing so cartridges 29 are crushed so that plastic and hardener come into contact with each other so that the hardening starts.
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Rock bolting device comprising a carrier (1), a bolting unit (2) arranged on the carrier, said bolting unit being swingable between a drilling position (fig 2) and a position (fig 5) for feeding in of hardenable mass into a drill hole (3), whereby said bolting unit carries a conduit (4) for transport of hardenable mass to the drill hole, and comprises a tube (5) surrounding said conduit (4), characterised in that the conduit is provided with a thickened part (6) which by means of pressure fluid is movable to-and-fro in said tube under sealing cooperation with the tube, whereby the conduit is displaceable towards or away from the mouth (7) of said drill hole (3).
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ATLAS COPCO CONSTR & MINING; ATLAS COPCO CONSTRUCTION AND MINING TECHNIQUE AB
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WALLIN PER; WALLIN, PER
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EP-0489701-B1
| 489,701 |
EP
|
B1
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EN
| 19,960,228 | 1,992 | 20,100,220 |
new
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B23B27
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B23B5
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B23B27, B23B5
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B23B 27/14B, B23B 5/12
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Cutting insert and cutting tool for a peeling operation
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A multi-cornered cutting insert includes a corner cutting edge at each corner, and a chipbreaking recess spaced inwardly of each corner cutting edge. The recess is curved as the insert is viewed in plan. A clearance face for each corner cutting edge has a clearance angle which progressively increases toward the respective corner.
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Background of the InventionThe present invention relates to a cutting insert and cutting tool for turning operations. More specifically the invention relates to a turning insert for a bar peeling operation performed on solid or hollow bars formed of stainless steel or other heat resistant materials. The insert has a polygonal form including an upper chip face, an opposite bottom face and a clearance face located therebetween, whereby the intersection of the chip face and the clearance face forms a cutting edge. Bar peeling as a metalworking operation means that a non-rotatable bar is axially displaced through a central hole of a rotary cutter head. The cutter head is provided with several tools which remove from the bar a thin layer of millscale, surface cracks, etc., that results from the hot rolling of such bars or tubes. In order to achieve the best results regarding tolerances and surface finish, two different types of inserts, i.e., roughing and finishing inserts, are usually combined in the same holder. One of the most commonly used inserts for bar peeling is a so-called trigonal insert as shown and described in U.S. Patent 4,035,888. That insert is in the form of a regular polygonal body the corners of which are configured symmetrically about a corner bisector. Such inserts, however, have somewhat limited utility because they do not enable desired results to be achieved in terms of tolerances and surface finish when large feeds are involved (see for example US-A-4 214 847 and FR-A-2 359 667). The metalworking tool and insert described in US Patent 4,214,847 includes the provision of a recess in the upper chip face of the insert which recess extends parallel to and spaced from the edge of the insert. However the recess is not curved in plan view as provided in our insert. Also, there is no corner clearance face with increased clearance angle in a direction towards the insert corner. In view of these differences in features such insert would not allow the favorable chipbreaking function for both small and large cutting depths as achieved with the presently proposed new insert. Also, such insert will not enable to reduce the tendency for vibrations in a manner comparable with an insert such as defined in the present specification. In view thereof, it is a purpose of this invention to provide a new type of insert with non-symmetrically formed cutting corner portions which will satisfy close tolerance demands and enable good surface finish to be achieved, even at very high feeds. It is another purpose of the invention to provide an insert with an extended lifetime. It is yet another purpose of the invention to provide an insert which can more efficiently reduce the tendency for vibrations to occur during a metal cutting operation. Summary of the InventionThese and other objects of the invention are achieved by a cutting insert for bar peeling which comprises a multi-cornered polygonal body of wear resistant material, according to claim 1. The body includes top and bottom surfaces and peripheral edge surface extending therebetween. The peripheral edge surface includes corner clearance faces disposed at respective corners of the body. The corner clearance faces intersect the top surface to form corner cutting edges. Each corner cutting edge is convexly curved as the top surface is viewed in plan. The top surface defines a chip face and includes chip breaker recesses located adjacent respective ones of the corner cutting edges. Each recess is spaced from its respective corner cutting edge in a direction toward a center of the insert. Each of the recesses is curved such that a near wall thereof located closest to the corner cutting edge is convex as the insert is viewed in plan, and a far wall thereof located farther from the corner cutting edge is concave as viewed in plan. Preferably, each of the corner clearance faces extends at an acute clearance angle relative to the top surface, and the clearance angle preferably becomes progressively larger as a respective corner is approached. The peripheral edge surface preferably includes side clearance faces which intersect the top face to form therewith side cutting edges. An imaginary line extending perpendicularly from a side cutting edge and passing through a geometric center of the insert preferably intersects a respective one of the corner cutting edges such that a portion of the corner cutting edge disposed on one side of that line is longer than the remainder thereof located on the other side of the line. Each of the recesses is preferably elongated so as to be longer in a direction generally parallel to its respective corner cutting edge than a direction generally perpendicular to its respective corner cutting edge. In another aspect of the present invention, a tool for bar peeling comprises a tool holder on which are removably disposed a circular roughing insert and a finishing insert according to claim 14. The finishing insert is substantially triangular shaped with a curved corner cutting edge in each corner thereof. Brief Description of the DrawingThe objects and advantages of the invention will become apparent from the following detailed description of a preferred embodiment thereof in connection with the accompanying drawings in which like numerals designate like elements, and in which: FIG. 1 is a top view of an insert according to the invention; FIG. 2 is a perspective view of the insert of the invention; FIG. 3 is a cross-sectional view taken through the insert along the line 3-3 in FIG. 2; FIG. 4 is a cross-sectional view taken through the insert along the line 4-4 in FIG. 2; FIG. 5 is a side view of a toolholder equipped with an insert according to the invention; and FIG. 6 is a top view of the toolholder shown in FIG. 5 as a workpiece is being cut. Detailed Description of a Preferred Embodiment of the InventionAn insert according to the invention is shown in the figures. The insert comprises a polygonal body 10 of wear resistant material. The body includes an upper chip face 11 of substantially triangular form, an opposite bottom face 12 that is parallel with the chip face 11, and a clearance edge surface located between the faces 11, 12. The clearance edge surface includes side clearance faces 13 and curved corner clearance faces 18. The side clearance faces 13 are oriented perpendicularly in relation to faces 11 and 12. The insert body has a central aperture 14 which extends entirely through the insert body to receive a suitable clamping screw or lever arm of an associated toolholder 15. Side cutting edges 16 are defined by the intersection between faces 11 and 13. The corner clearance faces 18 intersect the upper chip face 11 to form corner cutting edges 17. In accordance with the invention, each corner cutting edge 17 is curved as the insert is viewed in plan (FIG. 1). Also, the corner clearances faces 18 are convexly curved such that the major portion of the corner cutting edge 17 is located on one side of an imaginary line B which passes through the corner. That line B extends perpendicularly from the center of an opposite edge 16 and passes through the center C of the insert. Each face 18 has a clearance angle α which increases progressively towards the cutting corner from an intersection line 19 formed by the intersection of faces 18 and 13. The angle α is zero at juncture line 19 and then increases along the edge 17 up to a value of 7° at the end of the edge 17. As regards the curvature of the corner cutting edge 17, that curvature could be defined by a constant radius of curvature R₁ (see FIG. 2) or by a continuously variable radius whereby the degree of curvature of the corner cutting edge progressively increases from the line 19 to the corner. The corner cutting edge 17 acts as a main cutting edge, whereas the side cutting edge 16 acts as a supporting edge in contact with the machined surface on a workpiece A. The chip face of the insert at the corner is provided with a smoothly curved recess 20 which is located at a distance from the cutting edge and is intended to act as a chipbreaker. This chipbreaker 20 is provided with a smaller radius of curvature R₃ than the radius R₁ of the corner cutting edge 17. The recess 20 is curved as viewed in plan such that the near wall 20′ thereof located closest to the corner 22 is concave as viewed in plan, and the far wall 20″ thereof located farthest from the corner is convex as viewed in plan. The recess is elongated such that its length L directed generally parallel to the corner cutting edge is longer than its width W directed generally perpendicular to the corner cutting edge. As appears from FIG. 3, this chipbreaker recess 20 has a cross-sectional configuration in the form of a portion of a circular arc. A strengthening land area 21 is provided between the chipbreaker 20 and the corner cutting edge 17. That land has a width (shown in FIG. 3) which increases progressively towards the corner 22. This land strengthens the corner cutting edge, thus enabling higher feeds. Although the edge 16 could be straight, it is preferable that the edge 16 be convexly curved about a large radius of curvature R₂, which is larger than the radius R₁ of the corner cutting edge 17. That radius, like the radius R₁, would lie in the plane of the chip face 11. At the same time, it is advantageous to provide each corner clearance face 18 with a small strengthening beveled face 23 inclined at an angle β in relation to the chip face 11, preferably in the range 10-20°. Further, it is suitable to provide each side clearance face 13 with a supporting beveled face 24, as shown in FIG. 4, which is suitably inclined at an angle γ relative to normal to the chip face 11, that angle γ being in the range of 3-5°. In order to be able to increase the feed, while maintaining good surface finish, the radius of curvature of cutting edge 17 can be made to progressively decrease from the intersection line 19 towards the corner 22. As shown in FIGS. 5-6, the insert 10 is intended to be supported by a toolholder 15, which is secured to a rotating cutting head (not shown). That head rotates about an axis L which coincides with the axis of a non-rotatable workpiece A. A circularly shaped heavy duty insert 22 is also provided in the same toolholder 10 at some distance from the insert 10. In the alternative, one or several heavy duty inserts with a shape other than round could be arranged in combination with the insert 10. The circularly shaped insert 22 is a roughing insert for performing roughing operations to a cutting depth h₁ in the workpiece A whereas the insert 10 is a finishing insert, which creates the final surface in workpiece A at a cutting depth h₂. The roughing insert 22 is inclined relative to the plane of the toolholder 15. That is, the roughing insert is inclined forwardly by angle e (FIG. 4) in that its front side (i.e., left side in FIG. 6) is lower than its rear side (right side in FIG. 6). The angle e is preferably in the range of 2-4°. Also, the roughing insert 22 is inclined sidewardly in that its inner side (i.e.,the side farthest from the workpiece axis L) is higher than its outer side (i.e., the side closest to the workpiece axis L); that inclination is also in the range of 2-4°. Although the invention has been described in connection with a preferred embodiment thereof, it will be appreciated by those skilled in the art that additions, modifications, substitutions and deletions not specifically described may be made without departing from the spirit and scope of the invention as defined in the appended claims.
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A cutting insert for bar peeling comprising a multi-cornered polygonal body of wear resistant material, said body including top and bottom surfaces (11,12) and a peripheral edge surface extending therebetween, said peripheral edge surface including corner clearance faces (18) disposed at respective corners of said body, said corner clearance faces intersecting said top surface (11) to form corner cutting edges (17), each corner cutting edge being convexly curved as said top surface (11) is viewed in plan, said top surface (11) defining a chip face and including chipbreaker recesses (20) located adjacent respective ones of said corner cutting edges, each recess (20) being spaced from its respective corner cutting edge in a direction toward a center of said insert, characterized in that each of said recesses (20) being curved such that a near wall (20') thereof located closest to said corner cutting edge is convex as said insert is viewed in plan, and a far wall (20'') thereof located farther from said corner cutting edge is concave as viewed in plan. A cutting insert according to claim 1,characterized in that each of said corner clearance faces (18) extends at an acute clearance angle (α) relative to said top surface. A cutting insert according to claim 1,characterized in that said clearance angle (α) becomes progressively larger as a respective corner is approached. A cutting insert according to claim 1,characterized in that said peripheral edge surface includes side clearance faces (13) which intersect said top face (11) to form therewith side cutting edges (16). A cutting insert according to claim 4,characterized in that each of said side cutting edge (16) being convex as viewed in plan and having a radius of curvature (R₂) substantially larger than that of said corner cutting edges (17). A cutting insert according to claim 1,characterized in that said body is generally triangular. A cutting insert according to claim 1,characterized in that said curvature of said corner cutting edge (17) is defined by a constant radius of curvature (R₁). A cutting insert according to claim 1,characterized in that said curvature of said corner cutting edge varies so that the degree f curvature increases toward said corner. A cutting insert according to claim 1,characterized in that said top face (11) includes a land (21) disposed between each of corner cutting edges and its respective recess, said land (21) becoming wider as said corner is approached. A cutting insert according to claim 4,characterized in that each of said side clearance faces (13) includes a bevel (24) intersecting a respective side cutting edge, said bevel forming an angle (γ) with a line normal to said chip face, said angle being in the range of about 3 to 5 degrees. A cutting insert according to claim 1,characterized in that each of said corner clearance faces (18) includes a bevel (23) intersecting a respective corner cutting edge at an angle in the range of 10 to 20 degrees. A cutting insert according to claim 4,characterized in that an imaginary line (β) extending perpendicularly from a side cutting edge and passing through a geometric center of said insert intersects a respective one of said corner cutting edges such that a portion of said corner cutting edge disposed on one side of said line is longer than the remainder thereof located on the other side of said line. A cutting insert according to claim 1,characterized in that each of said recesses (20) is elongated so as to be longer in a direction generally parallel to its respective corner cutting edge than in a direction generally perpendicular to its respective corner cutting edge. A cutting tool for bar peeling comprising a rotatable cutter head equipped with a plurality of toolholders (15), each of which is carrying a circular roughing insert (22) of wear resistant material and a multicornered finishing insert (10), each said insert including top and bottom surfaces and a peripheral edge surface extending therebetween, said edge surfaces intersecting said top and bottom surfaces to form cutting edges, characterized in that each corner cutting edge of said finishing insert (10) being convexly curved as said top surface is viewed in plan, said top surface (11) defining a chip face and including chipbreaker recesses (20) located adjacent respective ones of said corner cutting edges, each recess (20) being spaces from its respective corner cutting edge in a direction toward a center of said insert, each of said recesses being curved such that a near wall (20') thereof located closest to said corner cutting edge is convex as said insert is viewed in plan, and a far wall (20'') thereof located farther from said corner cutting edge is concave as viewed in plan. A tool according to claim 14,characterized in that said finishing insert (10) lies within the plane of said toolholder, and said roughing (22) insert is inclined at an angle of from 2 to 4 degrees relative to said plane. A tool according to claim 14,characterized in that said finishing insert (10) includes a top face (11) and a peripheral edge face (13) which includes a side clearance face and a corner clearance face (18) which intersect said top face to form a side cutting edge and a corner cutting edge, respectively; said corner clearance face, at a junction with said side clearance face, forming a zero degree clearance angle relative to a plane extending perpendicular to said top face, said clearance angle progressively increasing from said junction to a respective corner of said insert. A tool according to claim 14,characterized in that an imaginary line (B) extending perpendicularly from one of said side cutting edges and passing through a geometric center (C) of said insert intersects a corner cutting edge such that a portion f said corner cutting edge located on one side of said line is longer than a remainder of said corner cutting edge located on another side of said line. A tool according to claim 14,characterized in that said roughing insert (22) is arranged to make a deeper cut than said finishing insert (10).
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SANDVIK AB; SANDVIK AKTIEBOLAG
|
DAHLLOEF YNGVE; HANSSON SOELVE; DAHLLOEF, YNGVE; HANSSON, SOELVE; Dahllöf, Yngve; Hansson, Sölve
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EP-0489702-B1
| 489,702 |
EP
|
B1
|
EN
| 19,951,025 | 1,992 | 20,100,220 |
new
|
B23C5
| null |
B23C5
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B23C 5/22B1B
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Cutting insert and cutting tool for chip removing machining
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An insert (10) for a milling cutter has a chip face (11) and a bottom face (12) which are interconnected by side surfaces. The intersection of side surfaces (14-17) with the chip face forms four cutting edges (12A-12D). Each side surface is beveled at its intersection with a cutting edge to form a planar clearance face, the width of which increases toward one of the cutting corners. Each cutting edge includes a main edge portion (17′), a corner edge portion (17″′), and a secondary edge portion (17″). Each secondary edge portion (17″) extends inwardly from an associated secondary edge at an angle no greater than four degrees. At each corner, a secondary edge portion of one cutting edge forms an actual angle with a main edge portion of another cutting edge greater than ninety degrees. The insert is mounted at a negative radial rake and a positive axial rake such that such actual angle presents to a workpiece an effective angle of ninety degrees to cut a ninety degree shoulder in the workpiece.
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The present invention relates to an indexable cutting insert for chip cutting machining comprising a body of generally polygonal shape having an upper chip face, an opposite planar bottom face and side surfaces therebetween intersecting the upper chip face to define main cutting edges therewith. A prior art insert of the afore-mentioned type to be mounted in milling cutters of radial negative and axially positive cutting angle is disclosed for instance in Swedish Patent Publication No. 419,834, corresponding to U.S. Patent No. 3,955,259. When milling with such inserts is carried out, however, the chip formation has not always been satisfactory under certain conditions. Also, with such milling cutters the desired cutting depth has not been achieved, especially with 90° shoulder mills, due to the fact that the required large positive chip angle could not be used with such inserts having four main cutting edges. It is an object of the present invention to provide an indexable cutting insert that enables 90° shoulder milling operations to be carried out with a positive chip angle. A further object is to provide such an insert which has four indexable cutting edges. It is another object of the invention to provide an insert that reduces the energy needed for its engagement with a workpiece. It is yet another object of the invention to provide an insert whose lifetime can be maximized. These objects are achieved with a cutting insert having the features of claim 1. In EP-A-392 729 representing the closest prior art a cutting insert is disclosed according to the precharacterising part of claim 1 which comprises a clearance face between two adjacent corners and has a width extending in a direction transversely of the adjacent cutting edge, this width being largest adjacent one of the two cutting corners and decreasing toward the other of the two corners. However, this cutting insert has no protruding ribs on its upper chip face. Moreover, it has only two useful cutting edges, instead of four. According to the invention, preferrably the wider end of the clearance face extends around one of the corners and is smoothly rounded at such corner. The bottom face is preferrably polygonal and angularly displaced relative to the polygonal chip face as the insert is viewed in plan. The cutting edges preferably include main edge portions, corner edge portions, and secondary edge portions. Each secondary edge portion interconnects a main edge portion with a corner edge portion. The main edge portion is inclined inwardly relative to a respective secondary edge portion to form an acute angle therewith. That angle is no greater than about 4°. The insert has four corners, each adjoining a secondary edge portion and a main edge portion. A secondary edge portion located on one side of a corner of the insert forms an actual angle with a main edge portion located on an opposite side of the corner, which angle is greater than ninety degrees. The insert is mounted in a cutter body at a negative radial rake angle and a positive axial rake angle such that the main and secondary edge portions located at a respective corner form an effective angle of ninety degrees with one another as seen by a workpiece, in order to cut a ninety degree shoulder in the workpiece. The objects and advantages of the invention will become apparent from the following detailed description of a preferred embodiment thereof in connection with the accompanying drawings in which like numerals designate like elements, and in which: FIG. 1 is a plan view of an insert according to the invention; FIG. 2 is a cross-sectional view taken along the line 2-2 in FIG. 1; FIG. 2A is an enlarged fragmentary view of an insert cutting through a workpiece; FIG. 3 is a perspective view of the insert shown in FIG. 1; FIG. 4 is an end view of a shoulder milling cutter equipped with inserts as shown in FIGS. 1-3; FIG. 5 is a side view of the milling cutter shown in FIG. 4; The insert shown in FIGS. 1-5 is an indexable polygonal insert 10 of square shape. It is to be understood that other polygonal shapes can be used within the scope of this invention. The insert 10 comprises an upper chip face 11, an opposite planar bottom face 12 bordered by edges 12A, 12B, 12C, 12D, and four identical side surfaces S intersecting the upper and bottom surfaces to form cutting edges E. Two of the side surfaces extending to a cutting corner 13 are designated as surfaces 14 and 15 in the drawings, and those two surfaces form two cutting edges 16 and 17, respectively (see FIG. 3). The insert has a positive geometry which means that the side surfaces intersect the bottom surface 12 at obtuse angles X while intersecting an upper plane P₂ of the upper face 11 at an acute angle Y (see FIG. 2). A central aperture 18 is provided which extends through both of the upper and bottom faces 11 and 12 and is oriented perpendicularly to the bottom face 12. The central aperture is intended for the receipt of a suitable fastener such as a screw. The bottom face 12 has a polygonal shape, which is angularly displaced relative to the polygonal shape of the upper face 11 about the axis of the hole 18, i.e., as viewed in plan (FIG. 1). Each cutting edge E includes a main edge portion, a corner edge portion, and a secondary edge portion interconnecting the main and corner cutting edge portions. Thus, for example, the cutting edge 17 includes a main cutting edge portion 17′, a secondary edge portion 17″, and a corner edge portion. The cutting edge 16 includes similar portions 16′, 16″. The main edge portion 17′ extends slightly inwardly from the associated secondary edge portion 17″ (i.e., toward the center of the insert) at a very slight angle G (see FIG. 1) which is in the range of 0.5 to 4.0°. Therefore, for example, in the case of an angle G of 4.0°, the actual angle I (see Fig. 1) formed between the secondary edge portion 17″ located on one side of the corner 13 and the main edge portion 1G′ located on the opposite side of the corner 13 is 94°. The secondary edge portion 17″ extends into the smoothly rounded corner cutting edge portion. Instead of being smoothly rounded, the corner edge portion could be constituted by a number of small facets. Each edge 12A-D of the bottom face 12 extends parallel with a respective secondary cutting edge 17″, i.e., edge 12A is parallel to secondary edge portion 17″ (see FIG. 1). Accordingly, the secondary edge portion will generate the surface WS of the workpiece with which the insert is in engagement (see FIG. 2A). The edge 12A forms an acute angle with the main cutting edge 17′ (as viewed in plan (FIG. 1 ). The insert 10 is, along a major portion of its side surface S, provided with a bevel which forms a planar clearance face 20. The clearance face 20 is situated between two respective corners 3 and has a width dimension extending perpendicularly relative to the respective cutting edge. The width increases progressively towards one cutting corner 13 and extends smoothly around such cutting corner. The clearance face 20 is oriented in a plane that extends perpendicularly to the plane P₂, while intersecting with the rest of edge surface S at an obtuse angle L (see FIG. 2). At the corner 13, the clearance face 20 extends into a convexly rounded surface 21 having a radius R which then extends to the adjacent side surface S to form therewith an intersection line. For example, the clearance face 20 of side surface 14 extends into a convexly rounded surface 21 at the corner 13, and then extends to the adjacent side surface 15 to form therewith an intersection line 22. The intersection line 22 is oriented obliquely in relation to the adjacent upper cutting edge 17. The clearance face 20 extends to an upper strengthening land 23. The land 23 has a maximum width at the cutting corner 13. This can be achieved by a land which is of constant width except at the corner where it expands, or by a land of continuously increasing width as shown. The land 23 is located in the same plane as four raised surface portions 24, 25, 26, 27, which are raised from inner portions of the upper surface 11. Each of these raised surface portions 24-27 extends frog an edge towards the upper end of the central aperture 18 and is symmetric relative to the respective corner 13 in that it is located at some distance from a bisector B of the corner. More specifically, each such raised portion 24 forms an angle K with the bisector B (see FIG. 3), the angle preferably being 0-20°. Each raised surface portion 24-27 has a constant width W′ (see FIG. 1) although the width could vary under certain conditions. The surface area 11A located between two adjacent raised surface portions 24 and 27 is a recess which is concave in cross-section. A chip angle γ is thus provided between the surface 11 close to cutting edge 16 and a normal N to the plane P₂ (see FIG. 2), which is preferably in the range of 60-85°. Close to the insert's center the raised surface portions 24-27 extend into concave surface portions 24A-27A which then extend to a cylindrical upper end of the aperture 18. Each recessed surface area 11A extends from cutting edge 16 at an increasing depth which at most amounts to H and then extends inwards at a decreasing depth. The decreasing depth is smallest close to the central aperture 18 as shown in FIG. 2. The maximum depth H of each recessed surface area 11A occurs along a midplane 2-2 of the inserts, and that depth could be of the same size as the width of clearance face 20 taken in the same cross-section. However, the size of depth H could also be different than the width of the face 20. Further, the inner intersection line 28 between the concave surface portions 24A-27A, and the recessed surfaces 11A are in the shape of a wave-shaped line, as best appears from FIG. 1. This wave-shaped line 28 then extends to a straight line 29 which is the inner intersection of the raised surface portion 27. Thereafter, the line 29 intersects with another adjacent wave-shaped line 30, which provided the inner intersection line of recessed surface area 11B. The insert is intended to be radially oriented in a milling cutter body 19 (see FIGS. 4-5) such that the upper face 11 serves as a chip face and the beveled portion of the side surface S is a clearance face. When the insert cuts through a workpiece in a directicn of feed F during a milling operation, the secondary cutting edge 17″ is oriented parallel to the direction of feed and thus also is parallel to the plane P₁ of the cut being made in the workpiece (see FIG. 2A). The secondary edge portion 17″ thus generated the final surface WS in the workpiece along plane P₁. Furthermore, it is desired that the shoulder being cut by the insert be a ninety-degree shoulder, i.e., that the surface WS′ shown in Fig. 2A be oriented at ninety degrees relative to the surface WS. In order to be able to cut such a ninety-degree shoulder by the insert 10 which has a real angle I greater than ninety degrees, the insert is mounted in the milling cutter in such fashion that the effective angle I′ which is seen by the workpiece during a milling operation is ninety degrees. This is achieved by orienting the insert 10 at a negative radial angle α (see FIG. 4) and a positive axial angle β in the cuter body 1. Accordingly, the effective angle I′ seen by the workpiece (see FIG. 2A) can be made to be ninety degrees. Thus, in FIG. 2A, as the insert 10 moves toward the viewer during its rotation, the point Q₁ is located farther from the viewer than is the point Q₂, and the point Q₃ is located farther from the viewer than are both of points Q₁ and Q₂ (see also FIG. 5). The entering angle of the insert is from 90-95 degrees, preferably 90-92°. Since the main edge portion 16' extends at an angle relative to the secondary edge 16'', it is possible to provide the insert with four identical cutting corners capable of cutting a ninety-degree shoulder angle I'.
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A cutting insert for chip removing machining of metal workpieces, comprising a body having a polygonal upper chip face (11), a substantially planar bottom face (12), and side surfaces (14, 15) intersecting one another to form corners of said insert and intersecting said chip face and said bottom face, cutting edges (16, 17) being formed by the intersection of said chip face with respective side surfaces, a lower portion of each side surface extending upwardly and outwardly from said bottom face, an upper portion (20) of each side surface being beveled to form a planar clearance face which intersects a respective cutting edge, each clearance face (20) being disposed between two adjacent corners and having a width extending in a direction transversely of said cutting edge, said width being largest adjacent one of said two corners and decreasing toward the other of said two corners, said insert including a strengthening land (23) extending inwardly from said cutting edge (16, 17), a central portion of said chip face (11) is recessed toward said bottom face (12), said chip face including descending walls extending downwardly from said lands to said recessed central portion, characterized in that said descending walls being separated from one another by raised ribs (24-27), said ribs being situated adjacent respective corners and including upper surfaces lying in a common plane oriented parallel to said bottom face (12), whereby each raised rib (24-27) is located at some distance from the bisector of the corner. A cutting insert according to claim 1, wherein said strengthening land (23) lies in a plane, each of said clearance faces (20) forming a substantially ninety degree angle with said plane. A cutting insert according to claim 1, wherein said bottom face (12) is polygonal and being angularly displaced relative to said polygonal chip face as said insert is viewed in plan. A cutting insert according to claim 1, wherein said cutting edges (16, 17) include main edge portions (16', 17'), corner edge portions, and secondary edge portions (16'', 17''), each secondary edge portion interconnecting a main edge portion with a corner edge portion, said main edge portion being inclined inwardly relative to a respective secondary edge portion by a slight angle as said chip face is viewed in plan. A cutting insert according to claim 4, wherein said angle is no greater than four degrees. A cutting insert according to claim 4, wherein a secondary edge portion (16'', 17'') located on one side of a corner forms an angle greater than ninety degrees with a main edge portion located on the other side of said corner. A cutting insert according to claim 4, wherein each secondary edge portion is oriented parallel to a respective edge of said bottom face. A cutting insert according to claim 4, wherein said insert has four said corners each adjoining a said secondary edge portion and a main edge portion. A cutting insert according to claim 1, wherein said land (23) has a maximum width at said corners. A cutting insert according to claim 1, wherein each of said ribs (24-27) forms an acute angle with a respective corner bisector, said angle being no greater than twenty degrees.
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SANDVIK AB; SANDVIK AKTIEBOLAG
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PANTZAR GOERAN; PANTZAR, GOERAN; Pantzar, Göran
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EP-0489703-B1
| 489,703 |
EP
|
B1
|
EN
| 19,960,207 | 1,992 | 20,100,220 |
new
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H01L39
|
C04B35
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C04B35, H01L39
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C04B 35/638, H01L 39/24J10, C04B 35/45, C04B 35/634, H01L 39/24J, C04B 35/622F2H, C04B 35/634D
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Method to form a superconductive ceramic product and the product thus obtained and the intermediate product
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Method to form a superconductive ceramic product according to which a suspension is formed of an organic solvent, an organic polymer binding agent and a superconductor- powder, being a superconductor- powder or a superconductor- precursor or a mixture of powders becoming superconductive after a thermal treatment, or a mixture of two or more of these materials, this suspension is brought into the required form, the solvent is removed from the suspension, the binding agent is removed thermally and the then obtained product undergoes a thermal treatment, characterized in that polysulphone is used as an organic binding agent and the solvent is removed from the suspension brought into form by means of extraction with a non solvent.
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The invention relates to a method for the realization of a superconductive ceramic product, according to which a suspension is produced of an organic solvent, an organic polymer binding agent and a superconductor- powder, this is a superconductive powder or a superconductor- precursor of a mixture of powders becoming superconductive after a thermal treatment, or a mixture of two or more of these materials, the suspension is brought to the desired form, the solvent is removed from the suspension, the binding agent is removed thermally and the obtained product is then subjected to a thermal treatment. It is generally known that such ceramic powders based on yttrium, bismuth or thallium show superconductive properties already at temperatures higher than those of liquid helium and even of liquid nitrogen. In this respect yttrium-barium-copper oxide is appropriate. These superconductive powders, in the practical application, must be brought into a usable shape such as wire, film or tape, which due to the non flexible character of ceramic materials, may create problems. EP-A-0 341 030 describes a method of aforementioned kind to from superconductive products such as wire. A suspension is developed from a superconduct or-powder, in fact a so-called superconductor oxide precursor, in a watery solution of a water soluble polymer. After extrusion of the suspension into wire, it is dried and treated thermally during which the polymer disappears and a certain sintering takes place. The mechanical properties of the wire leave a lot to be desired. Another method of aforementioned kind is described in EP-A-0 341 030. According to this method a suspension is prepared with yttrium-barium-copper oxide powder, a perfluoroisobutyle acrylate polymer as binding agent and methyl ethyl ketone as organic solvent. This suspension is applied as a film on a substrate, the solvent is evaporated, the polymer is removed thermally and the film is then further thermally treated at 900 degrees Celsius in an oxygen atmosphere. The invention aims to provide a method of the aforementioned kind in which a superconductive product and, more particularly, wire, film or tape, with very good mechanical properties can be obtained in a simple manner. With this aim in mind, polysulphone is used as organic binding agent and the solvent is removed from the suspension brought into form by means of extraction with a non solvent. The removal of a solvent by means of extraction with a non solvent is known as such. Surprisingly so it appeared that by application of such an extraction combined with the use of polysulphone as an organic binding agent a very rapid crystallization of the binding agent is obtained which is especially advantageous with uninterrupted forming methods such as extrusion and wire spinning and where a finished product with good mechanical properties is obtained. In a special embodiment of the invention an organic and silicone free thixotropic agent is added to said suspension, before the forming of the suspension, said agent being removed together with the binding agent during the thermal removal process. In a remarkable embodiment of the invention the weight ratio of polysulphone to solvent in the suspension is between 10 and 40 %. In an effective embodiment of the invention the polysulphone is first mixed with the solvent and this mixture is then mixed with the superconductor- powder. The weight ratio polysulphone to superconductor- powder is then preferably between 2 and 30% A very suitable superconductive powder is a powder based on yttrium, bismuth or thallium and, for instance, yttrium-barium-copper oxide : YBa₂Cu₃O(7-δ) (YBCO). In a preferably applied embodiment of the invention the binding agent is thermally removed from the suspension by keeping it under a vacuum at a temperature of 200 to 700 degrees Celsius during a period up to five hours. The thermal treatment includes preferably the sintering at a temperature of 800-1000 degrees Celsius and a calcination under an oxygen or air atmosphere at a temperature of 400 to 500 degrees Celsius. One additive at least can be added to the suspension for the improvement of the mechanical and/or superconductive properties. The inventions also relates to the formed ceramic superconductive product obtained according to the method according to one of the former embodiments. The invention, finally, also relates to the intermediate product obtained after the removal of the solvent, which intermediate product as such can be brought on the market for further treatments. Other particularities and advantages of the invention will appear from the following description of a method to form a superconductive ceramic product and of the thus obtained product or intermediate product according to the invention. This description serves only as an example and does not limit the scope of the invention. In order to prepare a superconductive ceramic film or wire or a superconductive tape based on superconductive ceramic powder based on yttrium, bismuth or thallium, a suspension of this powder is prepared in a solution of polysulphone in an organic solvent, the suspension is brought into the required form, the solvent is removed by extraction with a non solvent, the polysulphone is thermally removed and a thermal treatment is then further applied with a sintering and a calcination in an oxygen or air atmosphere. Polysulphone with an ash contents of less than 0.1 % is used as a temporary polymer binding agent, such as for instance the type P 1800 NT of Union Carbide which possesses an extremely low residue ash contents of 0.08%. Other temporary binding agents used in known methods for the preparation of formed superconductive products such as polyvinylalcohol and hydroxypropylcellulose possess a higher residue ash contents. The organic solvent in which the polysulphone dilutes must possess a sufficiently high boiling point (60 degrees Celsius or higher) in order to avoid that the suspension brought into form would unmix as a consequence of evaporation before the extraction of the solvent occurs. The ratio polysulphone to solvent varies between 10 and 40 percent of weight in accordance with the required viscosity needed for the formation. Adequate solvents are, among others, N-Methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide. If the average grain size of the superconductive oxide is too large the oxide powder is submitted to wet breaking in an anhydrous suspension, for instance in anhydrous alcohol until the grain size preferably is between 1 and 15 micrometers. A ball mill is used for breaking small quantities. The suspension must be anhydrous in order to avoid that the powder reacts with water. The possibly broken superconductive ceramic powder is mixed with the polysulphone solution for instance in a ball mill in which a de-agglomeration occurs. The weight ratio polysulphone/superconductive powder is situated between 2 and 30%. This high degree of filler is required in order to permit sintering at a later stage and to obtain a sufficient mechanical strength after sintering. The viscosity of the obtained suspension varies between S centipoise and 20,000 centipoise. In case the formation of the suspension occurs by brushing of spraying only a few centipoises suffice but for a formation by extrusion the viscosity must remain between 10,000 and 20,000 centipoise. The viscosity is adjusted by adapting the ratio solvent to polysulphone. One possibly can, prior to shaping, add up to maximum 1 percent of weight of an organic and silicium free thixotropic agent to the obtained suspension. A thixotropic agent is a stabilizer producing web formation by means of an H-binding and creating a high viscosity in a state of rest. In the case of strong movement of the product to which the agent is added, the viscosity is low but the viscosity will increase to the rest value again shortly after recovery of the state of rest. This agent avoids the precipitation of the superconductive powder. This agent will be removed thermally later on together with the poiymer binding agent. This agent may increase the residual ash contents with 0.05 % maximum which means that the asn contents of the thixotropic agent itself may amount to 5 % maximum. The agent must absolutely be free of silicium as silicium has a negative influence on the superconductive properties of the superconductive product. The suspension is brought into the required form by means of the usual techniques. In order to form a film the suspension is for instance applied to a substrate by means of spraying, brushing or immersion. In order to prepare a tape, the so-called doctor blade method can be used. Wire can be prepared by spinning or extrusion. After this modelling the solvent is removed by immersion of the formed suspension in a non solvent, more particularly isopropanol or pentanol during at least 5 minutes, for instance during 5 minutes to 24 hours. Water only cannot be used as a non solvent unless very briefly and followed by an immersion in an organic non solvent, as the immersion period cannot be chosen long enough due to the negative effect of water on the superconductive powder. The non solvent must be protected from air in order to limit contamination. After removal by extraction of the solvent the porosity or the product amounts to 30 to 90 %. This product, called a green product, must be stored in a controlled atmosphere in order to avoid contamination by air humidity. The polysulphone is now removed from the green product by heating it in a vacuum during 2 to 5 hours between 380 and 500 degrees Celsius. The polysulphone starts to dissolve at 390 degrees Celsius and is normally completely dissolved at 500 degrees Celsius. Vacuum is required to avoid that the thermal decomposition products would chemically or physically compound with the superconductive powder. After removal of the polysulphone, the product is cooled to room temperature. Finally, the product is subjected to a thermal treatment including a sintering process. In a first phase, the product is heated from room temperature to 800-1000 degrees Celsius in an oxygen or air atmosphere and mostly for a period of 1 to 72 hours. Thereafter the product remains during a certain period of time with a maximum of 72 hours (for instance 1 to 72 hours) in this oxygen or air atmosphere at said temperature. It is principally during this phase that sintering takes place. In a third phase the product is slowly cooled down, for instance to a temperature of 400 to 500 degrees, for instance 450 degrees Celsius and the product is calcinated for a period of 1 to 72 hours at this temperature. More particularly during this last period of time which also takes place in an oxygen or air atmosphere, oxygen is absorbed so that the adequate oxygen stoichiometry is obtained. Instead of starting from a superconductive ceramic powder, more particularly a superconductive oxide, one may start from a so-called superconductive precursor which, during the thermal treatment in superconductive powder, is transformed to for instance superconductive oxide, or one may start with a mixture of powders which become superconductive after thermal treatment, such as a mixture of oxide and carbonate, or for instance a mixture of barium-copper oxide ant yttrium-copper oxide. Obviously one can start from a mixture of two or more of the three aforementioned materials. One or more additives can be added to the suspension which improve the mechanical and superconductive properties, such as silver and/or silver oxide. The invention will be further clarified by means of the following examples. Example 1.20 grams polysulphone (type P 1800 NT11 from Union Carbide) were dissolved at room temperature in a ball mill in 80 grams N-Methyl-2-pyrrolidone. 25 g of this solution were mixed in a ball mill with 45 g yttrium-barium-copper oxide (YBCO) powder (type SU from Rhône-Poulenc). The thus obtained suspension was sent through a spinning head with a flange opening of 1 mm. diameter and the formed wire was directly immersed in a bath filled with isopropanol where it was left during two hours. The green product was placed on a small aluminum plate in an oven and heated to 430 degrees Celsius at a vacuum of 28 kPa. Said product was kept at this temperature during two hours and later cooled down to room temperature. The product was then heated in an oven filled with oxygen in a period of three hours to 940 degrees Celsius and maintained during 12 hours at this temperature. Finally, during a period of 4 hours the oven was cooled down to a temperature of 450 degrees Celsius and kept at this constant temperature during two hours. The sintered wire which finally was removed from the oven possessed a diameter of 0.75 mm and a critical temperature of 88 degrees Kelvin and a critical current density of 125 A/cm² at 77 degrees Kelvin. Example 2.20 g polysulphone (type P 1800 NT11 from Union Carbide) were dissolved at room temperature in a ball mill in 113.3 g N-Methyl-2-pyrrolidone. Superconductive YBa₂Cu₃O(7-δ) powder with an average grain size of 6.5 micrometers was mixed with ethanol. The mixture was broken during two hours in a ball mill followed by an evaporation of the ethanol at 60 degrees Celsius. The average grain size after breaking was 4.5 micrometer. 45 g of this powder was mixed in a mill tube with 33.3 g of the polysulphone solution. The obtained suspension was poured into a casting head with a blade opening adjusted at 600 micrometer. This casting head was moved at a constant speed of 0.05 m/s over a glass plate. Immediately after casting the suspension said giass plate was immersed in an isopropanol bath and remained in it for two hours. A green product with a thickness of 0.320 mm and a porosity of 62 % was obtained. Said green product was placed in an oven on an aluminumoxide plate and heated up to 430 degrees Celsius at a vacuum of 28 kPa. This temperature was constantly maintained during three hours after which the product was cooled down to room temperature. After this treatment, the oven was filled with oxygen and heated in three hours to 940 degrees Celsius. This temperature was kept constant for 12 hours after which the oven was cooled down to 450 degrees Celsius. Said temperature was kept constant for 2 hours. The obtained sintered tape had a thickness of 275 micrometer and a Hg-porosity of 47 % with an average pore size of 1598 nm. The critical temperature of this tape was 83 degrees Kelvin. Example 3.Example 2 was repeated but with pentanoi as a non solvent instead of iso-propanol. The thickness of the green product was 320 micrometer with a porosity of 62 %, after sintering the Hg porosity amounted to 47 % with an average pore size of 1398 nm. Contrary to example 2 where a fully opened porosity was noticed, a 3 % closed porosity was measured in this example. Example 4.20 g polysulphone (Type P 1800 NT from Union Carbide) were dissolved at room temperature in 122.65 g of N-Methyl-2-pyrrolidone. A quantity of superconductive Bi₂Sr₂CaCu₂Ox powder from Hoechst with a grain size smaller than 125 micrometer was mixed with ethanol and broken during 3 hours at 100 r.p.m. in a planetary ball mill. The ethanol was dried at 60 degrees Celsius in a drying kiln. 45 g of this powder was mixed in a ball mill with 19.9 g of the polysulphone solution and a thin layer was cast on a glass plate by means of a casting head with a blade opening adjusted at 600 micrometer and moving at a constant speed of 0.05 m/sec. Immediately thereafter the glass plate was immersed in an isopropanol bath for two hours. The obtained green product was subsequently placed in an oven on an aluminumoxide plate after which the oven was heated up to 430 degrees Celsius in a vacuum of 28 kPa. Said temperature was kept constant during 2 hours after which a cooling down to room temperature occurred. The oven was then subsequently filled with air and heated up in 30 minutes to 860 degrees Celsius. The oven was kept at that temperature during 48 hours and thereafter cooled down within a few minutes to room temperature. The obtained sintered tape had a thickness of 150 micrometer. The critical temperature of this tape was 84 degrees Kelvin. Example 5.250 grams polysulphone (type P 1800 NT11 from Union Carbide) were dissolved in a High Speed Dissolver at room temperature in 750 grams N-Methyl-2-pyrrolidone. 20 g of this soiution was then mixed in a ball mill with 44.5 g yttrium-barium-copper oxide (YBCO) superconductive powder (Hoechst Hign. Chem.) with an average grain size of 3 micrometer and with 4.5 g silver oxide powder. The thus obtained suspension was sent through a spinning head with a flange opening of 1 mm. diameter and the formed wire was directly immersed in water and afterward in a bath filled with isopropanol where it was left during two hours at least. This so-called green product was placed on an aluminum oxide plate in an oven and heated to 440 degrees Celsius in a vacuum of 10 Pa, kept at that temperature during four hours and thereafter heated up to 820 degrees Celcius at an oxygen pressure of 0.6 kPa. After three hours at this pressure and temperature, the oxygen pressure was increased to 100 kPa and the same temperature maintained during 6 hours. The product was thereafter heated up in this oven at 100 kPa oxygen pressure during a period of three hours to 955 degrees Celcius and kept during twelve hours at this temperature. Finally, the oven was cooled down over a period of seven hours to 450 degrees Celcius and kept constant at this temperature during ten hours. The sintered wire which was finally removed from the oven had a diameter of 0.75 mm and the superconductive properties above liquid nitrogen temperature could be shown by means of the Meissner effect and electric measurements. The critical current density was of 310 A/cm².
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Method of forming a superconductive ceramic product, according to which a suspension is formed of an organic solvent, an organic polymer binding agent and a superconductor- powder, being a superconductor- powder or a superconductor- precursor or a mixture of powders becoming superconductive after a thermal treatment, or a mixture of two or more of these materials, this suspension is brought into the required form, the solvent is removed from the suspension, the binding agent is removed thermally and the then obtained product undergoes a thermal treatment. characterized in that polysulphone is used as an organic binding agent and the solvent is removed from the suspension brought into form,by means of extraction with a non solvent. Method according to the aforementioned claim, characterized in that before the suspension is brought into form, an organic and a silicium-free thixotropic product is added, said product being removed as well during the thermal removal of the binding agent. Method according to one of the aforementioned claims, characterized in that the weight ratio polysulphone to solvent in the suspension lies between 10 and 40 %. Method according to one of the aforementioned claims, characterized in that a polysulphone to superconductor-powaer weight ratio between 2 and 30 % is chosen. Method according to one of the aforementioned conclusions characterized in that a polysulfone with an ash content lower than 0.1 % is used. Method according to one of the aforementioned claims, characterized in that an organic solvent is used from the group formed by N-methyl-2-pyrrolidone, dimethylformamide and dimethylacetamide. Method according to one of the aforementioned claims, characterized in that a superconduct or- powder is used with an average grain size between 1 and 15 micrometer. Method according to one of the aforementioned claims, characterized in that a powder based on yttrium, bismuth or thallium is used as a superconductor-powder. Method according to one of the aforementioned claims, characterized in that an alcohol is used as a non solvent. Method according to one of the claims 1 to 8, characterized in that water is briefly used as a non solvent followed by the immersion of the obtained product in an organic non solvent. Method according to one of the aforementioned claims, characterized in that the extraction is performed by immersion of the formed suspension in a bath of a non solvent during 5 minutes to 24 hours. Method according to one of the aforementioned claims, characterized in that the binding agent is removed thermally from the suspension by keeping it during a period of time up to 5 hours at a temperature of 200 to 700 degrees Celsius in a vacuum. Method according to one of the aforementioned claims, characterized in that the thermal treatment includes a sintering at a temperature of 800 to 1000 degrees Celcius and a calcination in an oxygen or air atmosphere at a temperature of 400 to 500 degrees Celsius. Method according to the aforementioned claim, characterized in that the sintering in an oxygen or air atmosphere is performed as well and, moreover, that the product is kept at a temperature of 800 to 1000 degrees Celsius from a few hours to a few days. Method according to the aforementioned claim, characterized in that after the sintering the product is cooled down to 400-500 degrees Celsius and is kept at this temperature in an oxygen or air atmosphere up to 72 hours. Method according to one of the aforementioned claims, characterized in that at least one additive is added to the suspension for the improvement of the mechanical and/or superconductive properties. Method according to the aforementioned claim, characterized in that silver and/or silver oxide is added as an additive. Intermediate product obtained through the method according to one of the aforementioned claims after extraction of the solvent from the suspension brought into form said intermediate product comprising the polysulphone as an organic binding agent.
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VITO; VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK , AFGEKORT V.I.T.O.
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ADRIANSENS WALTER; CORNELIS JOZEF; DOYEN WILLY; LEYSEN ROGER; WEYTEN HERMAN; ADRIANSENS, WALTER; CORNELIS, JOZEF; DOYEN, WILLY; LEYSEN, ROGER; WEYTEN, HERMAN
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EP-0489711-B1
| 489,711 |
EP
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B1
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EN
| 20,031,001 | 1,992 | 20,100,220 |
new
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C12N15
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C12P21, C12N15
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C12N15, C12R1, C07K14, A61K38, A61K35, C12P21, C07K1, C12N9
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C12N 9/48, C07K 14/61, C12P 21/06, C07K 14/555
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Method for producing human growth hormone
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The invention relates to a method of producing a human growth hormone having the amino acid sequence of naturally occurring human growth hormone which comprises a) producing in a microbial host a first polypeptide which is characterized by the presence of one or more additional amino acids at the N-terminus of the amino acid sequence of naturally occurring human growth hormone; b) contacting the first polypeptide so produced with an enzyme, preferably an aminopeptidase, so as to produce a second polypeptide having the amino acid sequence of naturally occurring human growth hormone; and c) recovering the second polypeptide so produced. A preferred microbial host is a bacterium, especially E. coli.
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Background of the InventionRecombinant DNA technology permits large scale production of eucaryotic proteins in bacteria. However, the proteins so produced, are frequently characterized by the addition of an extra methionine residue at their N-terminus. This occurs because translation is always initiated at the AUG codon which codes for methionine. In procaryotes, the N-terminal methionine is frequently enzymatically removed. However, it appears that this is not the case for many eucaryotic proteins produced in bacteria. Possibly this is due to the fact that the proteins are massively overproduced and thus overwhelm the bacteria's processing capabilities. Another possible explanation is that the bacterial processing enzymes do not recognize the foreign eucaryotic proteins as their substrates.In eucaryotes, mature proteins often lack an N-terminal methionine because they have undergone extensive processing by both endopeptidases and exopeptidases, during transport from the site of synthesis to their final location.As the presence of an N-terminal methionine on eucaryotic proteins may cause an immune reaction when administered to eucaryotes, it would be desirable to process eucaryotic proteins produced in bacteria to remove the N-terminal methionine, thus producing the mature eucaryotic protein. Most available aminopeptidases are zinc metalloenzymes. They are comprised of several subunits and have very high molecular weights. (For a review see Delange and Smith, The Enzymes, 3rd edition, P.D. Boyer ed., 1971, vol. 3, pp. 81-118). Thus, leucine aminopeptidases from pig kidney and from bovine lens have molecular weights of 255,000 and 320,000, respectively. Although the exact role of these enzymes is not known, it is likely that such high molecular weight enzymes predominantly act on peptides. We demonstrate that one such leucine aminopeptidase is incapable of selectively removing the N-terminal methionine from methionyl-human growth hormone (Met-hGH). Some mammalian brain aminopeptidases capable of acting on low molecular weight peptides are either membrane bound or soluble enzymes, the latter having molecular weights of approximately 100,000. These enzymes often contain SH groups in addition to the essential metal atom and they are extremely unstable. All these enzymes seem to be of a rather little practical value for the processing of methionyl-polypeptide derivatives to mature polypeptides.On the other hand, two microbial aminopeptidases that have been described in the literature with molecular weights of about 30,000 are promising candidates for the processing of met-polypeptides. The two enzymes are fairly thermostable as well as stable and optimally active at alkaline pH. The aminopeptidases most suitable for processing of Metpolypeptides are Aeromonasproteolytica aminopeptidase and Streptomycesgriseus aminopeptidase.Aeromonas aminopeptidase has been purified and characterized by Prescott and Wilkes [Methods in Enzymology 46:530-543 (1976)], and Wilkes et al., [Eur. J. Biochem, 34:459-466 (1973)]. Although they appear to demonstrate liberation of amino acids from the N-terminus of several polypeptides and proteins, there is no demonstration of the removal of just N-terminal methionine from proteins. Removal of N-terminal methionine is demonstrated for an oligopeptide of 11 residues; however, many other residues are also removed, in addition to the methionine. Furthermore, there is no demonstration of the activity of the enzyme on non-denatured hormones of a molecular weight greater than 10,000. There is also no indication whether the reactions carried out by Wilkes and Prescott are quantitative. Also, while the paper indicates several stop signals for the aminopeptidase, there is no indication that the stop signals Asp or X-Pro, where X is any amino acid except for proline, are also stop signals when the enzyme is reacted with proteins. Furthermore, preliminary results indicate that not all proteins are susceptible to attack by Aeromonasproteolytica aminopeptidase. It appears that mature eucaryotic proteins are locked into a conformation such that the N-terminus is inaccessible to the aminopeptidase. However, the methionyl form of the eucaryotic protein has a methionine which is susceptible to removal by the aminopeptidase. Similarly eucaryotic protein derivatives containing several additional amino acids at their N-terminus, will also be susceptible to removal by the same enzyme. We have discovered that Aeromonas aminopeptidase is capable of removing the N-terminal methionine from Met-human growth hormone (Met-hGH) and from methionine - Asp-Gln-bovine growth hormone (Met-Asp-Gln-bGH). We have also demonstrated that Aeromonas aminopeptidase is capable of removing the N-terminal methionine and its adjacent leucine from Met-Leu-hGH. The reaction is quantitative and there is no other degradation of the proteins. Summary of the InventionA method of sequentially removing the N-terminal amino acid residues from an analog of a eucaryotic polypeptide synthesized in a foreign host comprises contacting the eucaryotic polypeptide analog with the aminopeptidase under suitable conditions permitting sequential removal of N-terminal amino acid residues. The polypeptide analog contains an amino acid residue or sequence of residues which stops the action of an aminopeptidase located at a position other than the N-terminal end of the polypeptide analog.In preferred embodiments of the invention the foreign host in which the eucaryotic polypeptide analogs are produced is a bacterium.The aminopeptidase enzyme used is preferably stable at a temperature up to about 65°C, and stable and active at neutral pH, i.e. about 7.0, and at an alkaline pH, i.e. from about pH 8.0 to about pH 10.0. The aminopeptidase is preferably of a molecular weight of less than about 100,000, and of bacterial origin. The enzyme can be an extracellular aminopeptidase. In specific embodiments an aminopeptidase which is insoluble in water may be used. The aminopeptidase may also be used while it is bound to a solid support, or may be removed at the end of the reaction by use of an affinity resin.In a preferred embodiment of the invention the aminopeptidase is Aeromonas aminopeptidase. Other aminopeptidases may also be used, such as Streptomycesgriseus aminopeptidase and Bacillusstearothermophilusaminopeptidase II or III. The eucaryotic polypeptide analog may be a protein or any other peptide molecule such as apolipoprotein E, interferon, specifically gamma-interferon, or somatomedin, specifically somatomedin C.The polypeptide can also be a hormone, lymphokine, growth factor or derivatives thereof.The N-terminal amino acid residue may be any amino acid. In specific embodiments of the invention the N-terminal amino acid residue is methionine or methionine followed by leucine. The N-terminal amino acid residue or a sequence of amino acid residues is bound to the N-terminal end of an amino acid residue or sequence of residues which acts as a stopping signal and stops the action of the aminopeptidase. In the embodiment in which Aeromonas aminopeptidase is used, the amino acid stopping signal may be an aspartic acid residue, a glutamic acid residue, or a sequence of residues comprising a residue other than proline bound to the N-terminal end of a proline residue. In a specific embodiment the amino acid stopping signal comprises a phenylalanine residue bound to the N-terminal end of a proline residue.A specific embodiment of the invention involves the removal of N-terminal methionine residues from growth hormone analogs or derivatives thereof produced in bacteria. N-terminal methionine residues are removed from Met-hGH, Met-Asp-Gln-bGH, Met-bGH, and Met-pGH by contacting these growth hormone analogs with an aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue.Another embodiment of the invention involves the removal of both methionine and leucine residues from the N-terminal ends of growth hormone analogs or derivatives thereof produced in bacteria. An N-terminal methionine residue and its adjacent leucine residue are removed from Met-Leu-hGH by contacting this growth hormone analog with an aminopeptidase under suitable conditions permitting the removal of the two residues.Another aspect of the invention is a method of adding N-terminal amino acid residues to a polypeptide molecule which comprises contacting the polypeptide molecule with an aminopeptidase and a sufficient excess of the free N-terminal amino acid to be added under suitable conditions permitting the addition of the amino acid to the N-terminus of the polypeptide. Aeromonas aminopeptidase is the preferred aminopeptidase for use in this embodiment of the invention.In specific embodiments of the invention the Aeromonas aminopeptidase can be hyperactivated by metal substitutions of the coenzyme. In preferred embodiments Cu(II)is partially substituted for Zn(II) and Ni(II) is partially substituted for Zn(II).The invention also concerns polypeptide analogs produced by the methods of the invention. Growth hormones and analogs of growth hormones such as human and bovine growth hormones have been produced according to the methods of the invention e.g. hGH, Asp-Gln-bGH and bGH.Another aspect of the invention is a method of preparing analogs of eucaryotic polypeptide molecules which comprises producing a first analog in bacteria by expression of a gene encoding the analog of the eucaryotic polypeptide, removing the N-terminal methionine residue and its adjacent amino acid residue by the methods of the invention with an aminopeptidase and recovering the resulting analog. The recovery of the analog can be optimized by removing the N-terminal methionine residue'and the adjacent amino acid residue that are removed by the aminopeptidase by use of ultrafiltration or dialysis. Brief Description of the DrawingsFigure 1 shows the time course for the release of the N-terminal methionine from Met-hGH by Aeromonas proteolytica aminopeptidase as described in Example 1. By way of comparison, the release of leucine is also shown.Figure 2 shows the time course for the release of the N-terminal methionine from Met-Asp-Gln-bGH by Aeromonasproteolytica aminopeptidase as described in Example II. By way of comparison, the release of leucine is also shown. Detailed Description of the InventionA method of sequentially removing one or more amino acid residues from the N-terminus of an analog of a eucaryotic polypeptide synthesized in a foreign host comprises contacting the eucaryotic polypeptide analog with an appropriate aminopeptidase under suitable conditions permitting sequential removal of N-terminal amino acid residues, the polypeptide analog containing an amino acid residue or sequence of residues located at a position other than the N-terminus of the polypeptide analog which stops the action of the aminopeptidase.The foreign host in which the analog of the eucaryotic polypeptide is synthesized can be a bacterium or any other microorganism or organism which by use of recombinant DNA methods is capable of expressing a gene encoding for the analog and producing the resulting polypeptide.The aminopeptidase is preferably an enzyme which remains stable at a temperature up to about 65°C. The aminopeptidase should also be stable and active at a neutral pH of about 7.0 and preferably at alkaline pH from about 8.0 to about 10.0.In a preferred embodiment of the invention the aminopeptidase is of a molecular weight of less than about 100 , 000 and is of bacterial origin. The aminopeptidase can also be extracellular, insoluble in water or bound to a solid support such as agarose, or another polymeric substance. In specific embodiments of the invention an affinity resin may be used to remove excess aminopeptidase from the reaction mixture.In the preferred embodiment of the invention the aminopeptidase is Aeromonas aminopeptidase. Other types of aminopeptidase may also be used, e.g. Streptomycesgriseus aminopeptidase, Bacillusstearothermophilus aminopeptidase II or III.Suitable conditions permitting the removal of the N-terminal amino acid residue are known to those of ordinary skill in the art and will vary according to the type of aminopeptidase used. In the case of Aeromonas aminopeptidase suitable conditions comprise an aqueous solution at alkaline pH of about 9.5 and a temperature of about 37°C.The eucaryotic polypeptide analog may be any polypeptide or analog of a polypeptide, such as a hormone, lymphokine, or growth factor. Suitable eucaryotic polypeptides are apolipoprotein E, interferon, namely gamma-interferon, and somatomedin, namely somatomedin C. Specific embodiments of the invention concern removing N-terminal amino acids from analogs of eucaryotic growth hormones such as human, bovine, porcine, chicken or other animal growth hormones. In these embodiments an N-terminal methionine is added to the analogs of these polypeptide growth hormones when they are produced in bacteria by recombinant-DNA methods. This invention provides a method of removing the N-terminal methionine and its adjacent amino acid from human, bovine, porcine and chicken growth hormone molecules or analogs of such molecules after they have been produced in bacteria.In certain embodiments of the invention the amino acid residue or sequence of residues which stops the action of the aminopeptidase is located adjacent the N-terminal methionine. In this situation the aminopeptidase will remove the N-terminal methionine residue only.In another embodiment of the invention the amino acid residue or sequence of residues which stops the action of the aminopeptidase is located adjacent the leucine in the molecule Met-Leu-hGH. In this situation, the aminopeptidase will remove both the N-terminal methionine residue and the leucine residue.In other embodiments of the invention the residue or sequence of residues which stop the action of the aminopeptidase is separated from the N-terminal methionine by one or more amino acid residues. In this embodiment the aminopeptidase will also remove these other amino acid residues preceding the stopping signal, after it removes the N-terminal methionine.In the case of Aeromonas aminopeptidase the amino acid residue which stops the action of the enzyme can be either aspartic acid or glutamic acid. In addition, a residue sequence comprising an amino acid other than proline bound to the N-terminus of a proline also functions as a stopping signal. In specific embodiments this stopping signal sequence comprises the amino acid phenylalanine bound to the N-terminal end of proline. This Phe-Pro sequence is the N-terminus of many natural animal growth hormone molecules. In a specific embodiment of the invention the N-terminal methionine is removed from animal growth hormone molecules produced by recombinant DNA methods in bacteria and which as a result of such production have a Met-Phe-Pro sequence at their N-terminus. In another embodiment of the invention the N-terminal methionine and its adjacent leucine residue are both removed from animal growth hormone molecules produced by recombinant DNA methods in bacteria and which as a result of such production have a Met-Leu-Phe-Pro sequence at their N terminus.In specific embodiments of the invention the eucaryotic polypeptides are analogs of bovine growth hormone (bGH). These analogs contain the sequences Met-Asp-Gln or Met-Phe as their N-terminal sequence. The methionine is added to the N-terminus of these growth hormones when they are produced by recombinant DNA methods in bacteria. After removal of the N-terminal methionine by aminopeptidase, Asp-Gln-bGH and bGH are recovered respectively. The bGH used in this experiment was the phenyalanine form of bGH which has a phenyalanine residue as its N-terminus in its natural state. These methods also apply, however, to removal of N-terminal methionine from the terminus of the alanine form of bGH, which contains an alanine on the N-terminus of its natural form although in this case the alanine residue may also be removed.A preferred embodiment of the invention concerns a method of removing the N-terminal methionine residue from a eucaryotic growth hormone analog such as animal and human growth hormone analogs, produced in bacteria by expression or a gene encoding the hormone which comprises contacting the growth hormone analog with Aeromonas aminopeptidase under suitable conditions permitting removal of the N-terminal 'methionine residue or the N-terminal methionine residue and its adjacent leucine residue.A specific embodiment of the invention concerns a method of removing the N-terminal methionine residue from a human growth hormone (hGH) analog produced in bacteria by expression of a gene encoding the hormone, the human growth hormone analog having a methionine residue added to the N-terminus of authentic human growth hormone, which comprises contacting the analog with Aeromonas aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue.Another specific embodiment of the invention concerns a method of removing the N-terminal methionine residue and its adjacent leucine residue from a human growth hormone (hGH) analog produced in bacteria by expression of a gene encoding the hormone, the human growth hormone analog having a methionine residue followed by a leucine residue added to the N-terminus of authentic human growth hormone, which comprises contacting the analog with Aeromonas aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue and its adjacent leucine residue.Another specific embodiment of the invention concerns a method of removing the N-terminal methionine residue from a bovine growth hormone analog produced in bacteria by expression of a gene encoding the bovine growth hormone analog, the bovine growth hormone analog having a methionine residue added to its N-terminus, which comprises contacting the analog with Aeromonas aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue. Another specific embodiment of the invention concerns a method of removing the N-terminal methionine residue from an interferon analog, such as gamma-interferon, produced in bacteria by expression of a gene encoding the interferon analog which comprises contacting the interferon analog with Aeromonas aminopeptidase under suitable conditions permitting removal of the N-terminal methionine residue.Another specific embodiment of the invention concerns a method of removing the N-terminal methionine residue from a somatomedin analog, such as somatomedin C, produced in bacteria by expression of a gene encoding the somatomedin analog, the somatomedin analog having a methionine residue added to the N-terminus, which comprises contacting the analog with Aeromonas aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue.Another specific embodiment of the invention concerns a method of removing the N-terminal methionine residue from an apolipoprotein E analog produced in bacteria by expression of a gene encoding the analog, the analog having a methionine residue added to the N-terminus, which comprises contacting the analog with Aeromonas aminopeptidase under suitable conditions permitting the removal of the N-terminal methionine residue.The invention also concerns a method of adding an N-terminal amino acid residue to a polypeptide molecule which comprises contacting the polypeptide molecule with an aminopeptidase and a sufficient excess of the free N-terminal amino acid residue to be added under suitable conditions permitting addition of the amino acid to the N-terminus of the polypeptide. Any aminopeptidase enzyme may be used; however, Aeromonas aminopeptidase is preferred. The aminopeptidase will be able to add any amino acid residue to the N-terminus of the polypeptide as long as that amino acid does not function as a stopping signal for the enzyme and it would preferably add an amino acid to the N-terminus which serves as a stopping signal. Since the aminopeptidase reaction is a reversible reaction, the conditions for the addition reaction are the same as that of the cleavage reaction except for the concentration of the free amino acid to be added.The activity of the Aeromonas aminopeptidase can be increased by metal substitutions. The greatest enhancement of activity occurs by partial or mixed metal substitutions essentially according to the methods J.M. Prescott et. al., Biochemical and Biophysical Research Communications, Vol. 114, No. (pp. 646-652) 2 (1983). The partial or mixed metal substitutions may be Cu(II) for Zn(II) or Ni(II) for Zn(II)The invention also concerns polypeptide analogs produced by the methods of this invention such as human, bovine, porcine and chicken growth hormones or growth hormone analogs such as Asp-Gln-bGH.Another aspect of the invention is a method of preparing an analog of a eucaryotic polypeptide which comprises providing a first analog in bacteria by expression of a gene encoding the analog of the eucaryotic polypeptide. The N-terminal methionine residue or an N-terminal methionine residue and its adjacent leucine residue of this analog is then removed by the method of this invention with an aminopeptidase, e.g. Aeromonas aminopeptidase. The resulting analog is then recovered by using methods known to those of ordinary skill in the art. The recovery of the analog may be optimized by removing the free N-terminal methionine and leucine residues cleaved from the polypeptide analog by the aminopeptidase. Removal of the free amino acids drives the reaction to completion. The removal may be by any method known to those of ordinary skill in the art, e.g. ultrafiltration or dialysis. The invention also concerns analogs of eucaryotic polypeptides prepared by the methods of this invention such as growth hormones, e.g. human, bovine, and porcine growth hormone. EXPERIMENTAL DETAILSMaterialsandMethodsMet-hGH and Met-Asp-Gln-bGH were prepared by recombinant DNA techniques. Coomasie blue staining of polyacrylamide gels (15% gels) of the proteins, electrophoresed in the presence of sodium dodecyl sulfate and 2-mercaptoethanol reveals: a) a major band of Mw approximately 22,000 corresponding to Met-Asp-Gln-bGH and a very faint band with a slightly higher (lot 108-) (Bio-Technology General (Israel) Ltd.) or lower (lot 113D) (Bio-Technology General (Israel) Ltd.) molecular weight for the Met-Asp-Gln-bGH molecules; b) major band Mw approximately 22,000 and a very faint band with a slightly lower molecular weight for the Met-hGH (lot 1/100) molecule (Coomassie Blue). Scanning of S.D.S. gels reveals 88-93% purity for both proteins. Purity of 95% and greater has been obtained in other preparations. No detectable contaminating endopeptidase activity was present as judged by electrophoresis of the proteins on SDS-poly-acrylamide gels after 24 hour incubation at 37°C.Aeromonas aminopeptidase was prepared from the extracellular filtrate of Aeromonasproteolytica obtained from the American Type Culture Collection (ATCC 15338), essentially according to Prescott, J.M. and Wilkes, S.H., Methods Enzymol. 46: 530-543 (1976). The purification procedure included the following steps: sedimentation and filtration of bacteria, ammonium sulfate precipitation of the filtrate (367g per liter), acetone fractionation (43.7% to 70% acetone), heat treatment at 70°C (for 8 hrs.) to destroy endopeptidase activity, gel filtration on Sephadex G-75 and ion-exchange chromatography on DEAE-Sephadex A-50. In all experiments 10 mM Tris-HCl buffer, pH 8.0 replaced 10 mM tricine buffer, pH 8.0 employed by Prescott and Wilkes. Preequilibration and elution from the G-75 column were performed in the presence of 5 micromolar ZnCl2 rather than 50 micromolar ZnCl2 employed in the original procedure. Purification on the DEAE-Sephadex A-50 column was performed by preequilibration of the column with 0.1M NaCl in 10 mM Tris-HCl, pH 8.0 containing 5 micromolar ZnCl2, application of the sample and gradient elution with 0.6 M NaCl in the same buffer (containing 5 micromolar ZnCl2). After the salt concentration increased to about 0.5M the column was eluted with 0.7M NaCl in the same buffer. The major peak which eluted from the column was collected and dialyzed against 10 mM Tris-HCl, 0 .1 M NaCl, pH 8.0 containing 5 micromoles ZnCl2 and then kept frozen to -20°C. Prior to reaction with the growth hormones the enzymesolution was incubated at 70° for 2 hrs. to inactivate any possible traces of endopeptidase activity that might have been retained in the preparation and reactivated after prolonged storage. For large-scale experiments the enzyme was incubated at 70°C for 3 h prior to reaction with the hormone.Amino acid analysis was performed on a Dionex D-502 amino acid analyzer. Amino acid sequence analysis was carried out with an Applied Biosystems Gas Phase Sequencer followed by high performance liquid chromatography of the PTH-amino acids. Example ITime dependence of the release of free methionine from Met-hGH by Aeromonas aminopeptidasePrior to reaction with Met-hGH a sample of the aminopeptidase eluted from the DEAE-Sephadex A-50 column, 0.63 mg/ml in 10 mM Tris-HCl, 0.1M NaCl, pH 8.0, was incubated at 70°C for 2h to inactivate traces of endopeptidase activity. The enzyme was then diluted 3:1 with 2M Tris-HCl, pH 9.5 to a final concentration of 0.4725 mg/ml enzyme.Met-hGH was dissolved to 8mg/ml (by weight) in 10mM Na Borate, pH 9.5.Nine hundred microliters of Met-hGH solution and 19 microliters of the aminopeptidase solution were mixed and incubated at 37°. 50 microliter aliquots were taken after 2 min, 5 min, 10 min, 15 min, 30 min, 60 min, 2h, 4h and 22h and precipitated by adding an equal volume of 3% sulfosalicylic acid solution in water, incubating at 37° for 15 min and then centrifuging in an Eppendorf bench centrifuge. 50 microliter samples of the supernatant were taken for direct amino acid analysis (without acid hydrolysis). Control experiments were run by precipitating Met-hGH solution (8 mg/ml) alone, directly after dissolution at time to or after incubation of the Met-hGH alone at 37° for 4h and for 22h. Again for each of the controls 50 microliters of hormone solution was precipitated with an equal volume of 3% sulfosalicylic acid, and 50 microliters of the supernatant were taken for amino acid analysis. Assuming a molecular weight of approximately 21,800 and that 85% of the weighed material is hormone (5%-10% water, 90%-95% purity of hormone), each analysis corresponds to 7.63 nmoles of Met-hGH starting material. The amount of methionine and several other amino acids liberated by the enzyme are listed in Table 1.The release of methionine and that of leucine are depicted as a function of time in Figure 1. The N-terminal sequence of Met-hGH is shown in Table IV. Polyacrylamide gel electrophoresis of the products reveals no detectable degradation of the hGH. Example IITime dependence of the release of free methionine from Met-Asp-Gln-bGH by Aeromonas aminopeptidasePrior to reaction with Met-Asp-Gln-bGH a sample of the aminopeptidase eluted from the DEAE-Sephadex A-50 column was heated at 70°C and diluted as described in Example I.Met-Asp-Gln-bGH was dissolved to 8mg/ml (by weight) in 10 mM Na Borate, pH 9.5.750 microliters of Met-Asp-Gln-bGH solution and 32 microliters of the aminopeptidase solution were mixed and incubated at 37°. 50 microliter aliquots were taken after 5 min, 10 min, 15 min, 30 min, 60 min, 2h, 4h and 22h and precipitated by adding an equal volume of 3% sulfosalicylic acid solution in water, incubating at 37°C for 15 min and centrifuging in an Eppendorf bench centrifuge. Again 50 microliter samples were taken for amino acid analysis. Control experiments were run by precipitating Met-Asp-Gln-bGH solution (8 mg/ml) alone either directly after dissolution at to or after incubation at 37°C for 22h. Precipitation of protein and amino acid analysis of the supernatant were carried out as described in Example 1. Assuming a molecular weight of approximately 22,000 and that 85% of the weighted material is hormone (5-10% water, 90-95% purity of hormone), each analysis corresponds to 7.41 nmoles Met-Asp-Gln-bGH starting material. The amount of methionine and several other amino acids liberated are listed in Table II.The release of free methionine as well as of leucine as a function of time is depicted in Figure 2. The N-terminus sequence Met-Asp-Gln-bGH is shown in Table IV. Polyacrylamide gel electrophoresis of the products reveals no detectable degradation of bGH analog. Example IIIComparison of Aeromonas aminopeptidase and leucine aminopeptidase (Microsomal from porcine kidney, Sigma L5006) Aeromonas aminopeptidase, 0.63 mg/ml in 10 mM Tris-HCl, 0.1 M NaCl, pH 8.0 was incubated at 70°C for 2h to inactivate traces of endopeptidase activity. The enzyme was then diluted 3:1 with 2M Tris-HCl, pH 9.5 to a final concentration of 0.4725 mg/ml. Leucine aminopeptidase (porcine kidney, microsomal, Sigma L5006), 1 mg/ml suspension in 3.5 M (NH4)2 SO4, 10 mM MgCl2 , pH 7.7, 100 microliters was mixed with 0.5M Tris HCl, pH 9.5, 25 microliters H2O, 150 microliters, and 0.025 M MnCl2, 25 microliters, and the mixture incubated at 37°C for 2h. Met-hGH, was dissolved 11 mg/ml in 10 mM NaBorate, pH 9.5. 1) 290 microliters of Met-hGH solution, 11 mg/ml + 110 microliters 10 mM Na Borate, pH 9.5 + 17 microliters Aeromonas aminopeptidase solution (final enzyme concentration: 19.3 micrograms/ml), or 2) 400 microliters of Met-hGH solution, 11 mg/ml + 85 microliters leucine aminopeptidase activated enzyme + 85 microliters 0.125 M MgCl2 (final incubated enzyme concentration: 49.7 micrograms/ml), were incubated at 37°C and 75 microliter aliquots were taken after 5 min, 3h and 22 h and precipitated with an equal volume of 3% sulfosalicylic acid. After incubation at 37°c for 15 min the mixture was centrifuged and 50 microliters of the supernatant were taken for direct amino acid analysis. Assuming a molecular weight of approximately 21,800 and that 85% of the weighed material is the hormone, each analysis corresponds to 7.46 nmoles and 7.53 nmoles Met-hGH of starting material for the reaction with the Aeromonas enzyme and the porcine leucine aminopeptidase respectively.Control experiments were run by precipitating Met-hGH with an equal volume of 3% sulfosalicylic acid after dissolution or after 22h of incubation at 37°C. The precipitated mixture was incubated for 15 min at 37°C, centrifuged, and 50 microliters of the supernatant taken for direct amino acid analysis. The results of the experiment are given in Table III. These results show that the leucine aminopeptidase does not remove the N-terminal methionine and that the small amount of methionine released is likely due to the release from small peptides formed by contaminants of endopeptidase activity (see amounts of Ile and Leu). This conclusion is confirmed by polyacrylamide gel electrophoresis showing some degradation of the hormone by the enzyme after 22h incubation at 37°C. Example IVRemoval of N-terminal methionine from Met-Asp-Gln-bGH and preparation of the sample for sequence analysis.2.5 ml Met-Asp-Gln-bGH, 8mg/ml in 10 mM Na Borate pH 9.5, was incubated with 106 microliters enzyme, 0.4725 mg/ml in 0.5 M Tris-HCl, pH 9.5, 22h at 37°C. For the determination of the amino terminal sequence, 2 ml of the mixture were diluted 1:1 with 10 mM Na Borate, pH 9.5 and 1 ml 15% sulfosalicylic acid were added, the mixture incubated at 37°C for 15 min and precipitated by centrifugation. The pellet was resuspended in 5 ml 3% sulfosalicylic acid and recentrifuged. The pellet was suspended in 5 ml 10 mM Na Borate, pH 10.5 and dialyzed against three 2 liter changes of water containing 1 ml, 0.3 ml and 1 ml of concentrated ammonium hydroxide, respectively, and then was dialyzed against water. The sample was brought to 20% acetic acid (by glacial acetic acid) and used for sequence analysis. The results of the sequence analysis, shown in Table IV, demonstrate that more than 95% of the molecules have the N-terminal sequence Asp-Gln-Phe-Pro. Example VUse of ultrafiltration or dialysis to drive the reactionsThe reactions carried out by the enzyme are reversible. Thus, removal of one of the products will tend to further drive the reaction to completion. We have demonstrated this by removing the liberated methionine residue during the course of the reaction, thus driving the reaction to further produce hGH. The liberated methionine residue was eliminated by ultrafiltration.Twelve grams of Met-hGH in 1500 ml, 10 mM NaBorate, pH 9.5, was incubated with 12.4 ml of enzyme 0.4725 mg/ml in 0.5 M Tris-HCl, pH 9.5, at 37°C for 2h. An additional amount of 6.2 ml of the same enzyme solution was added and incubation at 37°C was continued for 3 1/2 h. The solution was placed for ultrafiltration and about 50 liters of 10 mM NaBorate, pH 9.5, were passed through the material during 4h to remove free methionine and drive the enzymatic reaction to completion. Incubation at 37°C was then continued for 12 1/2 h. Total duration of the incubation and ultrafiltration was 22h. The material was absorbed on DEAE-Sephacel and the resin washed with 10 mM NaBorate, pH 9.0 and then with 10 mM NaBorate, pH 9.0 containing 25 mM NaCl, 50 mM NaCl and 75 mM NaCl. The hormone was eluted with 10 mM NaBorate, pH 9.0, containing 100 mM NaCl. The eluted hormone was concentrated, and dialyzed by ultrafiltration and lyophilized. A sample was dissolved in 20% acetic acid and subjected to sequence analysis. The results of analysis are shown in Table IV. The results demonstrate that in more than 99% of the molecules, the N-terminal methionine was removed and there was no further degradation of the protein. Example VITime dependence of the release of free methionine and free leucine from Met-Leu-hGH by Aeromonas aminopeptidasePrior to reaction with Met-Leu-hGH, a sample of the aminopeptidase eluted from the DEAE-Sephadex A-50 column was heated at 70°C and diluted as described in Example I.Met-Leu-hGH was dissolved to 8 mg/ml (by weight) in 10 mM Na Borate buffer, pH 9.0. The pH was raised to 10.6, then dropped to 8.8, and finally the mixture was centrifuged to remove a small amount of precipitate. The supernatant solution was used for reaction.One thousand microliters of the Met-Leu-hGH solution and 21 microliters of the Aeromonas aminopeptidase were mixed and incubated at 37°. Seventy-five microliter aliquots were taken after 2 min., 5 min., 10 min., 30 min., 60 min., 2 h. and 22 h. and precipitated by adding an equal volume of 3% sulfosalicylic acid solution in water, incubating at 37° for 15 min. and then centrifuging in an Eppendorf bench centrifuge. Fifty microliter samples of the supernatant were taken for direct amino acid analysis (without acid hydrolysis). Control experiments were run by precipitating the Met-Leu-hGH solution (8 mg/ml) alone with an equal volume of 3% sulfosalicylic acid, at a time to or after incubating the Met-Leu-hGH solution at 37° for 22 h. Again 50 microliters of the supernatant solutions were taken for direct amino acid analysis. The results of this experiment are summarized in Table V.The N-terminal sequence of Met-hGH is shown in Table IV. Polyacrylamide gel electrophoresis of the products reveals no detectable degradation of the hGH. EXAMPLE VIIRemoval of Met from a commercial preparation of Met gamma-Interferon.Thirty microliters of gamma-interferon (Amgen; Interferon-gamma-4A; ARN 3010, batch 1), containing the authentic sequence of the lymphokine and having a specific activity of 1-5 x 107 units/mg, was subjected to microsequence analysis. Analysis of the first three amino acids indicated that the material contains Met-gamma-Interferon with the N-terminal sequence Met-Gln-Asp (with some trace of Arg found in the third cycle).This gamma-interferon derivative was acted upon by the Aeromonas aminopeptidase and found to release free methionine as determined by amino acid analysis using a particularly sensitive amino acid analyzer with picomole sensitivity and ortho-phthalaldehyde post-column derivatization. Note that allother amino acid analyses in the application were carried out at nanomole sensitivities using a Dionex D-502 amino acid analyzer. All sequence analyses were carried out on an Applied Biosystems Model 470A protein sequencer and followed by HPLC of the PTH-amino acids. The procedure of the removal of the methionine is as follows:Methionyl-gamma-interferon: Interferon-gamma4A ARN 3010, batch 1, 107 units/ml (1-5 x 107 units/mg) in 0.04 M Tris·HCl, ph 7.0.Aeromonas aminopeptidase: (Lot 2), 0.5 mg/ml in 0.1 M NaCl-10 mM Tris-HCl 5 micromolar ZnCl2, ph 8.0 was heated at 70° for 2 h, prior to use. It was then diluted 1:9 with 0.1 M NaCl, 10 mM Tris·HCL, 5 micromolar ZnSO4, pH 8.0, to 0.05 mg/ml enzyme.Procedure: 12 microliters of the gamma-interferon solution and 3 microliters of the enzyme solution (0.05 mg/l) were incubated at 37°C for 35 min and the mixture cooled on ice. After 30 min, 14 microliters of the mixture were dried by lyophilization and loaded on the amino acid analysis column without further treatment. Control experiments were run by incubating 12 microliters of the gamma-interferon alone and 3 microliters of the enzyme alone, at 37°C for 35 min, drying the samples as above and applying them on the amino acid analysis column.The amount of methionine released was 96 picomoles and the background of other amino acids was fairly normal: Asp, 15 picomoles; Thr, 24 picomoles; Ser, 39 picomoles; Glu, 8 picomoles; Gly, 53 picomoles; Ala, 23 picomoles; Val, 10 picomoles; Leu, 8 picomoles and Phe, 11 picomoles; there was another large contaminating peak, at the position where the enzyme reference also showed a peak.- Relatively large background peaks of Ser and Gly were also seen on the gamma-interferon reference. Assuming that the specific activity of the sample is 5x107 units/mg and mol wt. for gamma-interferon of approximately 17,000, the amount of methionine released amounts.to 73% of the theoretical value. If the specific activity of the-material is lower than the above assured value, percentage of removal of Met could be lower.This experiment indicates that the N-terminal methionine can be selectively and efficiently removed from Met-gamma-interferon by Aeromonas aminopeptidase. EXAMPLE VIIIRemoval of an N-terminal Met from an interferonA recombinant interferon analog having a Met at its N-terminus was processed according to the method of the present invention. Met was selectively removed from the N-terminus of the molecule by the Aeromonas aminopeptidase. EXAMPLE IXRemoval of an N-terminal Met from a Somatomedin C polypeptideA recombinant somatomedin C polypeptide having a Met at its N-terminus was processed according to the method of the present invention. Met was selectively removed from the N-terminus of the molecule by the Aeromonas aminopeptidase. EXAMPLE XRemoval of Met from Met-Porcine Growth Hormone (PGH) and non-removal of N-terminal Ala from the mature recombinant Cu2-Zn2 human superoxide dismutase.Aeromonas aminopeptidase lot 2, 0.5 mg/ml (in 0.1M NaCl-10mM Tris HCl pH 8.0 was heated at 70°C for 2 hours prior to use, then diluted 3:1 with 2M Tris HCl, pH 9.5.Met-PGH (lot 5/100) and Cu2-Zn2 human superoxide dismutase (SOD lot 1) were prepared by recombinant techniques. The latter has the authentic N-terminal sequence of the mature protein except that the N-terminal Ala is not N-Acetylated.Procedure: The proteins were dissolved, 8 mg/ml in 10mM sodium borate, pH 9.5. To 600 microliters of the protein solutions were added 34 microliters of the enzyme solution and the mixtures were incubated at 37°C. Samples were taken with time and precipitated with equal volume of 3% sulfosalicylic acid and incubated at 37°C for 15 minutes, then centrifuged. 50 microliters of the supernatant solutions were taken for amino acid analysis. Control experiments were run by incubating the proteins alone at 37°C for 22h and proceeding with the amino acid analyses as above. Assuming 85% content of the weighed proteins and molecular weights of 22,000 and 16,000 (per subunit) for Met-PGH and Cu2-Zn2 superoxide dismutase, respectively, the theoretical amount of N-terminal residues in each analysis are 7.31 nmoles and 10.17 nmoles, respectively. The amount of Met and Ala released are shown in Table VI. Release of Met from Met-PGH and Ala from recombinant Cu2-Zn2 human superoxide dismutase by Aeromonas aminopeptidaseMet-PGH30 min3 hr22 hrt22 hr (control)Met released1.952.414.630.11Recombinant Cu2-Zn2 human superoxide dismutase30 min3 hr22 hrt22 hr (control)Ala released.15.32.530.10There could be several reasons for the non-stoichiometric removal of Met from Met-PGH (in contrast to the stoichiometric removal of Met from Met-hGH). One explanation could be that the molecules could be present as non-covalently associated dimers and that the N-terminal methionine of only one of the molecules in the dimer is accessible to the enzyme attack, whereas the N-terminal methionine of the other molecule in the dimer is sterically hindered. For this reason, only about 50% - 60% of the N-terminal methionine residues were removed. Met-hGh, on the other hand, is monomeric, Another possibility is that in Met-pGH part of the molecules are still formylated and the enzyme does not remove formyl-methionine. In order to prove any of these or other possibilities further experiments would be required. EXAMPLE XIRemoval of Met, Lys and Val from Apolipoprotein E by Aeromonas AminopeptidaseMethionyl-ApolipoproteinE (Lot CC 017) with the N-terminal sequence Met-Lys-Val-Glu was prepared in E. coli and purified. It was used as a solution of 2.53 mg/ml in 5mM NH4HCO3.Aminopeptidase.Aeromonas aminopeptidase (Lot 2) was used in the experiment. The enzyme, 0.5 mg/ml in 0.1 M NaCl 10 mM Tris-HCl 5 micromolar ZnCl2, pH 8.0 was heated for 2.5 hours prior to reaction with the protein.Procedure. 600 microliters of Methionyl-Apolipoprotein E and 12.25 microliters of enzyme were incubated.at 37°C and 90 microliter aliquots of the mixture were taken with time and precipitated with 10 microliters of 15% sulfosalycilic acid in water. The mixture was incubated at 37°C for 15 minutes and centrifuged. 50 microliters of the supernatant were taken for direct amino acid analysis (without acid hydrolysis). A control experiment was run by incubating the protein alone without the enzyme for 22 hours, and proceeding with the analysis as above. The amounts of methionine, lysine and valine released from the protein are given in Table VII. Release of Met, Lys and Val from Methionyl-Apolipoprotein E by Aeromonas Aminopeptidase(nmoles amino acid released)10 min30 min1 h4 h22 ht22 (control)Met2.642.772.732.883.09less than 0.1Lys2.112.372.442.642.80 Val1.872.192.102.413.22 The amount of methionine, lysine and valine released agree with the theoretical amount expected, based on the specified concentration of the sample and assuming a molecular weight of approximately 35,000 for the protein (i.e. 3.19 nmoles each). Yet, the removal of the third amino acid, Val is somewhat slower than the other amino acids. Within the first 1 hour of reaction no release of Glutamic acid could be observed indicating the stopping characterofthisaminoacid for the aminopeptidase. After 22 hours of incubation, a small amount of degradation of the protein could be observed on polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulfate (SDS) and 2-mercaptoethanol. This could reflect traces of endopeptidase activity in either the substrate or the enzyme. The SDS gels show that the new ApoE derivative, without the three amino acids Met, Lys, and Val, migrates slightly faster than the parent protein. Interestingly, the enzyme in the reaction mixture lost activity after incubation for 22 hours, probably caused by the Apolipoprotein E which is cytotoxic and may also inactivate the enzyme. With all other substrates tested so far, the enzyme activity in the reaction mixture is fairly well preserved after 22 hours at 37°. EXAMPLE XIIRemoval of Met from Met-bGHThis example shows the removal of N-terminal methionine from Methionyl-bGH, where bGH is the phenylalanine form of bGH, having the N-terminal sequence Met-Phe-Pro.Met-bGH (Lot 178) was prepared in E. coli for the purpose of the present experiments.Aminopeptidase.Aeromonas aminopeptidase (Lot 2), 0.5 mg/ml in 0.1 M NaCl - 10 mM Tris - HCl, 5 micromolar ZnCl2, pH 8.0 was preheated at 70°C for 2 h prior to use, then diluted 3:1 with 2 M Tris HCl, pH 9.5 to a final concentration of 0.375 mg/ml.procedure. The hormone was suspended, 8 mg/ml, in 10 mM sodium borate buffer, pH 9.5, the pH was raised to 12 with 1N NaOH, then lowered back to pH 9.4 with 1N HCl, then centrifuged to remove a slight amount of precipitate, and yielded a solution of approximately 7 mg/ml.One thousand microliters of the Met-bGH solution and 56.3 microliters of the enzyme solution were incubated at 37°C and 75 microliter aliquots of the mixture were taken with time and precipitated with an equal volume of 3% sulfosalycilic acid. After incubation of the mixture at 37°C for 15 min. the precipitate was centrifuged and 50 microliters of the supernatant taken for direct amino acid analysis (without acid hydrolysis). Control experiments were run by precipitating the hormone alone at time zero or after incubation at 37°C for 22 h and proceeding with the analyses as above. The results of the experiment are given in Table VIII. Release of Met from Methiohyl-bGH by Aeromonas Aminopeptidase(nmoles Met/50 ul sample)Control2 min5 min10 min30 min1 h2 h4 h22 ht0t223.483.673.763.773.773.814.194.450.10.29The experiment demonstrates that the reaction of Aeromonas aminopeptidase with Met-bGH is very rapid since at 20 micrograms/ml of enzyme most of the reaction is complete in 2 min.The stoichiometry of the reaction is about 65% as opposed to stoichiometries of 90-100% which were observed for the reaction of the enzyme in several reactions with two different batches of Met-hGH, with Met-Asp-Gln-bGH and with Met-Apolipoprotein E as well as with Met-gamma-interferon and Met-somatomedin. On the other hand, reaction with Met-Leu-hGH and Met-bGH showed only approximately 65% of Met released/mole substrate and with Met-pGH only approximately 50%-60%. We have recently observed that with certain new batches of Met-Asp-Gln-bGH the stoichiometry is also in the 50-60% range. We previously assumed that this partial stoichiometry would be due to either a) not completely pure materials; b) incomplete removal of the N-formyl group by the E. coli host deformylating enzyme(s) and/or; c) to dimer formation of some hormones and accessibility of the enzyme to only one of the monomers in the dimer. We found indications for yet another likely explanation for the incomplete stoichiometry, namely, that the host E. coli processing enzyme system partially removes some of the N-terminal methionine, e.g. in Met-pGH and Met-bGH, before purification of the proteins. EXAMPLE XIIIBiological Activity of Authentic Recombinant hGH, Obtained from Met-hGH by Removal of Met with Aeromonas AminopeptidesThe authentic recombinant hGH obtained from Met-hGH by reaction with Aeromonas aminopeptidase by procedures essentially the same as those described in Examples I and V including use of ultrafiltration to remove free methionine is biologically active and displays high activity. Thus, the batch preparation of hGH described in Example 1 and 2 (lot 2/100), that was derived from Met-hGH lot 1/100 has an N-terminal Phe. Its immunoreactivity is the same as that of pituitary hormone from frozen glands and its biological activity by radioreceptor binding assay is 2.1 IU/mg. In addition, another batch preparation of Met-hGH (lot 4.1.1) that was passed on an anion-exchange column to remove deamidated forms of the hormone, then treated with the Aeromonas aminopeptidase, using the ultrafiltration techniques to remove free methionine that was released during the reaction in order to drive the reaction to completion, then passed on another column of an anion exchanger and lyophilized, was designated lot 4.2.1 and analyzed. The results were: a) The first 38 amino acids for N-terminus were identical to that of the natural pituitary derived product, with the amino acid at the N-terminus being Phe (at least 99%).b) The C-terminal residue was Phe, also identical to that of the pituitary derived product. c) The immunoreactivity is 1.35 times higher than that of a commercial preparation from pituitary.d) The activity by radio-receptor binding assay is 2.5 units/mg protein.DiscussionThe experiments and results presented above clearly demonstrate that Aeromonas aminopeptidase rapidly removes the N-terminal methionyl residue from Met-hGH, Met-Asp- Gln-bGH, Met-gamma-interferon, Met-Somatomedin C, Met-pGH, Met-Apolipoprotein E, and Met-bGH molecules prepared by recombinant DNA techniques. Also, the aminopeptidase can remove the N-terminal methionine residue and its adjacent leucine residue from Met-Leu-hGH, prepared by recombinant DNA techniques. Precautions taken to avoid endopeptidase activity both from the substrate and the aminopeptidase have proven successful in the sense that the enzymatic reactions contain very little if any detectable endopeptidase cleavages (Figures. 1 and 2 and Tables I-VIII) even after 22h of incubation of the hormones with the aminopeptidase. Thus, conditions under which completion of the enzymatic reaction takes place without significant endopeptidase activity are readily available.Additionally, the results of Example VI demonstrate that Aeromonas aminopeptidase can rapidly remove several amino acids from eucaryotic polypeptide analogs, not only one methionyl residue. In particular, it has been demonstrated that the N-terminal methionyl and leucyl residues can be removed from Met-Leu-hGH to yield authentic human growth hormone.The most striking conclusion of the experiment of Example VI is that the amount of methionine and leucine released is the same, even after only two minutes of reaction. This is due to the fact that the leucine residue is probably being removed at a faster rate than the methionine residue. Thus, a recombinant CNA. product of the design Met-Leu-hGH, where Met is followed by Leu, assures that the final product will be hGH with no detectable presence of Leu-hGH molecules. This experiment demonstrates that the authentic molecule can be obtained not only from a methionyl-derivative but also from a methionyl-x-derivative where x is another amino acid. Similarly, an authentic molecule would be obtained from (x)n-derivative where n is greater than two.The enzymatic reaction is specific. In the two reactions examined, there are clear Asp and X-Pro stops of the aminopeptidase that are in accord with the specificity of the enzyme towards small peptides.The reactions studied are quantitative. Confirmation of this conclusion was partly achieved by preliminary sequence analysis where at least 99% and 95% of the N-terminal residues of the products of reaction of the aminopeptidase and the hormones were found to be Phe and Asp for the human and bovine growth hormone products, respectively. Confirmation of the quantitative aspect of the reaction is confronted with obvious handicaps of the sequencing method (sensitivity, noise, by-products and separation limits) and the actual figures could be even higher than those given above.It should be noted in this regard that the enzymatic reaction Met-Protein ⇄ Met + Protein is reversible and it could in principle be driven to synthesis by adding excess methionine or to complete hydrolysis by continuous removal of the amino acid. In one of the examples (Example V) demonstrating a batch preparation of hGH we have indeed employed ultrafiltration for several hours at a progressive stage of the reaction to remove free methionine and assist completion of the reaction.Removal of the aminopeptidase from the reacted hormone is achieved by selective absorption and desorption of the hormone to an anion-exchange resin. Other alternative ways to remove the aminopeptidase after its reaction with the hormone could be the use of a water-insoluble derivative of the enzyme in a batch or packed in a column as well as the use of an affinity resin for the enzyme to absorb it at the end of the reaction.The procedure used for Met-hGH, Met-Asp-Gln-bGH, Met-Leu-hGH, Met-gamma-interferon, Met-somatomedin C, Met-pGH, Met-apolipoprotein E, and Met-bGH should be applicable to other growth hormones and polypeptides. Methods for obtaining the aminopeptidase can be improved (e.g. more economical process of isolation or genetically engineering the enzyme or developing microorganism overproducing aminopeptidase and endopeptidase-free mutants of the microorganism). Other aminopeptidases of low molecular weight (less than 100,000) like Streptomycesgriseus aminopeptidase and aminopeptidases which are thermostable and active at alkaline pH could possibly substitute for the Aeromonas enzyme.In addition to its action on growth hormones the amino-peptidase(s) can be useful for other recombinant DNA products such as hormones, growth factors, and enzymes that possess N-terminal sequences in accordance with the specificity of the enzyme or enzymes, e.g. somatomedins interleukin 3, interferons, apolipoprotein E. Furthermore, the recombinant DNA products can be designed in a manner which would allow the removal of several amino acids from the N-terminus, in addition to the methionine residue. For example derivatives like Met-Lys-bGH, Met-Leu-Tyr-bGH and Met-Phe-Asp-Gln-bGH when acted upon by aminopeptidase will yield hGH, bGH, bGH and Asp-Gln-bGH, respectively. It may be also possible to use the enzyme to add an amino acid by using excess of the amino acid in the incubation mixture, thus driving the synthesis reaction.
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A method of producing a human growth hormone having the amino acid sequence of naturally occurring human growth hormone which comprises: a. producing in a microbial host a first polypeptide which is characterized by the presence of one or more additional amino acids at the N-terminus of the amino acid sequence of naturally occurring human growth hormone and by the presence of methionine at its N-terminus;b. contacting the first polypeptide so produced with an aminopeptidase, other than leucine aminopeptidase [EC 3.4.11.1], so as to produce a second polypeptide having a sequence identical to the amino acid sequence of naturally occurring human growth hormone and release said one or more additional amino acids from the first polypeptide, wherein during said contacting said released amino acids are separated/removed from contact with said aminopeptidase;c. removing the aminopeptidase; andd. recovering the second polypeptide so produced.A method of claim 1, wherein the microbial host is a bacterium.A method of claim 2, wherein the bacterium is Escherichia coli.
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SAVIENT PHARMACEUTICALS INC; SAVIENT PHARMACEUTICALS, INC.
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BEN MEIR DANIELA; BLUMBERG SHMARYAHU; BEN MEIR, DANIELA; BLUMBERG, SHMARYAHU
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EP-0489712-B1
| 489,712 |
EP
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B1
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EN
| 19,960,828 | 1,992 | 20,100,220 |
new
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F42B10
| null |
F42B10
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F42B 10/66C
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Missile steering arrangement using thrust control
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A reaction control system for a projectile includes two oppositely directed nozzle assemblies (20) each including a control element (24). The control elements are operated inversely by a control member (30). Each control element (24) includes lost motion means (34) to accommodate movement between a sealing end (26) and a distal end (28) thereof.
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This invention relates to a reaction control system for a projectile, for example a missile or a mortar round and to projectiles including such systems. Directional control of missiles in flight may be achieved either aerodynamically using movable control surfaces, e.g. fins, or by using a reaction control system in which control thrusts are generated by emitting a reaction gas transversely of the missile. In the known examples of the latter method of control it is usual to employ single shot squibs or pulsed units. This is believed to limit the degree and accuracy of control and requires the missile autopilot to be specifically designed to deal with this method of control. In these systems the magnitude of the thrust remains generally the same; the only control available is control of the length of the impulse. Studies conducted by the applicants show that there is a need for a reaction control system which produces a thrust whose magnitude may be varied continuously. Furthermore, there is a need for such a system in which the relationship between the movement of the member controlling the reaction control system and the thrust thereby is generally compatible with that of a fin assembly so that the reaction system may be controlled by an existing autopilot without major modification. EP-A-244971 discloses a reaction control system according to the preamble of claim 1 and in which lost motion is provided between a lever and a pinion in the drive train between an electromechanical actuator and a valve control element, for the express purpose of avoiding the need to match the strokes of the actuator and the valve. According to the invention, there is provided a nozzle assembly including a nozzle control element movable to control the flow therethrough, and comprising a sealing end and a distal end, a control member for moving said nozzle control element, and lost motion means in the control path between said control member and said nozzle control element, said lost motion means comprises bias means arranged between said sealing end and said distal end, whereby said distal end may move relative to said sealing end against said bias. A preferred embodiment of the system is particularly useful where a projectile requires the control function exerted by the aerodynamic fins either to be augmented by the reaction control system, e.g., to execute a terminal manoeuvre, or to be replaced thereby when the projectile is travelling too slowly for the aerodynamic fins to be effective, e.g. at launch. The invention will now be described by way of non-limiting example, reference being made to the accompanying drawings, in which:- Figure 1 is a schematic rear view of an actuator assembly of an example of reaction control system according to this invention; Figure 2 is a section view of the actuator assembly of Figure 1 taken on lines II-II; Figure 3 is a diagrammatic view of the arrangement of one pair of nozzles in the arrangement of Figures 1 and 2; Figure 4 is a graph illustrating the relationship between piston deflection, thrust and fin deflection for an example of a missile incorporating a reaction control system and a fin assembly; Figure 5 is a diagrammatic view of an example of a missile incorporating a reaction control system and a fin assembly; Figure 6 is a block diagram of the control system of the missile of Figure 5; Figures 7 and 8 show an example of a control thruster assembly in the open and closed positions repectively; and Figure 9 shows schematically an example of a control thruster assembly configured in a servo loop. Referring to the Figures, the illustrated embodiment of reaction control system is intended to be operated in conjuction with a fin assembly by an autopilot. The reaction control system may however also be used in missiles which do not incorporate a fin assembly. Figures 1 and 2 illustrate an actuator assembly 10 for a reaction control system. The assembly 10 comprises a casing 12 which houses a gas generator 14 and which includes an outer flange 16. The outer flange carries four thruster assemblies 18 equispaced around the periphery of the missile. Each thruster assembly 18 comprises a pair of aligned nozzles 20 connected by conduits 22 to the gas generator 14 and each arranged to exhaust in opposite directions. The flow of gas from gas generator 14 through each nozzle 20 is controlled by means of a piston 24 slidably mounted with respect to the nozzle so as to be movable to vary the effective thrust area of the nozzle and thus the thrust generated. Each piston is continuously movable with respect to the throat of the associated nozzle - i.e. it can assume any position between fully open and fully closed. Each piston is provided with a conical sealing end 26 and a distal end 28. The respective distal ends of the pistons 24 of a pair of nozzles are acted upon by a cam member 30 rotatably secured to the flange 16 and attached to an operating lever 32. Rotation of the cam member causes inverse operation of the pistons, i.e. one piston moves to increase the flow through its associated nozzle as the other piston moves to decrease the flow through its associated nozzle. A spring arrangement 34 is provided between the sealing end 26 and the distal end 28 and is arranged so that in normal operation there is no relative movement between the sealing end and the distal end, but if the sealing end 26 should seize and be prevented from movement, the distal end may move relative to the sealing end 28 against the bias of the spring 34 so that the cam member 30 is not prevented from rotating. The four thruster assemblies 18 are equispaced around the periphery of the missile so that two assemblies (the upper and lower assemblies as viewed in Figure 1) lie in spaced planes parallel to the yaw plane and two assemblies (the left hand and right hand assemblies as viewed in Figure 1) lie in spaced planes parallel to the pitch plane. In use, as illustrated in Figure 5, the actuator assembly illustrated in Figures 1 and is mounted forwardly of the centre of gravity of the missile. Hence, when used in unison, the upper and lower assemblies effect control in the yaw sense and the left and right hand assemblies effect control in the pitch sense. If the upper and lower assemblies are not operated to generate the same magnitude of thrust in parallel directions, then a component of roll torque is generated. If the thrust generated by the upper and lower assemblies is equal and opposite then a simple roll torque will be generated. Similar considerations apply to operation of the left and right hand assemblies. The gas generator may be of any suitable form; in the illustrated embodiment, it takes the form of a hot gas generator which is ignited by means of an igniter 36. A burster disc assembly 38 is provided for safety purposes. Figure 3 illustrates schematically a single assembly showing the operating lever 32 and the cam 30. It will be understood that the direction and magnitude of the thrust vector generated by the assembly is dependent on the position of the operating lever 32. Figure 4 illustrates the variation of the thrust developed with the deflection of the piston; it will be seen that the thrust varies proportionally with movement of the piston. It should be noted that this is for the purposes of illustration only and that other characteristics will result for different designs. Figure 5 illustrates a missile with a reaction control assembly 10 located forwardly of the centre of gravity 40 of the missile and an aft fin assembly 42 comprising four movable fins 44 arranged at the aft of a missile. The fins are oriented around the missile body so that operation of one set of diametrically opposed fins in unison effects control in the yaw sense whilst operation of the other set of diametrically opposed fins in unison effects control in the pitch sense. Differential operation of either set of fins effects control in the roll sense. Figure 6 illustrates a navigation system for the missile of Figure 5. An autopilot 46 calculates the control movements required for the desired course corrections and controls a servomotor assembly 48 which controls movement of the fins 44 and also movement of the operating levers 32 of the associated thruster assembly. It will be understood that each of the thruster assemblies is operable to impart a control moment which is similar to that imparted by rotation of a fin member when the missile is in normal flight. Thus the control function exerted by thruster assembly 18' is analogous to that exerted by movable fin 44' etc. The thrust developed on deflection of the fin 44 is illustrated in Figure 4. It will be seen that, as with movement of the pistons of the thruster assemblies, that thrust/movement relationship is essentially linear for this example and that the thrust/movement characteristics for the thruster assembly are similar to those developed by angular movement of the fin. Thus, by linking the operating levers 32 to a normal fin servo system, the reaction control system may provide a thrust which is proportional to the fin deflections, so enhancing the control effectiveness of the fins. This is particularly useful when the missile is travelling too slowly for the fins to be effective e.g. at launch, or where an extra amount of control is desired e.g. for a terminal manoeuvre. Because of the similarity between the movement/thrust characteristics of the fins and reaction control system this method of control augmentation may be added to a missile with little or no change to the autopilot. In the arrangements of Figures 1 to 6, since the magnitude of the thrust developed can be adjusted across a large, continuous, range of values, the missile weave associated with squibs or pulsed thrusters can be avoided. Where the reaction control system is employed in conjunction with a conventional movable fin assembly, the spring 34 override mechanism in the reaction control system serves an important purpose because it prevents total failure in the event of a failure of the reaction control system, as it enables the movable fin assembly to continue operating. The spring override mechanism is of particular benefit where two nozzles are operated in back to back fashion by a single actuator as in the arrangements 18 of Figures 1 to 6, because in these types of arrangement the mechanism may compensate for slight dimensional inaccuracies of the piston members, the cam mechanism and/or the housing defining the bores in which the pistons slide which might otherwise jam or damage the drive motor when moving towards an end position. The mechanism means that the designer can ensure that the pistons may be moved into engagement with the nozzle throat, thus closing it, without jamming the servo control system or preventing movement of the corresponding fin member. The reaction gas may be a cold or hot gas and the storage reservoir or gas generator may be integrated with the nozzle units to provide a compact control package. The reaction gas may be bled off the main missile rocket motor; indeed a plurality of thruster assemblies may be inclined rearwards to provide not only lateral control but also the main source of rocket propulsion. Referring now to the examples illustrated in Figures 7 to 9, these are intended to provide a control thruster assembly in which the force or torque required to move the control element is greatly reduced, so that the assembly is suitable for use in flight vehicles such as guided missiles. Figures 7 and 8 illustrate an embodiment of control thruster assembly in the fully open and fully closed positions respectively. The assembly comprises a housing 50 defining an outlet throat 52 and a fluid supply manifold 54, and a plunger 56 which is slidably located in a pair of spaced bores 58,60 each of which includes a gas seal 62. The bore 60 at the rear of the plunger 56 is closed to define a variable volume chamber 63, together with the rear end of the plunger 56. A pressure balance bore 64 interconnects the two axial end faces of the plunger 56 to tend to equalise the pressure forces acting on the plunger 56. A pressure transducer 66 may be provided to sense the pressure in the variable volume chamber 63, the sensed pressure being a measure of the pressure of the fluid in the outlet throat 52 and also of the displacement of the plunger 56. Intermediate the bores 58 and 60, the housing 50 is relieved and receives for limited axial movement an actuating lever 68 secured to the plunger 56. The actuating lever 68 includes a rack portion 70 which engages the pinion 72 of a drive motor (not shown) for driving the plunger between the positions shown in Figures 7 and 8. A plunger position sensor linkage 74 may be connected to the actuating lever 68 for determining the position of the plunger. In this arrangement, the thrust can be switched on or off or modulated by movement of the plunger 56. For a proportional thrust system the drive may be in the form of a servo motor/gear box, whilst for a bang-bang system a stepping motor drive connected directly to the plunger may be used. An important part of the assembly of Figures 7 and 8 is the pressure balance bore 64, which allows the pressure at the outlet throat to be sampled. The magnitude of the sampled pressure will be a function of the plunger displacement. With this system only a modestly powered servo actuator drive will be required for the plunger as the resultant pressure force acting on the plunger will be low. Inthe off position, ambient pressure will act on both ends of the plunger. Plunger position data may be determined from a position sensor connected to the position sensor linkage 74 or it may be derived from a pressure transducer 66 which samples the pressure at the outlet throat via the pressure balance bore 64. For high gas temperature operation, refractory or ceramic materials may be used in the assembly. The gas supply to the thruster assembly may be taken from the main propulsion rocket motor system or from a dedicated hot or cool propellant gas supply. The number of thrusters will be a function of the particular control system required. It will readily be seen that this arrangement of Figures 7 and 8 may be incorporated into the proportional control systems illustrated in Figures 1 to 6 Alternatively, it may be incorporated in a bang-bang system. Figure 9 is a schematic illustration of a thruster assembly of the type illustrated in Figures 7 and 8 configured in a servo-control loop. Many of the component parts are similar and will not be described in detail again. In this arrangement the plunger 56 has an integral rack portion 70 which meshes with a pinion 72 connected via a gear train to an electric motor 80. A potentiometer 81 associated with the electric motor 80 provides a position feedback signal which is supplied to one input of a differential amplifier 82 which controls the motor 80. The position servo can control a single unit as shown with a pressure balance bore 64 to reduce actuation forces, or two units arranged back-to-back as in the arrangements of Figures 1 to 6, where the pressure balance bore would not be necessary. Similarly a servo control loop of the type illustrated in Figure 9 could be used to drive the cam mechanism of the arrangements of Figures 1 to 6. In the examples of Figures 7 to 9, the use of torque motors or gear motors to actuate the pistons means that it may be possible to transmit larger forces which might damage the cam-type arrangements of Figures 1 to 6. It will be understood that the reaction control systems described herein may be coupled to operate in tandem with the fin control system or they may operate independently of any fin control system.
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A reaction control system for a projectile, comprising a nozzle assembly (20) including a nozzle control element (24) movable to control the flow therethrough and comprising a sealing end (26) and a distal end (28), a control member (30) for moving said nozzle control element (24), and lost motion means in the control path between said control member (30) and said nozzle control element (24) characterisedin that said lost motion means comprises bias means arranged between said sealing end (26) and said distal end (28), whereby said distal end (28) may move relative to said sealing end (26) against said bias. A reaction control system according to Claim 1, wherein said bias means comprises a spring (34) located between said sealing end (26) and said distal end (28). A reaction control system according to Claim 1 or Claim 2, including a further oppositely directed nozzle assembly (20) including a further moveable nozzle control element (24) having a sealing end (26) and a distal end (28) and lost motion means (34) located between said sealing end (26) and said distal end (28), wherein said control member (3) is operable to move said further nozzle control element (24). A reaction control system according to any preceding claim, wherein the or each nozzle assembly (20) has an aerodynamic control surface means (44) operatively associated therewith for generating a control thrust or movement in generally the same sense as the control thrust generated in use by said nozzle assembly (20). A reaction control system according to any preceding claim, wherein the or each nozzle control element (24) comprises a piston means (56) having a sealing face which in use is exposed to the outlet pressure of said nozzle assembly (20). A reaction control system according to Claim 5, wherein said piston means (56) includes passage means (64) for communicating the pressure at said sealing face (26) to a distal face (28) of said piston means (56).
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BRITISH AEROSPACE; BRITISH AEROSPACE PUBLIC LIMITED COMPANY
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FOULSHAM PETER G; MACHELL ANTHONY; FOULSHAM, PETER G.; MACHELL, ANTHONY; Foulsham, Peter G., c/o British Aerospace Plc.; Machell, Anthony, c/o British Aerospace Plc.
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EP-0489720-B1
| 489,720 |
EP
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B1
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EN
| 19,970,702 | 1,992 | 20,100,220 |
new
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F23D14
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F26B3, F26B23, F26B13
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F26B13, F23D14, D21F7, F26B3, F26B23, D21F5
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F23D 14/60, F26B 3/30B, F26B 23/02, D21F 7/00C, D21F 5/18, F26B 13/00J, R23D207:00, F26B 13/10
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Method and apparatus for uniformly drying moving webs
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A flame intensity controller for controlling the air/gas mixture introduced into a conveying and/or mixing chamber (24). Plural heating arrays (106, 108, 110, 112) are transversely aligned to the direction of movement to dry the moving web (W). The controller (128, 130) selectively controls the heating intensity of each section (42) of the heating arrays to thereby control the amount of drying experienced by each longitudinal section of the web. The controller may be a countercurrent air controller (52, 54, 56, 58) or a mechanical restrictor (212). The energy output of each section is controlled between adjustable upper and lower energy levels. However, the lower energy level is preferably chosen to be sufficient to sustain combustion. The independent control of the dryer sections provides dramatic improvement in uniformity of the moisture profile across the web.
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The present invention pertains to drying an elongated web, in particular for the purpose of eliminating wet streaks and/or adjusting the moisture profile in the cross-direction of a moving web of paper or fiber as part of the drying cycle. The invention also relates to controlling the intensity of individual burner elements emitting infra-red radiation for use in said drying operation. A number of applications exist wherein it is desirable, for example, to selectively apply heat to a moving web, which is subject to drying by other means, for the purpose of eliminating wet streaks or areas of higher moisture concentration and/or to obtain a desired moisture pattern across the web. This process of selectively applying varying amounts of heat across a moving web for the purposes of eliminating and/or adjusting moisture variation across the web will hereinafter be termed profiling . For practical reasons, the energy density must be high to achieve profiling in drying operations. Therefore, fossil fuel burners or emitters are preferred rather than electric energy. The problem then becomes one of controlling the amount of fuel or the amount of combustible gases delivered to individual burners or emitters in such a manner as to effect profile control in increments corresponding to the moisture variations across the web without turning off the burner or emitter. For example, in the paper making field, paper is produced in the form of an elongated web, which web is comprised of wood pulp saturated with water. The water is removed from the wood pulp by squeezing the wood pulp as it passes between cooperating rollers and further by drying the web formed by the wood pulp through suitable drying means in order to reduce the moisture content to a value within a controlled range. An instrument for detecting moisture content is typically utilized to monitor moisture content of the moving web. The instrument may be located either upstream relative to and/or following the location of the dryer units. The variation in moisture content across the width of the moving web, i.e., in a direction transverse to the direction of movement of the web (the cross direction), frequently presents a serious problem for effectively and efficiently drying the web. To maintain a given moisture range in the final product, the moving web often has to be remoistened and/or overdried, resulting in expensive waste of energy, reduction in machine productivity, increased manufacturing cost and sacrifice of product quality. It is thus extremely desirable to provide apparatus for controlling the web drying operation in a localized manner to obtain the desired moisture range while, at the same time, either eliminating or significantly reducing the above-mentioned disadvantages. Controling individual burner/emitter elements (E) established in a grid consisting of (m x n) elements, as shown in Fig. 6 where (m) denotes the number of columns and (n) the number of rows in the grid, a minimum of one row but more frequently 4-6 rows are used depending on the amount of water that has to be evaporated in order to achieve a levelled moisture profile. The number of columns required is dependent on the width of the web and the size of the individual elements. For example, in a web 3048 mm (120 inches) wide, 20 elements could be typically used if the elements were 152,4 mm (6 inches) wide. For illustration purposes, it is simple to examine a small grid consisting of 4 x 5 elements as shown in Fig. 6, providing an arrangement of 5 columns and 4 rows of elements. Each burner/emitter E has a maximum output of 100% under normal operating conditions. By restricting the fuel flow to the burner, its energy output can be turned down to about 20% without the risk of flame-out. The turn-down ratio is therefore 80%. Let it further be assumed that the 80% turn-down corresponds to a water evaporation load of 4,536 kg (10 lbs)/element/hour. Each column (of 4 emitters) thus has a turn-down capability of 18,144 kg/h (40 lbs)/h and a maximum evaporation rate of 40/0,8 = 22,68 kg/h (50 lbs/h). By varying the number of rows that are turned down, it is possible to change the turn-down of each column to be either 18,144 kg (40 lbs), 13,608 kg (30 lbs), 9,072 kg (20 lbs), or 4,536 kg (10 lbs). 4,536 kg (10 lbs) turn-down for a column would thus be achieved by having 3 rows turned down and 1 row fully on. This particular illustration gives a total turn-down of 18,144 kg (40 lbs) per column in 4,536 kg (10 lbs) increments. It is also possible to change either the total turn-down by adding or deleting rows to the grid or by decreasing the increment by setting the amount of turn-down to a fraction of the 4,536 kg (10 lbs) per emitter rating. If one, for instance, set the turn-down of row 1 to half of the total turn-down or 2,268 kg (5 lbs), it would be possible to achieve a total column turn-down of 15,876 kg (35 lbs) in 2,268 kg (5 lb) increments as follows: Row # Turned Down kg (Pounds) of Turn-Down 12,268(5) 24,536(10) 1 + 26,804(15) 2 + 39,072(20) 1 + 2 + 311,34(25) 2 + 3 + 413,6080(30) 1 + 2 + 3 + 415,876(35) By varying the number of rows used and by selecting the proper turn-down fraction for each row, it is possible to vary the drying intensity to accurately match moisture variations across a moving web which is subject to drying to establish a levelled moisture profile. By changing the size of the elements in the cross web direction (i.e., to greater or less than 152,4 mm (6 inches)), it is also possible to vary the resolution of the drying intensity across the web. The present invention describes two different modes of altering the fuel flow to each burner/emitter in order to achieve the turn-down of the element. (a) Mechanically restricting the fuel or the air or the fuel/air mixture. (b) Pneumatically restricting the fuel or the fuel/air mixture by injecting a counter-current airflow downstream of the fuel orifice to serve as a pressure regulating device or achieve a blocking function through the use of an air curtain. Either method is characterized by the use of a flow blocking device which operates discretely in two different modes, open - high fire or closed - low fire. This approach makes it possible to use simple three-way solenoid actuators to operate the mechanical restrictor or the pneumatic air curtain or pressure control. The solenoid is fast, reliable and minimizes the number of moving parts and the low fire mode provides repeatability and easy flame monitoring and fast temperature response. The pneumatic restrictor injects a countercurrent air flow into an air/gas mixing chamber or a manifold located down-stream of the mixing value employed for metering/mixing of combustion gas and air. The back pressure created in the mixing chamber by the countercurrent air flow reduces the combustion air flow through the gas/air orifice of the mixing valve. The mixing valve typically utlilizes a venturi orifice. The venturi action in the orifice, created by the air flowing past the venturi establishes a vacuum which accurately meters the gas drawn into the mixing chamber. The back pressure established by the introduction of the countercurrent air flow through a control inlet, which counter-current air flow is of greater pressure than the pressure of the combustion gas/air mixture in the mixing chamber, reduces the flow of combustion gas passing through the venturi orifice, which in turn meters less gas into the mixing chamber. By varying the flow of countercurrent of air into the mixing chamber, the intensity of the burner can be varied continuously from high to low fire without the need for shutting off the burner completely, which would then require automatic reignition and flame monitoring for individual burners. A complete shut-off is disadvantageous since it also increases the heat-up period of the burner. The benefits of utilizing a reverse flow obtained through an air jet for changing the burner intensity reside in the ability to achieve continuous ignition and the elimination of unnecessary mechanical parts and in the safety of utilizing an air stream as a means of control. In one preferred embodiment, a solenoid valve can be utilized to control the flow of the air jet for switching between two discrete positions, viz., full fire and low fire. The air pressure of the air supply used to supply the reverse flow air jet is higher than that of the mixing chamber to prevent leakage of combustion gases back into the air supply line of the air jet. The operation of the solenoids for the countercurrent air jet can be controlled manually to change the flow rate or can be controlled automatically by control means which may include a microprocessor which, in turn, can be interfaced with a scanning moisture measuring device. The latter technique is extremely useful in moisture profiling applications, as will be more fully described. The countercurrent air flow nozzle may be designed to achieve countercurrent turbulence to directly alter the venturi effect and thereby reduce the ratio of the gas/air mixture. The countercurrent air flows can be utilized in a variety of different mixing chambers and/or gas/air manifolds. The mechanical restrictor utilizes a pneumatically operated solenoid having a needle valve which is rapidily and selectively driven between a portion which is a predetermined distance into an opening provided in the mixing valve which receives the combustible gas and a position withdrawn from the first position, the movement being responsive to the amount of drying desired. The depth of entry of the needle valve into the opening determines the amount of restriction. The depth may be controlled by placement of washers of different thickness or of a different number of washers of uniform thickness within the piston cylinder to control the entry depth of the needle valve into the mixing valve opening. Alternatively, the restrictor may comprise a solenoid operated shutter which provides a larger (full flame) or smaller (pilot flame) opening for controlling the air/gas flow and hence the heat intensity of the burner. A plurality of emitter assemblies may be utilized and control means for selectively operating the sectional units of these assemblies can be provided to accurately control the desired amount of drying (i.e., moisture reduction) by selective operation of each of the individual sectional units making up each assembly to thereby dry elongated sections of the paper web. For example, four such assemblies may be arranged at spaced parallel intervals and transverse to the path of movement of the web. Each assembly is comprised of a pluraltiy of sectional units. Each of the rows of air/gas mixing devices may be preadjusted to reduce moisture content by predetermined fractions of moisture reduction. As one example, the moisture content of the web may be reduced over a range of one-quarter precent to two and three-quarter percent at one-quarter percent increments. The invention is extremely useful for profiling . For example, when the moisture content profile across the web indicates that the web has a nonuniform moisture content and/or moisture content which departs significantly from a preferred moisture content, the individual sections of the emitter assemblies may be selectively controlled by the countercurrent air flow provided at the control inlet of each dryer unit section. The independent control of each dryer unit section provides a superior corrective adjustment of localized departures from the target moisture value at a significant reduction in total energy re-quirements. The control inlet for communicating the air jet with the mixing chamber may be designed to provide an air curtain having a fishtail shape for blocking the gas/air flow in addition to regulating the countercurrent flow. Other shapes of air blast may be provided if desired. The air jet velocity may be adjusted to provide either turbulent or laminar flow. The mechanical restrictors may be used in place of the pneumatic restrictors with equal success. The prior art fails to recognize the problems recognized by the inventor and also fails to teach the novel features of the present invention. More particularly: German Patent No. 475,075 discloses a mechanically controlled burner for adjusting the amounts of fuel and air, as well as the size of the mixing chamber, as a function of steam pressure developed in a steam boiler being heated by the burner. There is no teaching of regulation of the flame intensity of the burner between a higher and a lower intensity in a substantially instantaneous manner through the introduction of controlled air into the gas/air mixture to regulate the flame intensity. The published EPO application designated EP-A-0 062 316 discloses a control system for a gas burner in which a movable lance is adjusted to regulate the size of a plurality of openings which introduce air and gas into the burner mixing chamber. There is no teaching of employment of mechanical means which is utilized to rapidly adjust the gas/air mixture between a higher and a lower flame intensity. Swiss Patent No. 125,585 discloses apparatus for providing an air/gas mixture in which a needle is axially adjusted to regulate the position of its tapered point within an opening by manual rotation of a threaded end portion of the needle, to regulate the air/gas mixture. Again, there is no teaching of substantially instantaneously controlling the burner between a higher and a lower intensity level through mechanical means. German Published Application No. 2 251 994 discloses air/gas mixing apparatus in which a gas is initially mixed with air in a prechamber wherein the amount of air introduced into the prechamber is a function of gas pressure; and wherein air under pressure is mixed with ambient air in a second prechamber, the amount of ambient air introduced being a function of the pressure of the source of air under pressure, the two mixtures being combined a mixing chamber. Again, there is no teaching of mechanically adjusting the flame intensity between a higher and a lower intensity level in a substantially instanteous manner. The document DE-B-1 011 557 discloses manually adjustable means having a handle for manual manipulation for purposes of controlling the air flow, the gas flow being constant. US-Patent 3,214,845 discloses a methode and means for correcting the moisture profile drying in the manufacture of fibrous materials in which one drying section with a series of selective drying means is spaced across the material. The variations in moisture across the width of the material are determined, and in accordance with the measured moisture content the output of each of the selective drying means is adjusted. US-A-4 188 731 and DE-C-966 023 disclose radiant heating elements being positioned in a grid system adjacent a moving web, the heating elements being controlled either individually or in groups to be either in an in-position or in an off-position. Although it is conventional to measure moisture across a web, there is no teaching of the profiling technique disclosed herein wherein columns of emitters are selectively operated between upper and lower flame intensities to regulate moisture content in the cross-direction of a web to achieve a desired moisture profile. It is an object of the present invention is to provide a novel apparatus for drying moving webs and the like comprised of a plurality of drying units and which are adjustable preferably between first and second energy levels for controlling each infrared emitter unit to regulate the adjustment of the moisture level. Still another object of the present invention is to provide a novel method for regulating the moisture profile of a web in which the heat intensity of the drying units, arranged in a predetermined number of rows, each drying unit having a number of independently controllable emitter units extending in the cross-direction of the web wherein the percent of drying is regulated by selectively controlling the drying energy of elements in like columns of the rows of drying units to obtain incremental drying levels ranging between a maximum and a minimum drying level by selectively adjusting the air/gas mixture of each element in a like column to obtain flame intensities at a variety of graduations between an upper and a lower drying level. Still another object of the present invention is to provide a novel method for regulating the moisture profile of a web in which the heat intensity of the drying units, arranged in a predetermined number of rows, each drying unit having a number of emitter units extending in the cross-direction of the web wherein the percent of drying is regulated by controlling the intensity of elements in like columns of the rows of drying units to obtain incremental drying levels ranging between a maximum and a minimum drying level by selectively adjusting the air/gas mixture of each element in a like column to obtain flame intensities between an upper and a lower level and wherein the adjustments are made under the control of a moisture detection apparatus which is operated to determine the moisture profile across the web to appropriately regulate the individual drying elements within each drying unit. The invention is defined in claims 1 and 4, optional features being set out in the dependent claims. The invention will become apparent when reading the accompanying description of drawings in which: Fig. 1shows a portion of a dryer unit embodying the principles of the present invention. Fig. 2shows a simplified perspective view of a system employing a plurality of drying units embodying the principles of the present invention. Fig. 2ais a perspective view showing one of the dryer units of Fig. 2 in greater detail. Figs. 3a and 3bshow side and end views respectively of another type of dryer unit utilizing the principles of the present invention. Figs. 4a and 4bshow elevational and top views, respectively, of another preferred embodiment of the present invention. Figs. 5a and 5crespectively show diagrams of the heating system before profiling and with profiling responsive to a given moisture profile. Figs. 5b and 5drespectively show a moisture profile across a web before profiling and after profiling. Fig. 6shows a diagram of another simplified profiling system useful in understanding the present invention. Fig. 7shows a sectional view of another alternative embodiment of an infra-red burner for use in the profiling system of the present invention. Fig. 7ashows a detailed view of the mixing valve and mixing chamber of the burner units shown in Fig. 7. Fig. 7bis a sectional view of an alternative embodiment for the mixing valve shown in Fig. 7a. Fig. 1 shows a portion of a drying unit 10 embodying the principles of the present invention and comprised of a gas supply manifold 12 receiving a combustion gas from a combustion gas supply source (not shown) and for delivering the combustion gas through manifold 12 and coupling 14 to a hollow conduit 16 which may, for example, be a U-shaped tube having an arm 16a and an arm 16b, the yoke portion of the conduit 16 being omitted from Fig. 1 for purposes of simplicity. Conduit portion 16b delivers the combustion gas through coupling 18 to an L-shaped coupling 20 for introducing the combustion gas into the venturi orifice 22a of a venturi-type mixing valve 22. Mixing valve 22 is air-tightly fitted within the upper opening provided in mixing chamber 24. Mixing valve 22 is provided with a tapered intermediate portion 22c which tapers from a large diameter portion 22b to a small diameter portion 22d. The free end of small diameter portion 22d is tapered at 22e. A cylindrical disk 26 is provided with diagonally aligned openings 26a (see Fig. 7a) surrounding tapered portion 22e. A portion of the hollow region between mixing valve 22 and mixing chamber 24 is arranged to receive air introduced through an opening 24a in mixing chamber 24 and an opening 28a in an air supply manifold 28 for delivering air under pressure to the mixing chamber. Air under pressure is introduced through openings 28a and 24a and flows about the exterior portion of mixing valve 22 and downwardly into the hollow interior of mixing chamber 24, as shown by arrows 30. The air passing the venturi orifice 22a creates a vacuum condition which draws combustion gas through the orifice and into the mixing chamber 24 in a controlled and measured amount. The gas/air mixture continues to move downwardly and into a combustion chamber 32, passing through an opening 34a in a member 34 and through a plurality of hollow, cylindrically-shaped elements 36 to enter into the combustion chamber 32. The elements 36 are arranged within a wall formed of a suitable insulation material to provide a plurality of orifices for introducing the air/gas mixture into the combustion chamber. A spark ignitor 38 is arranged within hollow, cylindrical member 40, the centrally located electrode 38a extending into combustion chamber 32 to develop a spark for igniting the air/gas mixture within combustion chamber 32. Burning takes place in chamber 32 in order to heat the substantially U-shaped radiating elements 40. The combusted air/gas mixture heats elements 40 causing them to emit heat radiation in the infra-red range. Burning is sustained by continuous flow of the air/gas mixture into the combustion chamber 32. The infrared emitter unit 42 is positioned above a moving web W which web is moving, for example, in a direction out of and perpendicular to the plane of Fig. 1. Units 42' and 42'' are substantially identical to the infra-red emitter unit 42, and are arranged in an end-to-end manner. The emitter units 42' and 42'' are joined to unit 42 by pins 46 extending through openings in the walls 48, 50 of unit 42, as well as the walls 48', 50' and 48 , 50'' of the infra-red emitter units 42' and 42 , respectively. In order to regulate the flow of the air/gas mixture which is delivered to combustion chamber 32 through the mixing chamber 24, chamber 24 is provided with a control inlet 52, preferably in the form of a hollow externally threaded member, for coupling a second air supply 54 therethrough, preferably through an adjustable valve 56 and a solenoid controlled valve 58. The air pressure developed by source 54 is substantially greater than the pressure within air/gas mixing chamber 24 to prevent the passage of the air/gas mixture through inlet 52 and back to source 54. Adjustable valve 56 may be adjusted to regulate the flow of air from source 54. Solenoid control valve 58, in one preferred embodiment of the invention, is comprised of a solenoid operated, two position valve assembly, having a first position which is normally closed to prevent the passage of air from source 54 into control inlet 52 and likewise to prevent the air/gas mixture in mixing chamber 24 from passing through inlet 52 and toward source 54. By energizing the solenoid of the solenoid control valve assembly 58, the valve is moved to the open position to allow a jet of air from source 54 to pass through adjustable valve 56, open solenoid valve 58 and inlet 52 into mixing chamber 24. The introduction of a jet of air into mixing chamber 24 through control inlet 52 develops a back pressure condition resulting from the countercurrent air flow of greater pressure than that of the combustion gas/air mixture to reduce the venturi effect and thereby causing the gas/air mixing valve 22 to meter less gas through orifice 22a and into mixing chamber 24. The reduction in the proportions of air and gas in the air/gas mixture due to the back pressure developed in mixing chamber 24 reduces the burning and heating level within combustion chamber 32 to thereby reduce the intensity of infra-red radiation emitted from the radiating surfaces 40, the amount of reduction in heat intensity being a function of the pressure level of air pressure source 54 and the adjustment of adjustable valve 56. Care must be exercised in the selection of the size of inlet opening 52. If the opening is too small, the velocity of air jet moving through inlet 52 will be too great. This will create a vacuum effect causing more, rather than less, gas to be drawn into the mixing chamber through the venturi. It appears that turbulent air flow creates the undesirable vacuum condition whereas lamilar air flow blocks the flow of the air/gas mixture in the region of the countercurrent air jet. The moving web, which may be paper, cloth or any other material, is preferably monitored by a moisture level detection instrument 102 having a moisture detecting head 126 electrically connected thereto. The moisture detector apparatus may, for example, be of the type described in U.S. Patent No. 3,458,808 issued 29 July 1969 or U.S. Patent No. 3,829,754 issued 13 August 1974 as exemplary of satisfactory moisture detection devices which utilize microwave detection cavities. However, any other type of moisture detection device may be utilized including manual observation. A moisture level is thus detected and, if this moisture level is not within a desired moisture level range, control logic 128 coupled to the moisture detector head 126 is utilized to close solenoid 58 to provide radiation intensity at a level sufficient to reduce the moisture content of the web to an acceptable level. In the event that the moisture level content lies below the desired range, the moisture detector unit 102 develops a signal which opens normally closed solenoid 58 to significantly reduce the intensity (drying) level since the web is below the desirable moisture content level. The lower intensity level is preferably sufficient to provide only minimal drying while avoiding the need for reignition of the air/gas mixture, resulting in a saving of both electrical energy and combustion gas. The detector head 126 (see Fig. 2) may be comprised of a plurality of independent detector heads, each capable of measuring moisture content over a portion of the width of web W. Alternatively, a single scanning head may be employed. The single scanning head may be comprised of only one detector head 126 which scans across the width of the web. A moisture reading is taken at discrete intervals of the scan (i.e., movement) of the single detector head across the web. As one example of moisture level control, let it be assumed that the desired average moisture content across web W should be of the order of six percent. Considering Fig. 2a, let it further be assumed that the portions W1, W3 and W5 of the web W have a moisture content of the order of six percent; that the portion W2 of the web W has a moisture content of the order of five percent and that a portion W4 of the web has a moisture content of the order of nine percent. The average of these moisture contents exceeds six percent, which is the desired average. By utilizing a dryer unit having infrared emitter units whose air/gas mixtures are adjusted to reducing the moisture content in the associated section of the web by two percent, the moisture content can locally be reduced in section W4 sufficiently to bring the average moisture content across the web below the desired six percent average value. This may, for example, be accomplished through the use of a dryer unit having infrared emitter units 42 whose combustion gas/air mixtures are each adjusted to provide a marginal reduction in moisture content when the solenoid valve 58 is opened to reduce the intensity of the flame. Each infrared emitter unit 42 is further capable of being operated to provide a two percent reduction in moisture content by closing the solenoid valve 58 to thereby increase the flame intensity. The heat intensity (i.e. drying level) is further adjustable by controlling the pressure level of the air pressure source 54 and further by controlling the adjustment of regulating valve 56 (either manually or automatically), as shown in Fig. 1. Thus, the moisture profile is thus readjusted to an acceptable profile at a significant saving in energy consumption, while at the same time preventing portions of the web from being overdried. The arrangement 100 of Fig. 2 employs a plurality of dryer units 106, 108, 110 and 112, arranged in spaced parallel fashion and extending transversely across moving web W. The drying units 106 through 112 are each comprised of a plurality of infrared emitter units 42 which may be of the infra-red emitter type 42 shown in Fig. 1, or may be any other suitable type of dryer heated by an air/gas mixture. The size of each infrared emitter unit in the cross direction of the web is preferably small, such as 6'' or so, to improve monitoring resolution in the cross direction of the web. Fig. 2 shows the drying units in simplified diagrammatic fashion. Fig. 2a shows one typical unit 106 comprised of infrared emitter units 42 each having a mixing chamber 24 receiving air (for combustion) from air source 114 through line 116 and receiving gas from gas source 118 through line 120. Each control inlet 52 receives air under pressure (for control) from air source 122 through line 124. Valves 58 are electrically controlled by signals from control unit 130 which receives moisture content signals from the signal output portion 128 of scanning head 126 or from a manual input. The drying units 108-112 are substantially identical to unit 106. The electronic control unit 103 operating solenoid control valves may incorporate a microprocessor. The operation of the dryer system in Fig. 2 is as follows: Figs. 5a-5d illustrate the use of the profilng system on a typical paper machine operating to move the web W in the speed range of 1200-1800 fpm. In the example shown in Figs. 5a-5d, the system consists of 4 rows of burner units 106-112, each unit being comprised of infrared emitter units 42, measuring 4'' x 6'' in size. Each infrared emitter unit 42 can be individually controlled to a high or low heat intensity. The difference between the two levels is the turndown . Rows 1-3 have been set to yield a turndown (reduction) of 1% final moisture, whereas Row 4 has a turndown of 1/2% to allow the moisture control in 1/2% increments. The total turndown for this illustration is therefore 3-1/2%. This means a correction capability of +2%; -1-1/2% around a desired moisture target. The dryer system 100 is initialized with 50% of its capacity turned on (See Fig. 5a). The moisture profile at the reel (i.e., where the paper web is wound up) measured by scanning head 126 shows a tyical profile variation (see Fig. 5b) which requires a moisture target of 4% in order not to exeed a maximum of 6%. Each rectangle in Figs. 5a and 5c represents an infrared emitter unit 42. A shaded rectangle represents a section which is ON (i.e., high heat) while an unshaded rectangle represents a section which is OFF (i.e., low or marginal heat). The infrared emitter units 42 of the dryer system 100 are readjusted as shown in Fig. 5c to provide differential drying based on the moisture content profile shown in Fig. 5b either as measured by the scanning moisture head or as determined by an operator. The resulting final profile is shown in Fig. 5d as being tightly clustered around the original moisture target of 4%. The paper web can then be run faster or the amount of steam consumed in the paper making process can be reduced to increase the final moisture target from 4% to 5-1/2% resulting in substantial steam and fiber savings and allow a machine speed-up. This technique of providing localized corrections in the moisture profile also results in a significant reduction in fuel (i.e., gas) consumption. Obviously, any other adjustments may be made to provide the desired incremental reduction in moisture content and/or a greater or lesser number of drying units may be provided depending upon the needs of the particular application. Some other examples are given in the following chart: OTHER TYPICAL REDUCTIONS Increments Burner Units 1/4% 1/3% 1/2% 1% 11/41/31/21 21/22/311 31111 41111 Total:2.3/4%3%3-1/2%4% Figs. 3a and 3b show another alternative arrangement wherein an assembly 150 is comprised of a plurality of individual heating units 152-l through 152-n, each unit incorporating an elongated burner head 154 (shown in Fig. 3b) for heating a suitable refractory 156, 158 which provides a high rate of radiant heat transfer. Each unit receives an air/gas mixture which is introduced into the inlet end 160a of manifold 160 and is delivered to each unit through the branch conduits 162-l through 162-n. Each branch conduit 162 is provided with a control inlet 164-l through 164-n for introducing air from the supply source such as, for example, the supply source shown in Fig. 1, into each branch conduit in order to provide a back pressure. The coupling connected to one of the conduits 162 may be shaped in the manner shown in Figs. 4a, 4b in order to create a fishtail shape air curtain within conduit 162. Noting Fig. 4a, an air supply conduit 166 is provided with a narrowing exit portion 166a which narrowing exit portion flares outwardly as defined by the sidewalls 166b, 166c (shown in Fig. 4b) and the triangular shaped walls 166e, 166d (shown in Fig. 4a). This outlet communicates with an arcuate shaped opening 162a in conduit 162 to cause a narrow fishtail shape air curtain to be introduced within the interior of conduit 162 (see Fig. 4b) for blocking the gas/air flow in addition to regulating the countercurrent flow, i.e., the back pressure condition created in the region of the venturi orifice. Figs. 7 and 7a show an alternative arrangement for regulating the air/gas mixture wherein like elements are designed by like numerals, as compared with Figs. 1 and 7. The unit 200 comprises mixing valve 22 provided with central opening 22a, which selectively receives the reciprocating needle member 212 of a pneumatically driven assembly 210 comprised of housing 214 with an air inlet opening 214a for receiving air under pressure. Needle member 212 is joined to piston 216 arranged within cylinder 214. A return spring 218 is arranged between piston 216 in the bottom end 214b of cylinder 214. Return spring 218 normally urges piston 216 upwardly in the direction shown by arrow 220. Gas enters into a closure cap 222 having a gas inlet opening 222a and passes through an annular path described by needle 212 and central opening 22a. When no air under pressure is applied to the control inlet opening 214a, return spring 218 urges piston 216 and needle 212 upwardly, allowing unrestricted (maximum) gas flow to provide a rich gas/air mixture in mixing chamber 24. Application of air under pressure to control inlet opening 214a urges piston 216 and needle 212 downwardly to extend more deeply into central opening 22a and the reduced diameter portion 22a' thereof, thereby reducing the amount of gas entering into mixing chamber 24 and providing a leaner gas/air mixture which reduces the energy output of the burner. However, a sufficient amount of gas is preferably introduced into the mixing chamber to sustain combustion and thereby avoid the necessity of initiating a new start-up. The depth of entry of needle 212 into mixing valve opening 22a may be controlled by placing washers W within cylinder 214 or between cylinder housing 214 and the top of closure cap 222, or by adjusting the height of cylinder housing 214 relative to closure cap 222, thus limiting the depth of penetration of the needle 212 into opening 22a. The washers may either be of varying thickness or may be of one uniform thickness with the number of washers introduced controlling he overall depth reduction. The arrangement shown in Figs. 7 and 7a may be utilized with equal success in any of the dryer units described hereinabove and as a substitute for the countercurrent gas flow control means shown, for example, in Figs. 1, 2, 3 and 4. The air introduced into cylinder inlet 214a may be regulated by a solenoid controlled valve 215. Instead of applying needle member 212 to the flow of gas alone as shown in the above arrangement, an alternate arrangement as shown in Fig. 7b employs a needle member 212' of extended length to also control the flow of combustion air 30 or to regulate a mixture of gas and air as shown in arrangement 150 of Figs. 3a and 3b by replacing the air flow device by a mechanical needle device of the type shown in Fig. 7b. An additional variation may employ a solenoid blocking valve directly on the mixing tube (162) or (24), such blocking valve having an orifice opening in the blocking diaphram to allow passage of a lesser amount of combustible gas in the blocked or closed position. The blocking valve may be in the form of a shutter movable to a first position to provide a large opening (full flame) and a second position to provide a restricted opening (pilot flame). Since water layers of the type considered in this application have their maximum infra-red absorption in the wavelength region of 1.9 to 1.95 microns, it is highly advantageous to control the infra-red emitters to operate in this portion of the infra-red spectrum to the greatest extent possible. The present invention capitalizes on this phenomenon, since only some (but not all) of the emitters E in a column (see Fig. 6) are turned down while the remaining emitters of the column are operated at high fire, corresponding to the optimum wavelength. An alternative way to make intensity adjustments to a column having one long emitter would be to adjust the intensity of the entire column by conventional means, i.e., butterfly valves. As an example, a 50% turndown of a column would mean that, using the grid approach of the present invention, two out of four emitters E in a column would be in a low fire, whereas the burners of the remaining emitter would be operating at high fire, thus operating at their highest efficiency. A conventional control system would turn down a column emitter to a 50% level, moving the emitters out of the preferred wavelength range, which results in enormous fuel inefficiency. Although the present invention is described as being extremely useful for heater and dryer units, and for heater and dryer units of the infra-red type, it should be understood that the present invention may be utilized in any application wherein it is desired to alter an air/gas mixture automatically and without either having to shut-off the burner completely or, alternatively, without having to readjust the controls utilized with the lines coupling the combustion gas and air supply sources to the mixing valve and mixing chamber. A latitude of modification, change and substitution is intended in the foregoing disclosure, and in some instances, some features of the invention will be employed without a corresponding use of other features. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the spirit and scope of the invention herein.
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Apparatus for drying an elongated web (W) comprising: a plurality of infrared emitter units (42) each for drying a longitudinal portion of the web (W) passing adjacent to said infrared emitter unit (42), said infrared emitter units (42) being arranged in side-by-side fashion to form a drying unit (106, 108, 110, 112), utilizing at least two of the drying units (106, 108, 110, 112) being arranged in spaced parallel fashion, control means for each of the infrared emitter units (42) for selectively operating each infrared emitter unit (42) at a first high energy level and a second level significantly less than said high energy level, means for measuring the moisture content of the web (W) to determine the moisture profile across the web (W), means responsive to the moisture profile and to a desired moisture content for selectively operating the infrared emitter units (42) associated with a given longitudinal section of the moving web (W) between a first extreme condition wherein all of the infrared emitter units (42) for drying a common longitudinal section of the web (W) are operating at said second level and the opposite extreme wherein all of said infrared emitter units (42) associated with the longitudinal section of the moving web (W) are operating at said first level. Apparatus according to claim 1, characterized by a infrared emitter unit (42), comprising: a combustion chamber (32) and an apparatus for regulating an air/gas mixture delivered to said combustion chamber (32), a mixing device (22) having a central opening (22a) for receiving gas, a second inlet (22c) for receiving the air, a control member (212) positioned in the opening (22a) of said mixing device (22), whereby the proportionate amounts of gas and air reaching said mixing chamber first inlet is determined by the position of said control member (212). Apparatus according to claim 1, characterized by a infrared emitter unit (42) comprising a combustion chamber (32) and an apparatus for regulating an air/gas mixture delivered to said combustion chamber (32) comprising a conduit (24) having a first inlet for receiving air and a combustible gas and an outlet (34a), said conduit (24) delivering an air/gas mixture to said outlet (34a), said outlet (34a) communicating with said combustion chamber (32), the said apparatus for regulating the air/gas mixture further comprising a mixing device (22) having a first inlet (22a) for receiving gas, a second inlet (22c) for receiving air and a mixing region (26) for mixing said air and gas and delivering the mixture to the conduit first inlet, a control member (212) mounted within said conduit and means (214, 214a, 216) for moving said control member to a first position to provide a large opening for passage of gas therethrough and to a second position to provide a restricted opening for passage of gas therethrough. A method for optaining a moisture profile across a paper web (W) moving through a drying region within a desired moisture range, comprising the steps of: providing a plurality of infrared emitter units (42) each arranged side-by-side spanning across the width of the web (W) to form a drying unit (106, 108, 110, 112), providing at least two of the drying units (106, 108, 110, 112) being arranged in spaced parallel fashion, measuring the moisture content across the web (W) to provide a moisture profile (126), selectively operating all of those infrared emitter units (42) associated with a common longitudinal section of the web (W) whose moisture profile is above the desired range at an output energy level suitable to reduce the moisture level to achieve the desired moisture level. A method according to claim 3, comprising the step: selectively operating those infrared emitter units (42) adapted to dry a common longitudinal section of the web (W) whereby at least one of the said infrared emitter units (42) is operated at a higher output energy level whenever the portion of the moisture profile representative of the moisture content of the associated longitudinal section of the web (W) is greater than the desired moisture level, the number of such infrared emitter units (42) being operated at a higher output energy level being directly proportional to the magnitude of the difference between the actual moisture level and the desired moisture level.
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KRIEGER CORP; KRIEGER CORPORATION
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ROTH REINHOLD C; TERRA RICHARD C; ROTH, REINHOLD C.; TERRA, RICHARD C.
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EP-0489722-B1
| 489,722 |
EP
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B1
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EN
| 19,950,201 | 1,992 | 20,100,220 |
new
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C07C209
| null |
C07C209, B01J23
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B01J 23/89G18, B01J 23/89G16, C07C 209/26, B01J 23/89G, B01J 23/89G4, C07C 209/16, B01J 23/89F
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Process for preparing N-substituted amine
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An N-substituted amine is produced by reacting an alcohol or aldehyde with ammonia, a primary amine or a secondary amine in the presence of a catalyst comprising (1) copper, (2) a metal selected from chromium, manganese, iron, cobalt, nickel and zinc, (3) a metal of the platinum VIII group and (4) a metal selected from alkali metals and alkaline earth metals.
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The present invention relates to a process for preparing an N-substituted amine which comprises reacting an alcohol or an aldehyde with ammonia or a primary or secondary amine. The amine prepared according to the present invention is a material important from the industrial viewpoint as intermediates of a rust preventive, a surfactant, a germicide, a dyeing assistant and a fiber softener, etc. [Prior Art]It is known in the art that an alcohol or an aldehyde is reacted with ammonia or a primary or secondary amine to give the corresponding amine. However, it was difficult to selectively prepare a particular amine through a reaction of an alcohol or the like with an amine or the like. Examples of the process for preparing an amine from an alcohol and an amine include those disclosed in Japanese Patent Laid-Open Nos. 19604/1977 (a copper chromite catalyst and a cobalt catalyst) and 59602/1978 (copper/molybdenum and copper/tungsten catalysts), U.S. Patent No. 3 223 734 (Raney nickel catalyst and copper chromite catalysts), West German Patent Laid-Open No. 1,493,781 (a supported cobalt catalyst), Japanese Patent Publication No. 55704/1982 (a copper/nickel catalyst), etc. However, these catalysts are insufficient in both the catalytic activity and the selectivity and should be used in a large amount, which brings about a low yield of the intended amine. In order to solve these problems, processes described in Japanese Patent Laid-Open Nos. 15865/1986, 149646/1987, 149647/1987, and 149648/1987 have been developed. In these processes, a copper/nickel/group VIII platinum metal element catalyst is used to prepare an intended amine in a high yield. That is, in these processes, an intended amine is prepared in a high yield through the addition of a small amount of the group VIII platinum metal element to a conventional copper/nickel catalyst having insufficient activity and selectivity for the purpose of improving the activity and selectivity. However, the process in which the reaction is conducted in the presence of this catalyst is not always satisfactory from the viewpoint of the durability of the catalyst. Specifically, although this process is superior in the activity and the selectivity to other general processes and brings about little or no lowering in the activity of the catalyst even after recovery and reuse of tens of times, the selectivity is lowered. Therefore, with the consideration of the preparation of an N-substituted amine on a commercial scale, a further improvement in the durability is desired from the viewpoint of the yield and quality of the formed N-substituted amine. However, N-substituted amines which have been prepared in the presence of these catalysts bring about the deterioration of hue when converted into a quaternary ammonium salt (tetraalkylammonium salt, trialkylbenzylammonium salt, etc.), which unfavorably causes remarkable deterioration of performance in applications such as surfactants. Other documents which disclose the production of amines using catalysts are US-A-4625063, DE-A-3641666 and DE-A-3034433. US-A-4625063 and DE-A-3641666 disclose the reaction of an alcohol or aldehyde with a primary amine in the presence of a copper/nickel/group-VIII noble metal catalyst. DE-A-3034433 discloses the production of tertiary monoamines and polyamines by reacting various alcohols, ketones, aldehydes or ethylene oxide with ammonia, or a primary or secondary aliphatic amine, in the presence of a catalyst containing copper or silver carboxylate; group VIII, manganese or zinc carboxylate; and fatty acid, alkali metal or alkaline earth metal carboxylates. (Summary of the Invention)The invention provides a process for preparing an N-substituted amine, which comprises the step of reacting an alcohol or an aldehyde with ammonia, a primary amine or a secondary amine at 150 to 250°C at a pressure of the atmospheric pressure to 100 atm gauge, while water formed in the reaction is being removed out, in the presence of a catalyst comprising: (1) copper, (2) a metal selected from the group consisting of chromium, manganese, iron, cobalt, nickel and zinc, (3) a metal of the platinum VIII group and (4) a metal selected from the group consisting of alkali metals and alkaline earth metals. It is preferable that a molar ratio of the component (1) to (2) ranges from 10/90 to 99/1, preferably 1/9 to 9/1 or 50/50 to 99/1, a molar ratio of the component (3) to the sum total of (1) and (2) ranges from 0.001 to 0.1 and a molar ratio of the component (2) to (4) ranges from 1/0.01 to 1/1. The invention will be explained in detail in with reference to the catalyst. It has been found that the addition of a small amount of a fourth component metal element composed of an alkali or alkaline earth metal selected from among lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium to the copper/fourth period transition metal element/group VIII platinum metal element catalyst brings about a remarkable improvement in the selectivity while substantially maintaining the activity. At the same time, the present inventors have found that the quaternary ammonium salt prepared through the conversion of the starting material composed of the N-substituted amine prepared in the presence of this catalyst has a remarkably improved hue over that of the conventional quaternary ammonium salt. In this case, chromium, manganese, iron, cobalt, nickel, and zinc were useful as the fourth period transition metal element while platinum, palladium, ruthenium, and rhodium were useful as the group VIII platinum metal element. Consequently, the addition of a small amount of a fourth component metal element composed of an alkali or alkaline earth metal to a copper/fourth period transition metal element/group VIII platinum metal element catalyst enabled the development of a high-performance amination catalyst not only having activity equal to that of the copper/fourth period transition metal element/group VIII platinum metal element catalyst and selectivity far superior to that of the copper/fourth period transition metal element/group VIII platinum metal element catalyst but also capable of preparing an N-substituted amine which can be converted into a quaternary ammonium salt having very excellent hue. It is necessary that the catalyst used in the present invention contain copper, a fourth period transition metal element, a group VIII platinum metal element (hereinafter abbreviated to platinum group element ), and a fourth metal element (hereinafter referred to as fourth component ). In the catalyst metal composition used, the proportions of copper, the fourth period transition metal element, the platinum group element, and the fourth component may be arbitrary. However, the molar ratio of copper to the fourth period transition metal element is preferably 10 : 90 to 99 : 1, more preferably 50 : 50 to 99 : 1. The ratio of amount of addition of the platinum group element to the total of copper and the fourth period transition metal element is preferably 0.001 to 0.1 (molar ratio), more preferably 0.001 to 0.05. Further the molar ratio of the fourth period transition metal element to the fourth component is preferably 1 : 0.01 to 1 : 1, more preferably 1 : 0.01 to 1 : 0.5. The fourth period transition metal elements particularly suitable for the reaction according to the present invention are chromium, manganese, iron, cobalt, nickel, and zinc. The platinum group elements particularly suitable for the reaction according to the present invention are platinum, palladium, ruthenium, and rhodium. Further, the fourth component particularly useful for the reaction according to the present invention includes lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium. Although the catalyst metal composition should contain four components, i.e., copper, a fourth transition metal element, a platinum group element, and a fourth component, the catalyst suitable for the present invention may have various forms. Specifically, in the present invention, only when the four components, i.e., copper, a fourth period transition metal element, a platinum group element, and a fourth component are present in the reaction system as the catalyst composition, an effect can be attained through interaction among the four components. Therefore, this four component composition has a substantial function as a catalyst, and in the reaction the catalytic activity is not developed until each metallic component is reduced in a hydrogen atmosphere. For this reason, in the present invention, there is no limitation with respect to the form of the metals before the reduction and the state of the system after the completion of the reduction as far as the reduction in a hydrogen atmosphere according to the method described in the present specification brings about interaction among copper, the fourth period transition metal element, the platinum group element, and the fourth component. Therefore, the metals suitable for the process of the present invention may have any of the following forms as far as the four metal components indispensable to the present invention bring about interaction thereamong through reduction in a hydrogen atmosphere: 1) a form of a metal, an oxide or a hydroxide thereof and a mixture thereof which can be dispersed in a reaction medium; 2) a form of either a mixture of copper, a fourth period transition metal element, a platinum group element and a fourth component respectively supported on suitable carriers, or three components, i.e., copper, a fourth period transition metal element, a platinum group element, and a fourth component, homogeneously supported on a single carrier which can be dispersed in a reaction medium; 3) a form of an aliphatic carboxylic acid salt of these metals, a complex of these metals stabilized by a suitable ligand or the like which is converted into a metallic colloid in a reaction medium to form a homogeneous system; and 4) a mixture of a form described in the above items 1) and 2) which is dispersed in a reaction medium with a form described in the above item 3) which forms a homogeneous system in a reaction system, or a form which is in a dispersed state before hydrogen reduction but becomes homogeneous after hydrogen reduction. With respect to the form of the catalyst used in the process of the present invention, it is preferred from the viewpoint of the stabilization of the catalyst metal, i.e., immobilization of the active surface, and resistance to a catalyst poison that the above-described four metal components are homogeneously supported on a suitable carrier. When the four metal components according to the present invention, i.e., copper, a fourth period transition metal element, a platinum group element, and a fourth component, are to be supported on a carrier, suitable carriers are those commonly employed as catalyst carriers, e.g., alumina, silica/alumina, diatomaceous earth, silica, active carbon, and natural and artificial zeolite. Although the amount of the catalyst metal supported on a carrier may be arbitrarily determined, it is generally preferably 5 to 70%. Further, these four metal components may be supported on a carrier by various methods. In this case, the form of the raw metals of the catalyst may be an oxide, a hydroxide, or various salts of copper, a fourth period transition metal element, and a platinum group element. Examples of the form of the raw metals include chlorides, sulfates, nitrates, acetates, aliphatic carboxylates of copper, a fourth period transition metal element, a platinum group element, and a fourth component, or complexes of these metals, e.g., acetylacetone complexes and dimethylglyoxime complexes of copper, a fourth period transition metal element, a platinum group element, and a fourth component. Further, with respect to the platinum group element, carbonyl complexes, amine complexes, phosphine complexes, etc. may also be employed. The preparation of a catalyst through supporting of the metal components on a carrier by making use of these raw metal materials may be conducted by any of conventional known processes, e.g., a process which comprises adding a carrier to a solution of suitable salts of copper, a fourth period transition metal element, a platinum group element, and a fourth component, to sufficiently impregnate the carrier with the solution and drying and baking the impregnated carrier (impregnation process), a process which comprises conducting either a step of sufficiently mixing a carrier with an aqueous solution of suitable salts of copper, a fourth period transition metal element and a platinum group element and then adding an aqueous alkaline solution, such as an aqueous sodium carbonate or sodium hydroxide solution or aqueous ammonia, to the mixture to precipitate the metal salts on the carrier, or a step or simultaneously adding an aqueous solution of suitable salts of copper, a fourth period transition metal element and a platinum group element and an aqueous alkaline solution, such as an aqueous sodium carbonate or sodium hydroxide solution or aqueous ammonia, to a water slurry of a carrier in such a manner that the pH value of the slurry remains constant (e.g., a constant pH value of 7) to precipitate the metal salts on the carrier, drying and baking the metal salts supported on the carrier to prepare a copper/fourth period transition metal element/platinum group element catalyst, placing the resulting ternary catalyst in an aqueous solution of an alkali metal salt or an alkaline earth metal salt to impregnate the catalyst with the aqueous solution, and drying and baking the impregnated catalyst (a combination of the coprecipitation process with the impregnation process), and a process which comprises conducting an ion exchange with hydrogen or a metal contained in zeolite (ion exchange process). In the case of the coprecipitation process, the carrier is sufficiently washed with water after deposition of the metals, dried at about 100°C, and baked at 300 to 700°C to prepare a catalyst. An other effective process comprises supporting only copper or only copper and a fourth period transition metal element on a carrier through the above-described processes and adding, prior to the reaction, a supported platinum group element or fourth/component, or an aliphatic carboxylate or a complex thereof to form a composite comprising a combination of copper with the fourth period transition metal element, the platinum group element and the fourth component in a reaction medium in a hydrogen atmosphere. With respect to the form of the catalyst, it is more preferable that the four components be homogeneously supported on the same carrier. The four components, i.e., copper, a fourth period transition metal element, a platinum group element, and a fourth component, are indispensable to the present invention. The alcohol or aldehyde which is a starting material used in the present invention is a straight-chain or branched saturated or unsaturated aliphatic alcohol or aldehyde having 8 to 36 carbon atoms. Examples of the alcohol include octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, and a mixture thereof, a Ziegler alcohol prepared by the Ziegler process, an oxo alcohol prepared by the oxo process, and alcohols having a branched chain such as Guerbet alcohol. Examples of the aldehyde include lauraldehyde, oxo aldehyde, and aldehydes corresponding to the above-described alcohols. Further, various polyhydric alcohols may also be used, and examples thereof include 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, and triethylene glycol. Examples of other alcohol include aromatic alcohols, such as benzyl alcohol and phenethyl alcohol, polyoxy ether alcohols, such as adduct of an aliphatic alcohol with ethylene oxide or propylene oxide, and amino alcohols, such as ethanolamine and diethanolamine. The alcohol or aldehyde is particularly preferably an aliphatic alcohol or aldehyde selected from among saturated and unsaturated straight-chain and branched aliphatic alcohols and aldehydes having 8 to 36 carbon atoms and aliphatic glycols having 2 to 12 carbon atoms. The amine which is reacted with these alcohols or aldehydes may be a gaseous or liquid one, and examples thereof include aliphatic amines, e.g., primary amines such as monomethylamine, ethylamine and dodecylamine, and secondary amines such as dimethylamine, diethylamine and didodecylamine. In the present invention, it is necessary to remove water formed during a reaction of an alcohol or an aldehyde with an amine from the reaction system. When the formed water is not removed from the reaction system, no sufficient catalytic performance according to the present invention can be attained. That is, the catalytic activity and selectivity are lowered, so that it becomes difficult to easily prepare an N-substituted amine in a high yield. For example, when the reaction is conducted by making use of dimethylamine as the amine without removing the formed water, not only the amount of by-products, such as monoalkylmethylamine, which are difficult to separate through mere distillation is increased but also a high-boiling material, such as condensate of an aldehyde, is formed in a large amount, which brings about a lowering in the yield of the intended N-substituted amine. Water may be intermittently or continuously removed during the reaction as far as the formed water is properly removed so as not to remain in the reaction system for a long period of time. It is preferred to continuously remove water each time it is formed. More specifically, it is a common practice to introduce a suitable amount of hydrogen gas into the reaction system to distill the formed water and the excess amine (in the case of use of a gaseous amine) together with the hydrogen gas. In this method, it is also possible to reuse the hydrogen gas through condensation and separation of the formed water in a condenser. Further, a suitable solvent may be added to the reaction system, followed by distillation and removal of the formed water in the form of an azeotrope with the solvent. In the process of the present invention, although a catalyst which has separately been reduced with a hydrogen gas may be employed, a catalyst before reduction is placed in a reactor together with the starting material of the reaction, i.e., an alcohol or an aldehyde, followed by elevation of the temperature to the reaction temperature while introducing a hydrogen gas, thereby conducting reduction. That is, the copper/fourth period transition metal element/platinum group element catalyst according to the present invention has also a significant feature that since the reduction temperature is low, the reduction can be conducted in the step of elevating the temperature to the reaction temperature. The preferred embodiments of the process of the present invention will now be briefly described. A reaction vessel equipped with a tube for introducing hydrogen and an amine and a condenser and a separator for condensing and separating water formed during the reaction, the excess amine and oleaginous matter distilled off is charged with a starting material, i.e., an alcohol or an aldehyde, and a catalyst. The amount of the catalyst may be arbitrary. Since, however, the catalyst of the present invention has high activity, it is usually employed in an amount as small as 0.1 to 2 % by weight based on the feed alcohol or aldehyde. The system is purged with a nitrogen gas, and the temperature is then raised while introducing hydrogen. The reaction is usually conducted at a temperature of 150 to 250°c. However, the reaction temperature may be one outside the above-described range depending upon the kind of the reaction. The catalyst is converted into a reduced, active state during the elevation of the temperature. When the temperature reaches a predetermined value, ammonia or an amine is introduced to initiate the reaction. The amine may be gaseous or liquid. Further, the amine may be introduced into the system in a continuous or intermittent manner or at a time (in the case of a liquid amine). During the reaction, the formed water is discharged outside the reaction system together with gaseous substances (excess gaseous amine in the case of the use of hydrogen and a gaseous amine) and passed through the condenser and separator to separate the water from the oleaginous matter. The analysis of the gaseous substances (excess gaseous amine in the case of the use of hydrogen and a gaseous amine) has revealed that these gaseous substances are substantially free from by-products (e.g., hydrocarbon and amine by-product formed by disproportionation of the starting amine), i.e., has proved that the catalyst of the present invention has high selectivity. Therefore, it was found that these gaseous substances can be reused without any special step of purification. After the completion of the reaction, the reaction mixture itself is subjected to distillation or filtration to separate the reactant from the catalyst. The N-substituted amine obtained by the filtration can be distilled into a very pure form. Examples of the CatalystExamples 1 and 2 and Comparative Examples 1 to 4A copper/fourth period transition metal element/platinum group element/fourth component quaternary catalyst supported on synthetic zeolite was prepared as follows. A 1-ℓ flask was charged with synthetic zeolite, and an aqueous solution prepared by dissolving copper nitrate, nickel nitrate and palladium chloride in water in a copper : nickel : palladium molar ratio of 4 : 1 : 0.05 was then added thereto, followed by elevation of the temperature while stirring. An aqueous 10% Na₂CO₃ solution was gradually dropwise added thereto at 90°C. The mixture was aged for 1 hr, and the resultant precipitates were collected by filtration, washed with water, dried at 80°C for 10 hr, and baked at 400°C for 3 hr. The resultant ternary catalyst was impregnated with an aqueous lithium carbonate solution (a Ni to Li molar ratio of 1 : 0.05) and again dried at 80°C for 10 hr, followed by baking at 300°C for 1 hr. The amount of the resultant metallic oxide supported on the carrier was 50%. Then, a reaction of an alcohol with dimethylamine was conducted in the presence of the above-prepared catalyst. In Comparative Examples, the reaction was conducted in the presence of a copper/nickel/palladium catalyst and a copper/nickel catalyst prepared in the same manner as that described above. A 1-ℓ flask equipped with a condenser and a separator for separating the formed water was charged with 600 g of lauryl alcohol and 1.5 g (0.25% by weight based on the starting alcohol) of the above-described catalyst. The system was purged with nitrogen while stirring, followed by initiation of the elevation of the temperature. When the temperature reached 100°C, a hydrogen gas was blown into the system through a flowmeter at a flow rate of 10 ℓ/hr, and the temperature was raised to 200°C. At this temperature, a mixed gas comprising dimethylamine and hydrogen was blown into the reaction system at a flow rate of 40 ℓ/hr, and the reaction was monitored by measurement of an amine value and gas chromatography. The results are shown in Table 1. It was found from the results that as with the Cu/Ni/platinum group element (Pd) ternary catalyst system, the Cu/fourth period transition metal element (Ni)/platinum group element (Pd)/fourth component (Li) four component catalyst system according to the present invention exhibited higher activity than that of the conventional Cu/Ni binary catalyst system (Comparative Example 1) and a remarkable improvement in the selectivity thereover. catalyst composition molar ratio reaction time (hr) composition of reaction product (wt%) unreacted alcohol lauryldimethylamine Others Ex. 1Cu/Ni/Pd/Li = 4/1/0.05/0.0551.697.60.8 Comp. Ex. 1Cu/Ni = 4/1105.389.05.7 Comp. Ex. 2Cu/Ni/Pd = 4/1/0.0551.892.35.9 Then, lauryldimethylamine prepared in the presence of the above-described catalysts was purified by distillation, followed by a reaction with benzyl chloride or methyl chloride under ordinary conditions to synthesize a quaternary ammonium salt of lauryldimethylamine. The hue of the quaternary ammonium salt thus prepared was measured with Lovibond Red (by making use of a 1-in. cell). The results are shown in Table 2. It was found from the results that when the Cu/Ni/platinum group element (Pd)/fourth component (Li) quaternary catalyst system according to the present invention was used, the hue of the quaternary ammonium salt was far better than that of the quaternary ammonium salt in the case where the Cu/Ni binary catalyst system (Comparative Example 3) and the Cu/Ni/Pd ternary catalyst system (Comparative Example 4) were used. Examples 3 to 7With respect to a catalyst comprising copper, a fourth period transition metal element, a platinum group element, and a fourth component, the activity n a reaction of stearyl alcohol with monomethylamine was determined by using Cr as the fourth period transition metal element and Ru as the platinum group element and varying the kind of the fourth component among Li, Na, K, Rb, and Cs in the catalyst. These quaternary catalysts were prepared in the same manner as that of Example 1. Further the tertiary amine thus formed was purified by distillation and then reacted with methyl chloride, followed by observation of the hue (Lovibond Red) of the resultant quaternary salt. The results are shown in Table 3. It was found from the results that when distearylmonomethyl tertiary amine was prepared through a reaction of stearyl alcohol with monomethylamine, the Cu/Cr/Ru/fourth component catalysts wherein Li, Na, K, Rb, or Cs is used as the fourth component exhibited an excellent activity, brought about an improvement in the selectivity, and contributed to an improvement in the hue of the quaternary ammonium salt. Examples 8 to 11With respect to a catalyst comprising copper, a fourth period transition metal element, a platinum group element, and a fourth component, the activity in a reaction of dodecyl alcohol with ammonia was determined by using Zn as the fourth period transition metal element and Pt as the platinum group element and varying the kind of the fourth component among Mg, Ca, Sr, and Ba in the catalyst. These quaternary catalysts were prepared in the same manner as that of Example 1. The results are shown in Table 4. It was found from the results that when tridodecylamine was to be prepared through a reaction of dodecyl alcohol with ammonia, the Cu/Zn/Pt/fourth component catalysts wherein Mg, Ca, Sr, or Ba is used as the fourth component provided an excellent activity and improved in selectivity. Examples 12A reaction of lauryl alcohol with ammonia was conducted in the presence of a Cu/Co/Pd/fourth component (Ba) catalyst. In this reaction, ammonia was blown into the system at a feed rate of 30 ℓ/hr. The reaction was monitored by measurement of an amine value and gas chromatography. The secondary amine thus prepared was purified by distillation and then reacted with benzyl chloride, followed by observation of the hue (Lovibond Red) of the resultant quaternary salt. The results are shown in Table 5. It was found from the results that the use of the Cu/Co/Pd/fourth component (Ba) catalyst in a reaction of lauryl alcohol with ammonia enabled the preparation of a secondary amine with a high activity and brought about a remarkable improvement in the hue of the quaternary ammonium salt. Example 13A reaction of lauryl alcohol with stearylamine was conducted in the presence of a Cu/Mn/Ru catalyst. In this reaction, the stearylamine was introduced at a time in a liquid state into the reaction system. The reaction was monitored by measurement of an amine value and gas chromatography. The results are shown in Table 6. It was found from the results that the present catalyst system enabled the reaction to proceed with very high activity and the corresponding amine to be prepared with a high selectivity. Examples 14 to 17The effect of the catalyst of the present invention was examined with respect to reactions of various alcohols or aldehydes with dimethylamine to prepare the corresponding tertiary amines. The catalysts were prepared by the impregnation process. The results are shown in Table 7. It was found from the above results that the catalyst of the present invention enabled a tertiary amine to be prepared with very high activity and high selectivity even when a branched alcohol, a polyhydric alcohol (glycol), or an aldehyde was used as the starting material and reacted with a secondary amine. In general, the use of such a branched alcohol, a polyhydric alcohol, or an aldehyde as the starting material brings about an increase in the possibilities of causing side reactions such as decomposition or condensation of these substances. However, it was substantiated that the catalyst having a composition according to the present invention is an excellent catalyst capable of solving these problems. Examples 18A reaction of lauryl alcohol with stearylamine was conducted in the presence of a Cu/Fe/Pd/fourth component (K) catalyst. In this reaction, stearylamine was introduced at a time in a liquid state into the reaction system. The reaction was monitored by measurement of an amine value and gas chromatography. The reaction pressure was 50 atm (gauge). The results are shown in Table 8. It was found from the results that the present catalyst system enabled the preparation of an amine through a reaction of lauryl alcohol with stearylamine with a high activity and a high selectivity. Example 19The reaction mixture prepared in Example 1 was filtered to recover the catalyst therefrom, and the amination reaction was repeatedly conducted under the same conditions. The results are shown in Table 9. number of runs reaction time (hr) composition of reaction product (wt%) unreacted alcohol lauryldimethylamine Others 151.697.69.8 251.597.51.0 351.796.32.0 451.596.71.8 551.996.51.6 Example 20Behenyl alcohol and stearylamine, fed at a molar ratio of 1/1, were reacted with each other in the presence of 2 percent by weight, based on the alcohol, of a catalyst of Cu, Mn, Rh and K, having a molar ratio of 95/5/0.05/0.5 and an amount of support of 40 percent by weight, at 200°c. The stearylamine was introduced at a time in the form of liquid into the reaction system and the reaction procedure was followed with an amine value and gas chromatographic analysis. Results are shown in Table 10. It is found that a corresponding amine can be produced with a high reactivity and a high selectivity from a long chain alcohol and a long chain amine, with the catalyst of the invention. example 20 catalystCu/Mn/Rh/K reaction time (hour)5 composition of product mixture (weight percent) unreacted alcohol1.8 N-stearyl-behenylamine91.2 others7.0
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A process for preparing an N-substituted amine, which comprises the step of reacting an alcohol or an aldehyde with ammonia, a primary amine or a secondary amine at a temperature from 150 to 250°C and at a pressure from atmospheric pressure to 100 atm gauge, with removal of water formed in the reaction, in the presence of a catalyst comprising (1) copper, (2) a metal selected from chromium, manganese, iron, cobalt, nickel and zinc, (3) a metal of the platinum VIII group an (4) a metal selected from alkali metals and alkaline earth metals. A process as claimed in claim 1, in which the molar ratio of the component (1) to (2) ranges from 10/90 to 99/1, the molar ratio of the component (3) to the sum total of (1) and (2) ranges from 0.001 to 0.1 and the molar ratio of the component (2) and (4) ranges from 1/0.01 to 1/1.
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KAO CORP; KAO CORPORATION
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ABE HIROSHI; AIKAWA JUN; OKABE KAZUHIKO; SOTOYA KOHSHIRO; ABE, HIROSHI; AIKAWA, JUN; OKABE, KAZUHIKO; SOTOYA, KOHSHIRO
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EP-0489724-B1
| 489,724 |
EP
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B1
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EN
| 19,990,303 | 1,992 | 20,100,220 |
new
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H01L27
| null |
H01L27, H04N3
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H01L 27/146T, H04N 3/15E6
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Device and method of photoelectrically converting light into electrical signal
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A photoelectric transducer device controls a potential of a control electrode region of a semiconductor transistor through a capacitor to perform a storage operation for storing carriers generated upon light excitation of the control electrode region, a read operation for reading a signal from a main electrode region of the semiconductor transistor, the signal being controlled by a storage voltage generated by storage of the carriers, and a refresh operation for electrically neutralizing the carriers stored in the control electrode region. A semiconductor region having the same conductivity type as that of the main electrode region and having an impurity concentration lower than that of the main electrode region is formed in the control electrode region independently of the main electrode region. A photoelectric transducer device including a semiconductor region. Two main electrodes and a control electrode are formed between the main electrodes. A capacitor is provided for controlling a potential of the control electrode in a floating state. The photoelectric transducer device is adapted to control the potential of the control electrode in the floating state through the capacitor to store carriers generated by electromagnetic waves incident on the semiconductor region. Control means is provided for controlling the potential of the control electrode through the capacitor to electrically neutralize the carriers and means for injecting carriers into the control electrode immediately prior to electrical neutralization of the carriers by the control means is provided.
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BACKGROUND OF THE INVENTIONField of the InventionThe present invention relates to a device and method of photoelectrically converting light into an electrical signal wherein a potential at a control electrode region of a semiconductor transistor is controlled through a capacitor to store carriers excited with light in the control electrode region, thereby controlling an output from the semiconductor transistor.Related Background ArtFig. 1A is a plan view of a photoelectric transducer device described in EP-A-0 132 076, Fig. 1B is a sectional view of the device taken along the line I - I thereof, and Fig. 1C is a diagram of an equivalent circuit thereof.Referring to Figs. 1A to 1C, photoelectric transducer cells are arranged on an n-type silicon substrate 101. The photoelectric transducer cells are electrically insulated by an element isolation region 102 made of SiO2, Si3N4 or polysilicon.Each photoelectric transducer cell has the following construction. A p-type impurity is doped to form a p-type region 104 on an n -type region 103 having a low impurity concentration formed by an epitaxial technique or the like. An n+-type region 105 is formed in the p-type region 104 by impurity diffusion or ion implantation. The p- and n+-type regions 104 and 105 serve as the base and emitter of each bipolar transistor.An oxide film 106 is formed on the n--type region 103. A capacitor electrode 107 having a predetermined area is formed on the oxide film 106. The capacitor electrode 107 opposes the p-type region 104, with the oxide film 106 interposed therebetween, thereby constituting a capacitor Cox. Upon application of a pulse voltage to the capacitor electrode 107, the potential of the p-type region 104 in the floating state is controlled.An emitter electrode 108 connected to the n+-type region 105, a wiring 109 for extracting the signal from the emitter electrode 108, and a wiring 110 connected to the capacitor electrode 107 are formed at the upper surface side of the substrate 101. An n+-type region 111 having a high impurity concentration and an electrode 112 for applying a voltage to the collector of a bipolar transistor are sequentially formed on the lower surface of the substrate 101.The basic operation of the photoelectric transducer device will be described below. Assume that the p-type region 104 as the base region of the bipolar transistor is set in the initial state of a negative potential. Light 113 is incident on the p-type region 104 and carriers corresponding to the amount of light are stored in the p-type region 104 (storage operation). The base potential is changed by the charged carriers. The change in base potential controls a current supplied to an emitter-collector path, and an electrical signal having a level corresponding to the amount of incident light is extracted from the floating emitter electrode 108 (read operation). In order to remove the carriers stored in the p-type region 104, the emitter electrode 108 is grounded and a refresh positive voltage pulse is supplied to the capacitor electrode 107. Upon application of this positive voltage, the p-type region 104 is forward-biased with respect to the n+-type region 105, thereby removing the charged carriers. When the refresh pulse falls, the p-type region 104 returns to the initial state of the negative potential (refresh operation). The cycle of storage, read, and refresh operations is repeated.According to the method proposed here, the carriers generated upon reception of light are stored in the p-type region 104 as the base region, and the current supplied between the emitter and collector electrodes 108 and 112 is controlled by the stored carriers. Therefore, the stored carriers are amplified by the amplification function of each cell, and the amplified carriers are read out. Therefore, a high output with high sensitivity and low noise can be obtained.A potential Vp generated by the base by the carriers stored in the base upon light excitation is given by Q/C where Q is the charge of the carriers stored in the base, and C is the capacitance connected to the base. As is apparent from the above mathematical expression, both Q and C are reduced according to the reduction of the cell size when the transducer device is highly integrated. It is thus found that the potential Vp generated by light excitation is kept substantially constant. Therefore, the method proposed by the above prior art is advantageous in a future high-resolution implementation.The change in base potential Vb during the application of the positive refresh voltage to the capacitor electrode 107 is given as follows: (Cox + Cbe + Cbc)dVb/dt = -Ib where Cbe is the capacitance between the base and emitter of the bipolar transistor, Cbc is the capacitance between the base and collector thereof, and Ib is the base current.Fig. 2 is a graph showing changes in base potential Vb during the application of the positive refresh voltage as a function of time. Referring to Fig. 2, the initial base potential at the time of the application of the refresh pulse varies according to the magnitude of the storage voltage Vp. The negative potential in the initial state is changed in the positive direction by the storage voltage Vp during the storage operation. In this state, when the positive refresh pulse is applied to the capacitor electrode 107, the initial base potential is greater than a potential after refresh by the storage voltage Vp.As is also apparent from the graph in Fig. 2, the time for which the initial base potential is maintained varies according to the magnitude of the initial base potential. However, after the lapse of this period, the base potential Vb is decreased at a common rate regardless of the initial base potential. If the refresh time t is sufficiently long, the base potential Vb can be controlled to be substantially 0 V regardless of the magnitude of the storage voltage Vp. Therefore, the base potential Vb returns to the predetermined negative potential of the initial state when the refresh pulse falls.However, in order to achieve high-speed operation, the refresh operation is terminated at the refresh time t = t0 and the base potential Vb = Vk in practice. Even if a residual potential of the base potential Vb is present, the base potential Vb can return to the predetermined negative potential when the refresh pulse falls under the conditions wherein the refresh time t = t0 is established and the base potential Vb is constantly the predetermined potential Vk. Therefore, the negative potential can be set to be the initial state.However, in the conventional photoelectric transducer device described above, when the refresh operation is repeated, the residual potential Vk is gradually decreased to undesirably cause an after image phenomenon.Referring to Fig. 2, assume that the initial base potential of a cell receiving a large amount of light is 0.8 V and that the initial base potential of a cell receiving a small amount of light is 0.4 V. When the refresh time t has elapsed, the base potential Vb of the cell receiving a large amount of light becomes the predetermined residual potential Vk. However, the base potential Vb of the cell receiving a small amount of light becomes a residual potential Vl lower than the predetermined residual potential Vk. In this state, when the refresh pulse falls, the base potential Vb of the cell receiving a small amount of light becomes lower than the negative potential of the initial state. From a potential lower than the initial negative potential, storage and read operations are started. Therefore, if the refresh operation is repeated in a low illuminance state, the residual potential of the base is gradually decreased. Even if a high illuminance state is obtained, the resultant output has a level lower than that corresponding to the amount of incident light. In other words, the after image phenomenon occurs due to the following reason. When the refresh operation is repeated, the holes in the base region are recombined to result in their shortage. If the shortage of holes cannot be compensated for a long period of time, i.e., if the low illuminance state continues for a long period of time, the after image phenomenon typically occurs. Fig. 3 is a schematic circuit diagram of an area sensor using a conventional photoelectric transducer device. Referring to Fig. 3, conventional photoelectric transducer cells 120 of a 3 x 3 matrix are arranged in the area sensor. Emitter electrodes 108 of the cells 120 are connected to corresponding vertical lines in units of columns. Capacitor electrodes 107 are connected to horizontal lines in units of rows. A positive voltage from a vertical scanning unit 121 is applied to the photoelectric transducer cells 120 to perform read access or refresh operation in units of rows. EP-A-0132076 also proposes an arrangement in which the emitter of the bipolar transistor also functions as the drain region of an MOS transistor, and the source region of the MOS transistor is connected to the base region of the bipolar transistor by a conductor. At the time of the refresh operation the emitter (and therefore the drain region) is grounded and then the MOS transistor is turned on, so that a current flows to bring the base to zero potential. Then the MOS transistor is turned off and the base is refreshed by applying the refresh pulse to the capacitor electrode. In another embodiment EP-A-0132076 proposes that the refresh pulse is not used, and the base is refreshed only by applying a voltage to the base through an MOS transistor, which may be constructed as described above or may be completely separate from the emitter. EP-A-0206649 (which was published on 30 December 1986, after the filing date of the present application, but which has a filing date earlier than the filing date of the present application and a priority date earlier than the priority dates of the present application) proposes that the photoelectric transducer cell includes an additional semiconductor region, of the same conductivity type as the base region, underneath a cell isolation region, so as to form a pnpn structure. The additional semiconductor region acts as the emitter of a secondary bipolar transistor, the base of which is formed by the collector of the main bipolar transistor and the collector of which is formed by the base of the main bipolar transistor. This secondary bipolar transistor is used for injecting carriers into the base region of the main bipolar transistor before the refresh pulse is applied to the capacitor electrode. In an array of such cells the emitters of the main bipolar transistors are connected to vertical lines which are connected through transistors to storage capacitors, and then through further transistors to an output line. The emitter electrodes are also connected to ground through further transistors, for grounding the emitter electrodes during the refresh pulse.SUMMARY OF THE INVENTIONAccording to the present invention there is provided a photoelectric transducer apparatus as set out in claim 1 and a method of operating photoelectric transducer apparatus as set out in claim 5. Optional features are set out in the remaining claims.An embodiment of the present invention provides a device and method of photoelectrically converting light into an electrical signal, wherein a residual potential is not decreased even if refresh operation is repeated, and an after image phenomenon can be eliminated. BRIEF DESCRIPTION OF THE DRAWINGS:Fig. 1A is a schematic plan view of a photoelectric transducer device described in EP-A-0 132 076, Fig. 1B is a sectional view of the device in Fig. 1A taken along the line I - I thereof, and Fig. 1C is an equivalent circuit diagram of the device in Fig. 1A;Fig. 2 is a graph showing changes in base potential during refresh operation as a function of time;Fig. 3 is a circuit diagram of an image pickup device using the photoelectric transucer device described in EP-A-0 132 076. Fig. 4A is an equivalent circuit diagram of a photoelectric transducer device used in an embodiment of the present invention, and Fig. 4B is an equivalent circuit diagram of a photoelectric tranducer device used in another embodiment of the present invention;Fig. 5A is a circuit diagram of a one-dimensional image pickup device embodying the present invention, Fig. 5B is a timing chart for explaining an operation of the image pickup device in Fig. 5A, Fig. 5C is a timing chart for explaining another operation of the image pickup device in Fig. 5A, and 5D is a timing chart for explaining still another operation of the embodiment as shown in Fig. 5A.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS:Preferred embodiments of the present invention will be described with reference to the accompanying drawings below.Fig. 4A is an equivalent circuit diagram of a photoelectric transducer device used in an embodiment of the present invention.Referring to Fig. 4A, a p-type base region 703 of an npn bipolar transistor 701 is connected to a capacitor electrode 704 through a capacitor 702. The base region 703 is connected to the drain of a p-channel MOS transistor 707.The operation of the transducer device having the arrangement described above will be described below. In the storage operation, the p-type base region 703 is set in the initial negative potential, the emitter electrode 705 is set at zero potential in the floating state, and the capacitor electrode 704 is set at zero potential. The collector electrode 706 is maintained at a positive potential. The gate electrode 708 of the p-channel MOS transistor 707 is set at a positive potential, and the p-channel MOS transistor 707 is rendered nonconductive. In this state, upon reception of light, carriers (holes in this case) corresponding to the amount light are stored in the p-type base region 703.In the read operation, the emitter electrode 705 is set in the floating state, anda positive read voltage pulse is applied to the capacitor electrode 704. As previously mentioned, an electrical signal corresponding to the amount of incident light is read out to the emitter electrode 705.In the hole injection operation, the capacitor electrode 704 is set at zero potential, the emitter electrode 705 is set in the floating state or at zero potential, and a source electrode 709 of the p-channel MOS transistor 707 is set at a proper potential, e.g., the ground potential. Assume that a negative pulse is applied to the gate electrode 708 of the p-channel MOS transistor 707. If the potential of the p-type base region 703 is lower than that of the source electrode 709 in the dark state or a state wherein an amount of light is small, the holes are injected into the p-type base region 703 to increase its potential. However, if the amount of incident light is large and at the same time the potential of the p-type base region 703 is higher than that of the source electrode 709, some of the holes stored in the p-type base region 703 are erased. The potential of the p-type base region 703 is set to be equal to that of the source electrode 709. The potential of the source electrode 709 is set such that the potential of the p-type base region 703 is sufficiently higher than the residual potential Vk even in the dark state.In the refresh operation, the emitter electrode 705 is grounded, the gate electrode 708 of the p-channel MOS transistor 707 is set at a positive potential, and the p-channel MOS transistor 707 is rendered nonconductive. In this state, when the refresh pulse is applied to the capacitor electrode 704, the holes stored in the p-type base region 703 are recombined with the electrons injected from the emitter electrode 705 to the p-type base region 703, thus eliminating the holes. Since the potential of the p-type base region 703 is sufficiently high due to the hole injection operation even in the dark state, the initial base potential upon application of the refresh pulse is sufficiently higher than the residual potential Vk regardless of the amount of incident light (Fig. 2). Therefore, when the refresh time t0 has elapsed, the potential of the p-type base region 703 is set at the predetermined potential Vk regardless of the amount of incident light. In this state, when the positive refresh pulse falls, the p-type base region 703 is set at the predetermined initial negative potential. By inserting the hole injection operation in the transducer cycle, the holes in the p-type base region 703 are not subject to shortage even if the refresh operation is repeated. Therefore, nonlinearity of the photoelectric transducer characteristics and the after image phenomenon with a small amount of light can be completely prevented.In the above embodiment, the base region as the control electrode has a p conductivity type, and thus the carriers are holes. However, if the base region as the main control electrode of a pnp bipolar transistor has an n conductivity type, the carriers are electrons.In the embodiment of Fig. 4A, the means for injecting the carriers in the p-type base region is a p-channel MOS transistor. However, other means may be used in place of the p-channel MOS transistor. For example, as shown in Fig. 4B, an n-channel MOS transistor may be used. The control means for controlling the potential of the control electrode region through the capacitor to dissipate the carriers (holes) stored therein is the means for grounding the emitter region, applying the refresh pulse to the capacitor electrode, and then injecting electrons from the emitter region, thereby recombining the electrons and the holes.Fig. 5A is a circuit diagram of an image pickup device having photoelectric transducer cells arranged in a one-dimensional manner, and Fig. 5B is a timing chart for explaining the operation of the image pickup device in Fig. 5A.Referring to Fig. 5A, three photoelectric transducer cells 810 are one-dimensionally arranged. Collector electrodes 809 are commonly connected and receive a positive voltage. Capacitor electrodes 804 are commonly connected to a terminal 831 through a horizontal line 830. A read/ refresh pulse signal R is applied to the terminal 831. Emitter electrodes 805 are respectively connected to vertical lines 835, 835', and 835 . A gate electrode 808 of the transistor 807 is connected to a terminal 833 through a horizontal line 832 and receives a pulse signal c for hole injection. A source electrode of the transistor 807 is connected to a terminal 834 for receiving a hole injection voltage Vc.The vertical lines 835, 835', and 835 are respectively grounded through transistors 836, 836', and 836 . The gate electrodes of the transistors 836, 836', and 836 are commonly connected to a terminal 838 through a line 837. A signal vc is applied to the terminal 838.The vertical lines 835, 835', and 835 are respectively connected to charge storage capacitors 840, 840', and 840 through transistors 839, 839', and 839 and to an output line 844 through transistors 843, 843', and 843 . The gate electrodes of the transistors 839, 839', and 839 are commonly connected to a terminal 842 through a line 841. A signal T is applied to the terminal 842.The gate electrodes of the transistors 843, 843', and 843 are connected to the parallel output terminals of a shift register 845. Signals H1, H2, and H3 respectively appear at the parallel output terminals.The output line 844 is grounded through a transistor 846 for refreshing the output line 844 and connected to the gate electrode of a transistor 848 serving as an output amplifier and having an output terminal 849. The gate electrode of the refresh transistor 846 is connected to a terminal 847. A signal Hc is applied to the terminal 847.The operation of the image pickup device having the arrangement described above will be described with reference to Fig. 5B.The pulse signals T and vc rise to turn on the transistors 839, 839', 839 , 836, 836', and 836 . The emitter electrodes 805 of the photoelectric transducer cells 810 and the vertical lines 835, 835', and 835 are grounded, thereby removing the residual charges from the charge storage capacitors 840, 840', and 840 and the vertical lines 835, 835', and 835 .At time t1, the signal c rises so that the potential Vc applied to the terminal 834 is applied to the base region 803 of each photoelectric transducer cell 810. The holes are injected into the base region 803 of each photoelectric transducer cell 810 held in the dark state or receiving a small amount of light. As a result, the potentials at the base regions of the photoelectric transducer cells are set to be substantially equal to each other (hole injection operation).Before time t2, the signal c falls and at time t2 the signal R rises to apply the positive refresh voltage to the capacitor electrodes 804 of the photoelectric transducer cells 810. Since the emitter electrodes are grounded, the refresh operation is performed in the same manner as described with reference to Fig. 4A. When the signal R falls at time t3, the p-type base regions 803 of the photoelectric transducer cells 810 are reset in the initial negative potential state. When the refresh operation is completed, the signal vc falls to turn off the transistor 836, 836', and 836 .At time t4, the signal R rises again to apply the positive read voltage to the capacitor electrodes 804 of the photoelectric transducer cells 810. In this state, the holes of the electron-hole pairs excited by incident light are stored in the p-type base regions of the photoelectric transducer cells 810. The base potential of each cell is increased by the storage voltage component corresponding to the amount of light, and at the same time, the read operation is performed. The read signals corresponding to the optical information of the photoelectric transducer cells 810 are respectively stored in the charge storage capacitors 840, 840', and 840 . The store operation in this case is conducted under the condition that respective cells are forward-biased between base and emitter thereof.At time t5, the signals T and R fall to turn off the transistors 839, 839', and 839 . The signal Hc rises to remove the residual charge from the output line 844, and then the signal Hc falls. The signal H1 output from the first output terminal of the shift register 845 rises to turn on the transistor 843, so that the read signal stored in the charge storage capacitor 840 is read out onto the output line 844.The readout signal appears at the terminal 849 through the transistor 848. Subsequently, the signal Hc rises, and the output line 844 is grounded through the transistor 846, thereby removing the residual charge.In the same manner as described above, the signals 843' and 843 output from the shift register 845 sequentially rise to read out the read signals from the charge storage capacitors 840' and 840 onto the output line 844. Every time a read signal appears, the pulse signal Hc rises to refresh the output line 844. In this manner, the read signals from all the photoelectric transducer cells 810 serially appear at the terminal 849 through the transistor 848.Fig. 5C is a timing chart for explaining another operation of the image pickup device in Fig. 5A. Fig. 5C shows the operation mode wherein the signal R which rises at time t2 does not fall at time t3, and other signal timings are the same as those in Fig. 5B. In the case of Fig. 5C, a store operation is conducted under the condition that respective cells are forward-biased between base and emitter thereof, the signals generated by the transistors 805 of the photoelectric transducer cells are always read out onto the vertical lines 835, 835', and 835 . Such read operation can be allowed.According to this timing, a noise taken in the sensor cells responsive to the falling and rising of the pulse R, that is a fixed pattern noise due to an irregularity in configuration in cells of the capacitor electrode and a random noise due to a carrier produced by depressing the interface between the oxidization film and the semiconductor under the capacitor electrode, is removed. Therefore, a good signal without noise can be obtained.Fig. 5D is a timing chart for explaining still another operation of the embodiment as shown in Fig. 5A.Fig. 5D shows the operation mode wherein the signal T which has not fallen at the time t3, falls at the time t3 and rises again at the time t4 at which the store operation is completed. An operation of another timings is the same as that of Fig. 5C. In the case of the operation as shown in Fig. 5D, during the store operation, the signals produced at the transistors 805 of respective cells are readout to only the vertical lines 835, 835', and 835 . In case of long time store operation, since quantity of bias between base and emitter of the transistors 805 in respective cells is reduced as the store time continues, the emitter current of the transistor 805 also is reduced. Thereby, irregularity in operation of the cell is produced in the low current region in the transistor 805 as it is outputted as a signal to the vertical lines 835, 835', and 835 . According to this timing, when the pulse T rises again at time t4, the signals including the low current operation irregularity of the transistor 805 which has been read out to the vertical lines 835, 835', and 835 are once divided between the capacitors 840, 840', and 840 and the wiring capacitances of the vertical lines 835, 835', and 835 . Therefore, the voltage of the signals is dropped. Since the voltage of the vertical lines 835, 835', and 835 is dropped, the transistor 805 operates again. By the large emitter current, the signals stored in bases of respective cells can be read out to the capacitors 840, 840', and 840 . Thereby, the signals including low current operation irregularity of the transistor 805 produced during the long store time are removed. Signals without operation irregularity of transistors of respective cells can be read out to the capacitors 840, 840', and 840 .In the photoelectric transducer device of this embodiment as described above, a transistor and the like is formed in the control electrode region of the semiconductor transistor, and thus the potential of the control electrode is controlled. Therefore, the carriers can be injected into the control electrode at the proper time. For example, the potential of the control electrode region can be kept sufficiently high at the beginning of refreshing. The potential of the control electrode region at the end of refreshing can be maintained at a desired predetermined value. The conventional nonlinearity of the characteristics and the after image phenomenon of the photoelectric transducer can be improved.In particular, when the present invention is applied to the image pickup device as shown in Fig. 5A, unlike in the conventional control method, fixed pattern noise caused by variations of the capacitances inherent to the photoelectric transducer cells can be prevented. If the image pickup device picks up an image of an object, a video image with little noise can be obtained.
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Photoelectric transducer apparatus comprising: a plurality of photoelectric transducer cells (810), each cell comprising:a bipolar transistor having a base region, an emitter region, a collector region and a control electrode capacitively coupled to the base region, the transistor being operable to accumulate charge carriers in the base region in response to incident electromagnetic radiation, provide a signal from the emitter region in accordance with the quantity of charge carriers stored in the base region, and refresh the base region by neutralising charge carriers stored therein; andan insulated gate transistor (707, 707') for injecting charge carriers into the base region at least in the case that it has a relatively low quantity of charge carriers stored in it;a plurality of storage capacitors (840) for receiving and storing the said signals from the emitter regions;a plurality of first further transistors (839) for coupling the emitter regions to the storage capacitors;an output line (844);a plurality of second further transistors (843) for coupling the storage capacitors to the output line;a plurality of third further transistors (836) for coupling the emitter regions to a fixed potential; andcontrol means for controlling the bipolar transistor and the insulated gate transistor of each cell, and for controlling the first, second and third further transistors,the control means being arranged, in respect of each cell, (a) to cause the insulated gate transistor to inject charge carriers into the base region after a signal has been provided from the emitter region, at least in the case that the base region has a relatively low quantity of charge carriers stored in it, (b) subsequently to cause a refresh pulse to be applied to the said control electrode to neutralise charge carriers stored in the base region, (c) to cause the respective third further transistor (836) to couple the emitter region to the fixed potential while it causes the refresh pulse to be applied to the said control electrode, and (d) to apply a voltage (R) to the base region via the control electrode to forward bias the base-emitter junction during the accumulation of charge carriers so that the said signal is provided from the emitter region during the accumulation of charge carriers.Apparatus according to claim 1 in which the control means is arranged to control the first further transistors (839) to be conductive, so that the said signals provided from the emitter regions are stored in the storage capacitors (840), during the accumulation of charge carriers.Apparatus according to claim 1 in which the control means is arranged to control the first further transistors (839) to be non-conductive, so that the said signals provided from the emitter regions are not stored in the storage capacitors (840), during the accumulation of charge carriers, and to control the first further transistors (839) to be conductive, so that the said signals are stored in the storage capacitors (840), subsequently.Apparatus according to any one of the preceding claims in which the control means is arranged to cause the third further transistor (836) to hold the emitter region to the fixed potential before and while it causes the insulated gate transistor to inject charge carriers into the base region.A method of operating photoelectric transducer apparatus, which apparatus comprises: a plurality of photoelectric transducer cells (810), each cell comprising:a bipolar transistor having a base region, an emitter region, a collector region, and a control electrode capacitively coupled to the base region, the transistor being operable to accumulate charge carriers in the base region in response to incident electromagnetic radiation, provide a signal from the emitter region in accordance with the quantity of charge carriers stored in the base region, and refresh the base region by neutralising charge carriers stored therein; andan insulated gate transistor (707, 707') for injecting charge carriers into the base region at least in the case that it has a relatively low quantity of charge carriers stored in it,a plurality of storage capacitors (840) for receiving and storing the said signals from the emitter regions;a plurality of first further transistors (839) for coupling the emitter regions to the storage capacitors;an output line (844);a plurality of second further transistors (843) for coupling the storage capacitors to the output line; anda plurality of third further transistors (836) for coupling the emitter regions to a fixed potential,the method comprising the steps of, in respect of each cell, (a) injecting charge carriers into the base region after a signal has been provided from the emitter region, at least in the case that it has a relatively low quantity of charge carriers stored in it,(b) subsequently applying a refresh pulse to the control electrode to neutralise charge carriers stored in the base region,(c) holding the emitter region at a fixed potential by means of the respective third further transistor (836) during the step of applying the refresh pulse, and(d) applying a voltage (OR) to the base region via the control electrode to forward bias the base-emitter junction during the accumulation of charge carriers so as to provide the said signal from the emitter region during the accumulation of charge carriers.A method according to claim 5 which comprises rendering the first further transistors (839) conductive, and storing the said signals in the storage capacitors (840), during the accumulation of charge carriers.A method according to claim 5 which comprises rendering the first further transistors (839) non-conductive, and not storing the said signals in the storage capacitors (840), during the accumulation of charge carriers, and rendering the first further transistors (839) conductive, and storing the said signals in the storage capacitors (840), subsequently.A method according to any one of claims 5 to 7 which comprises holding the emitter region at a fixed potential before and during the step of injecting carriers into the base region. A method according to any one of claims 5 to 8 in which charge carriers are injected into the base region in step (a) regardless of the quantity of charge carriers stored in it.A method according to any one of claims 5 to 8 in which charge carriers are injected into the base region in step (a) only if the quantity of charge carriers stored in it is below a threshold level.A method according to claim 10 in which charge carriers are removed from the base region instead of being injected into it if the quantity of charge carriers stored in it is above the threshold level.
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CANON KK; CANON KABUSHIKI KAISHA
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HARADA TADANORI; OHMI TADAHIRO; SUGAWA SHIGETOSHI; SUZUKI TOSHIJI; TANAKA NOBUYOSHI; HARADA, TADANORI; OHMI, TADAHIRO; SUGAWA, SHIGETOSHI; SUZUKI, TOSHIJI; TANAKA, NOBUYOSHI
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EP-0489725-B1
| 489,725 |
EP
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B1
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EN
| 19,960,501 | 1,992 | 20,100,220 |
new
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H05B6
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H05B6
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H05B6
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T05B206:30, T05B206:70, H05B 6/66, H05B 6/68M2B3B, T05B206:02
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High-frequency heating apparatus
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A high-frequency heating apparatus comprises a semiconductor power converter (33) which is supplied with electric power from a commercial power supply, etc., a radio wave radiation section (32) which is energized by the semiconductor power converter (33), a control section (34) which controls the operation of a semiconductor element (28) of the semiconductor power converter (33), and a start control section (41) which controls the operation of the control section (34) at the start time of the high-frequency heating apparatus. The start control section (41) controls the operation of the control section (34) so that the radio wave output power from the radio wave radiation section (32) at the start time of the high-frequency heating apparatus becomes greater than that in the steady operation state thereof, whereby the optimization of the performance and price of the heating apparatus can be realized.
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BACKGROUND OF THE INVENTIONFIELD OF THE INVENTIONThe present invention relates to a high-frequency heating apparatus for heating such objects as foods and fluids, and, more in particular, relates to a high-frequency heating apparatus using a semiconductor electric power converter for generating high-frequency power in an electric a power supply section thereof. DESCRIPTION OF THE RELATED ARTThe high-frequency heating apparatus such as a home or domestic microwave oven often uses a power circuit of a a construction such as shown in Fig. 1. In Fig. 1, when an operation switch 1 is turned on, a commercial power supply 2 is connected to a high-voltage transformer 3. The output of the secondary winding of the high-voltage transformer 3 is rectified by a capacitor 5 and a diode 6 and is supplied to a magnetron 7. A heater winding 8 of the high-voltage transformer 3 is connected to the cathode of the magnetron 7 to heat the cathode. As a result, the magnetron 7 is caused to oscillate and produces a high-frequency electromagnetic wave (radio wave), thereby making it possible to effect induction heating. Fig. 2A is a diagram showing a change with the passage of time of the radio wave output P₀ of the magnetron 7 after turning on the switch 1 at a time point t = 0. When the switch 1 is turned on at time point t = 0, the magnetron 7 is supplied with a cathode heating power and a high-voltage power at the same time. At time point t₁ about one second or two later, the cathode temperature sufficiently increases and the radio wave output P₀ rises, and thereafter the radio wave output is kept substantially constant as shown in Fig. 2A. The radio wave output may, of course, decrease to some degree with the lapse of time due to such factors as the temperature characteristic of the magnetron 7 and the high-voltage transformer 3. Nevertheless, the radio wave output P₀ (for example, 500 W) predetermined as a rated output of the particular apparatus is basically maintained. Fig. 2B is a diagram showing an increase in the temperature of internal parts of a high-frequency heating apparatus after the operation of the heating apparatus has been started. The temperature TM of the magnetron 7 and the temperature Ta of the ambient air of the high-voltage transformer 3 increase in such a manner as shown in this diagram. Fig. 3 is a sectional view of a high-frequency heating apparatus. A housing 9 has an oven 10, a magnetron 7, a high-voltage transformer 3, etc. arranged therein in the manner shown in Fig. 3, and they are forcibly cooled by a cooling fan 11. The efficiency of the magnetron 7 is about 60% and that of the high-voltage transformer 3 is about 90%, so that in the case of an apparatus with an actual radio wave output rating of 500 W, the magnetron 7 develops a loss of about 300 W and the high-voltage transformer 7 about 100 W. As a result, the temperature of these parts gradually increases during the operation as shown in Fig. 2B. The rate of this temperature increase is comparatively high up to a time point of t₂ (say, 15 minutes) determined by the thermal time constant of each part, and thereafter the temperature of the whole apparatus reaches a maximum temperature level at time point t₃ (say, in 60 to 120 minutes) where the temperature becomes saturated. In this way, a high-frequency heating apparatus is composed of parts such as the magnetron 7 and the high-voltage transformer 3 which have comparatively low conversion efficiency and hence generate much heat loss, thus causing a comparatively high temperature increase during its operation and taking a long time before it reaches a stable temperature. In order to guarantee the rated output P₀ of a heating apparatus, it is necessary to have the heating apparatus constructed by using an insulating material and component parts capable of maintaining sufficient safety against such a heat loss. For this reason, the cooling conditions and the specifications of the parts of the apparatus are designed to meet the guarantee requirements. Specifically, the component materials, the parts specifications and the cooling structure are determined by sufficiently taking into consideration the temperature rise that occurs at the time point t₃ in Fig. 2B. The cooling conditions and the parts specifications for the rated output of 500 W are greatly different from those for the rated output of 600 W. The generation of a loss by the magnetron 7, for example, differs between both rated outputs, so that, in the case of the rated output of 600 W, the magnetron 7 must have a bulky cooling construction, which results in an increase in the size and cost thereof, and the high-voltage transformer 3 is also obliged to have a large size and increased cost. Thus, in a conventional high-frequency heating apparatus, as described above, specifications of respective component parts are determined in such a manner as to guarantee safety and reliability of the apparatus under a temperature condition where the temperature rise caused by the heat loss has saturated. However, a high-frequency heating apparatus uses a special method of heating called the induction heating, and a heating time thereof is comparatively short. It is often used with a very short heating time less than five minutes when it is used for the purpose of reheating which is often the case with general home applications. That is, as shown in Fig. 2B, very many operations come to end within the time t₀ or so, but the cooling reaching the time up to t₃ occurs rarely. Thus, most conventional high-frequency heating apparatuses that guarantee the temperature rise thereof to be reached at t₃, which is not required at all under many operating conditions, are operated within the time t₀. Thus, it can be said that such apparatuses have excessively high quality. Nevertheless, this substantially excessive quality has hitherto been considered as unavoidable in view of rare cases where the apparatus is operated under an operating condition that reaches the time point t₃. SUMMARY OF THE INVENTIONAccordingly, an object of the present invention is to provide a very low-cost high-frequency heating apparatus by optimizing the performance of the high-frequency heating apparatus for home applications to meet the operation mode in actual applications, while maintaining its minimum required performance. According to the present invention there is provided a high-frequency heating apparatus comprising: electric power supply means selected from at least one of a commercial power supply, a battery and an electric generator; high voltage electric power conversion means having voltage step-up means for converting electric power supplied from said electric power supply means into high voltage electric power; electromagnetic wave radiation means arranged to receive the high voltage electric power from said high voltage electric power conversion means and to radiate an electromagnetic wave; and operating condition control means for controlling the operating condition of said high voltage electric power conversion means, characterized by comprising increased output control means for controlling the operation of said operating condition control means so as to make the electromagnetic wave output during a limited time period have a level higher than that of a maximum electromagnetic wave output in a steady operation state of said heating apparatus under a continuously operable condition. In accordance with one embodiment of the invention, a control section of the heating apparatus is supplied with a rise signal from a start control section at the time of starting an operation of the high-frequency heating apparatus, whereby the control section controls the operation of a semiconductor element of the electric power converter to increase the electromagnetic wave output level to become higher than a steady operation level. As a result, in an initial stage of the operation of the high-frequency heating apparatus, it is possible to produce a radio wave output larger than that in a steady operation state thereby to shorten the heating time on the one hand and to keep the cooling structure, the heat resistance specifications and performance quality of the component parts at an appropriate level but not excessively high. When it is detected or anticipated that the heating time is long or repeated operations causes the temperature of heat-generating parts to rise higher than a predetermined level, the electromagnetic wave output is reduced to a steady state value. In this way,the amount of electric power handled by the heat-generating parts is reduced, which in turn reduces an amount of heat thereby generated, thus making it possible for the apparatus to operate within a temperature range in which reliability and safety are guaranteed. The apparatus can include a heating control section which makes it possible to adjust the operation time of the electric power converter in accordance with a rise signal or a signal substantially equivalent thereto supplied from the start control section. This heating control section detects the magnitude of the electromagnetic wave output, which is changed as mentioned above, in response to the rise signal from the start control section or a signal equivalent thereto, and the heating control section changes the operation time of the electric power converter in response to such a signal, with the result that, even under a varying electromagnetic wave output, a total amount of heating energy is maintained substantially constant. In other words, in the case of cooking an object of a predetermined amount, the heating control section controls to shorten the heating time when the level of the electromagnetic wave output is higher than the steady operation level, while, to lengthen the heating time when the electromagnetic wave output is on the same level as the steady operation level. As a result, the functions of the heating control section enables an operator of the heating apparatus to perform the same manner of operation when cooking the same object without worrying about the magnitude of the automatically varying electromagnetic wave output. The invention will be described now by way of example only, with particular reference to the accompanying drawings. In the drawings: Fig. 1 is a circuit diagram showing a conventional high-frequency heating apparatus. Figs. 2A and 2B are time charts showing a change with the passage of time of the radio wave output and the part temperature of the same apparatus. Fig. 3 is a sectional view showing the construction of the same apparatus. Fig. 4 is a circuit diagram of a high-frequency heating apparatus according to an embodiment of the present invention. Fig. 5 is a block diagram showing a control section in the circuit shown in Fig. 4. Figs. 6A and 6B are time charts showing a change with the passage of time of the radio wave output of the same apparatus. Fig. 7 is a circuit diagram showing another embodiment of the start control section of the same apparatus. Fig. 8 is a block diagram showing still another embodiment of the start control section of the same apparatus. Figs. 9A, 9B and 9C are waveform diagrams showing operation waveforms appearing in the circuit of another embodiment of the present invention shown in Fig. 4. Fig. 10 is a circuit diagram showing the circuit construction of a high-frequency heating apparatus of still another embodiment of the present invention. Fig. 11 is a circuit diagram showing a detailed construction of an embodiment of the essential parts of the apparatus. Fig. 12 is a circuit diagram showing the construction of another embodiment of the essential parts of the apparatus. Fig. 13 is a circuit diagram showing a detailed construction of the control section of the apparatus. Figs. 14A, 14B and 14C are explanatory diagrams for explaining the starting operation of the apparatus. DESCRIPTION OF THE PREFERRED EMBODIMENTS(Embodiments)An embodiment of the present invention will be explained below with reference to the accompanying drawings. Fig. 4 is a circuit diagram showing a high-frequency heating apparatus according to an embodiment of the present invention. In Fig. 4, a commercial power supply 20, a diode bridge 21, and a filter circuit composed of an inductor 22 and a capacitor 23 make up an electric power supply section 24 for supplying electric power to an electric power converter 33 including a capacitor 26, a step-up transformer 27, a transistor 28, a diode 29, a capacitor 30, a diode 31 and a magnetron 32. The electric power converter 33 includes an inverter having a capacitor 26, a step-up transformer 27, a transistor 28 and a diode 29, a high-voltage rectifier circuit having a diode 31 and a capacitor 30 for rectifying the output of the step-up transformer 27, and the magnetron 32 for generating high-frequency power. This magnetron 32 also serves as a radio wave radiation device for radiating the high-frequency power as electromagnetic energy. The electric power converter 33 may of course be alternatively formed of a semiconductor oscillator adapted to oscillate at 900 MHz or 2450 MHz and an antenna as a radio wave radiating element. The transistor 28 performs a switching operation in response to a switching control signal of, say, 20 KHz to 200 KHz applied thereto from the control section 34. The control section 34 supplies the transistor 28 with a gate pulse VGE shown in Fig. 9A, and therefore the current Ic/d flowing through the transistor 28 and the diode 29 and the collector-emitter voltage VCE of the transistor 28 take waveforms shown in Figs. 9B and 9C, respectively. This electric power converter 33 operates as what is called the resonance-type inverter. Thus, a high-frequency voltage is generated across the primary winding 35 of the step-up transformer 27. This high-frequency voltage is boosted and rectified and supplied to the magnetron 32. The cathode heater of the magnetron 32, on the other hand, is supplied with cathode heating power from the heater winding of the step-up transformer 27. Hence, the magnetron 32 oscillates, and radiates a radio wave. The control section 34 is supplied with a signal proportional to the input current from an input current detector 36. This input current detection signal, as shown in Fig. 5, is supplied to an operational amplifier 37 in the control section 34, and is compared with a signal generated by a reference signal generator 38. A resulting difference signal is supplied to a pulse width control circuit 39. In this way, the conduction time of the transistor 28, namely, the pulse width Ton of the gate pulse VGE shown in Fig. 9A is controlled. The input current is thus controlled to take a predetermined value by what is called the pulse width control. As a result, the electromagnetic wave (radio wave) output P₀ of the magnetron 32 is controlled to take a fixed value (such as 500 W). In actuating the high-frequency heating apparatus having such a construction as mentioned above, a heating start command is applied from the heating control section 40 to the start control section 41. The start control section 41, upon receipt of the heating control command, supplies a rise signal to the control section 34 so that the apparatus may operate to produce an output (say, 600 W), which is larger than the rated output (say, 500 W) in a steady operation state, for a predetermined initial operation time period. Fig. 6A is a diagram showing a manner in which the radio wave output P₀ changes with the passage of time. At the time point t₁ one second or two after the time point t = 0 when the transistor 28 is turned on, the magnetron 32 starts to oscillate, and the radio wave output P₀ is controlled to take a value of 600 W which is larger than a steady operation value (namely, a rated value). At a time point t₄, that is, after the lapse of an initial heating time period ts, the output P₀ is controlled to take a value of 500 W for the steady operation (that is the rated value). Fig. 6A shows a case in which the output P₀ is changed in steps. The same effect as this is obtained if the output P₀ is changed gradually during the time period ts as shown in Fig. 6B. As is seen from this, there are various methods that can be used to control the radio wave output P₀. As an example, this function can be easily realized by the method shown in Fig. 5 in which a signal generated by the reference signal generator 38 as a reference signal for the input current is controlled by the start control section 41. In other words, it is possible to realize this function by changing the reference signal for the input current after the lapse of the time ts so that a change in the output P₀ is caused as shown in Fig. 6A. The time ts shown in Fig. 6A is a time during which an output, whose level is higher than that in the steady state, is generated as long as the temperature of the apparatus and the parts are sufficiently low. Thus, as seen from the diagram of Fig. 2B showing the prior art, ts should be determined to indicate a time during which the internal temperature of the heating apparatus and the temperature of the component parts are lower than a predetermined temperature. Accordingly, the period of time ts may be determined on the basis of the temperature control principle in which, for example, as shown in Fig. 7, a thermistor 42 is used to detect the anode temperature of the magnetron 32 as well as the ambient temperature thereof or the temperature of a radiation fin of the transistor 28, and the temperature detection signal is compared with a reference signal supplied from the reference signal generator 43 by a comparator 44. While, with an increase in the anode temperature of the magnetron 32, the magnetic field intensity of the magnetron 32, if it is of the permanent magnet type, is reduced, resulting in a lower operating voltage. If the control section 34 is constructed in such a manner that the anode current of the magnetron 32 or the secondary current of the step-up transformer 27 which is regarded to be equivalent thereto is detected and this secondary current is controlled at a fixed value, then it is possible to effect substantially the same control of the radio wave output in an initial stage of operation without detecting the anode temperature of the magnetron 32 with the thermistor 42. In other words, in view of the fact that the operating voltage of the magnetron 32 is reduced with an increase in the anode temperature of the magnetron 32, the secondary current is regulated at a fixed value by the control section 34, thereby making it possible to reduce input power to the magnetron 32 by an amount corresponding to the operating voltage decrease. In this way, the radio wave output P₀ shown in Fig. 6B can be controlled in accordance with an increase in the anode temperature of the magnetron 32. As a result, the secondary current detector may be substituted for the temperature detector 42 shown in Fig. 7. As an alternative method, as shown in Fig. 8, a stop time counter 45 for counting a stop time of the units (that is, a time during which the apparatus and parts are cooled) may be inserted, so that a signal from this stop time counter 45 is used to determine the time ts, and a start modulation counter 46 is provided to count the time ts and to cause an output of the input current reference signal generator 38 to be changed, after the lapse of the count time ts, thus determining the time ts by detecting the operating conditions of the apparatus. As another alternative method, it is also of course possible to fix the time ts to a short time of about five minutes, and the start control section 41 may be made up only of a timer. In order to inform the operator of the heating apparatus that the radio wave output P₀ is controlled to take a value greater than that in a steady operation state, an indication section 47 as shown in Fig. 5 is provided and actuated by a signal from the start control section 41. Then, the operator is able to proceed with his cooking operation in recognition of whether the apparatus is powered up (that is, to 600 W) or in a steady operation state (500 W), thereby making it possible to perform a convenient and high speed cooking operation. The heating control section 40 will be described more in detail. The heating control section 40, as shown in Fig. 4, is constructed so as to give a heating command to the start control section 41 for heating an object within a predetermined heating time and simultaneously to receive a rise signal from the start control section 41. This construction is intended to detect the present magnitude of the radio wave output (600 W or 500 W, for example). The heating control section 40 adjusts the heating time for the object in accordance with this detection signal. For example, in Fig. 6A, assume that the heating time terminates within the time ts and one actual heating time is 100 seconds. However, in the case of frequent and repeated use of the heating apparatus where the heating operation is repeated with the initial heating time period ts being substantially zero, the heating control section 40 automatically adjusts the electromagnetic wave output level to be 500 W and the heating time to be 120 seconds (= 100 seconds × 600 W500 W ). There may of course be also a case inbetween, in which case, too, the heating time is adjusted according to the level of the electromagnetic wave output P₀. Thus the operator is able to operate the apparatus without worrying about the change in the level of output P₀ in the same manner as if the output P₀ remains always at, say, 600 W even in a rare heating case where the time t₃ is substantially zero. Thus, a high-frequency heating apparatus easy to operate and having no excessive quality becomes available. As another embodiment of the high-frequency heating apparatus described above, a configuration as shown in Fig. 10 using a microcomputer 54 is possible. In Fig. 10, those component parts designated with the same reference numerals as used in Fig. 4 are respective corresponding parts, and they will not be described any further. In the circuit construction shown in Fig. 10, the start control section 41 and the heating control section 40 described with reference to the embodiment of Fig. 4 are substantially included in the microcomputer 54. The timing control of the radio wave output P₀ such as shown in Fig. 6A or 6B is executed in accordance with a control program by this microcomputer 54. This control is easily realized by applying a detection signal from the thermistor 42 as an input signal to the microcomputer 54 in the case where the start control section 41 includes a sensor like the thermistor 42 as shown in the embodiment of Fig. 7. Further, in the case where the start control section 41 includes the stop time counter 45 and the ts counter 46 as in Fig. 8, all the functions of the start control section 41 are realized by the microcomputer 54. Any way, if the present invention is embodied as shown in Fig. 10 by using the microcomputer 54, the circuit construction is simplified and becomes compact, thus realizing high reliability due to reduced interconnections, etc. In Fig. 10, the step-up transformer 27 is provided with a high-voltage detection winding 50 as a fourth winding making up a high-voltage detector for producing a voltage proportional to a voltage across the high-voltage secondary winding 48. A detection signal from this high-voltage detection winding is applied to a fault decision section 51, in which the detection signal is compared with a reference signal upon the lapse of a predetermined time after the start of the heating apparatus which is counted by a timer (not shown) contained in the microcomputer 54. The result of this comparison is supplied to a safety circuit (safety means) 52. Referring to Fig. 14C, the fault decision section 51 decides whether VAK (that is, a detection signal) is larger than a reference signal (that is, Vth in Fig. 14C) and produces a result of decision at a predetermined time point between the time points t₁ and t₂ shown in Fig. 14C. The resulting signal is applied to the safety circuit (safety means) 52, which, if the voltage VAK is larger than the reference signal Vth, indicates the fact on the indicator 53 and sends a signal to the control section 34, thereby turning off the transistor 28 and de-energizing the power converter 33. Firstly, a conventional starting operation of a high-frequency heating apparatus will be explained with reference to Figs. 14A, 14B and 14C. As shown in Fig. 14A, the voltage value Vs of the reference voltage 38 in Fig. 13, which illustrates the construction of the control section 34 in further detail, was kept at a low value Vs1 during a time period tst, and the voltage value Vs was controlled to become an original set value of Vs2 after the lapse of the time tst (say, 3 seconds). As a result of this control, the input current Iin is controlled to be 2 A (the output P₀ is almost zero) during the period tst as shown in Fig. 14B, and thereafter it is controlled to be mainttained at 12 A (the output P₀ is 600 W). This control is effected to prevent the anode-to-cathode voltage VAK of the magnetron 32 from becoming excessive, before the completion of heating of the cathode of the magnetron 32. Fig. 14C shows the manner in which the voltage VAK changes in this process. Namely, the voltage VAK, immediately after the start of the heating apparatus when the cathode of the magnetron 32 is not yet fully heated, assumes the value of 7 KV for Iin of 2 A. After the lapse of tso, the cathode is fully heated to cause the magnetron to oscillate, and then the voltage VAK is reduced to about 4 KV and reaches a steady operation voltage of the magnetron. Even with an subsequent increase of Iin to 12 A, the VAK is kept to be about 4 KV, while, only the radio wave output is increased to 600 W, thus making it possible to maintain a normal operation. In this way, by switching the level Vs of the reference voltage 38 by a timer means provided in the control section 34, the apparatus may effect its cold starting without generating any abnormally high voltage before the cathode of the magnetron 32 is heated. If all the parts (especially including high-voltage circuit parts) are normal, a steady state is reached with the anode-to-cathode voltage VAK undergoing a change as shown by a solid line in Fig. 14C. However, in an abnormal state (for example, in such a case where one of the cathode terminals of the magnetron 32 is not connected), the anode-to-cathode voltage VAK undergoes a change as shown by a dashed line in Fig. 14C, generating an abnormally high voltage of 15 to 20 KV. This not only makes it impossible to obtain a radio wave output, but also generates a very dangerous discharge phenomenon. If the housing is not fully grounded, in particular, the potential of the housing reaches an abnormally high level by a discharge phenomenon, thereby giving rise to a high possibility of posing a danger to the operator. However, by arranging in the apparatus the above-described fault decision section 51, safety circuit 52 and indication section 53 shown in Fig. 10, it becomes possible to stop the operation of the transistor 28 and prevent the generation of an abnormally high voltage, thus guaranteeing high safety. It is thus possible either to indicate the generation of an abnormally high voltage due to a fault or a connection failure of the parts of the high-voltage circuit and/or to prevent the generation of such an abnormally high voltage. As a result, an accident such as the generation of a discharge phenomenon or electrical shock is prevented, thereby assuring safety upon occurrence of a fault of the parts. Especially when the power converter is constructed to stop its operation in case of a trouble, a fault of the parts or a smoking or firing accident thereof which might be caused by a discharge or excessive conduction of current is also prevented. Conflicts, if any, between the logical decision on a trouble or the stop or indication of the operation and the specifications of the cooking sequence control may be easily overcome by the double service of the microcomputer 54. Also, the operation of the power converter 33 is easily stopped by using a cooking sequence control relay or the like without adding any new part. Fig. 11 is a circuit diagram showing a more detailed embodiment of the fault decision section 51, the safety circuit 52 and the indicator 53. In Fig. 11, a detection voltage from the high-voltage detection winding 50 is converted into a DC voltage by a diode 64, a resistor 65 and a capacitor 66, and it is compared with a reference voltage in a comparator 67. This reference voltage 68 corresponds to the above-described voltage Vs shown in Fig. 14A. An output of the comparator 67 is applied to the microcomputer 54. After the lapse of a predetermined time after the start of the heating apparatus, the microcomputer 54, by its logical operation, reads the output of the comparator 67 and decides whether VAK is larger than Vth. If VAK is larger than Vth, it decides that a fault is involved and causes the indicator 53 to inform the fault. The microcomputer 54 also serves as a microcomputer for effecting the cooking sequence control of the high-frequency heating apparatus, in such a manner that the contact 57 of a relay 55 is opened or closed to control the control section 34 at the same time. This construction is adapted for the magnetron output control to execute the cooking sequence control. The high-voltage detection winding 50 is insulated electrically from the high-voltage output circuit of the step-up transformer 27, and therefore the potential of the microcomputer 54 is insulated from the high-voltage output circuit. As a result of this insulating construction, there occurs no potential conflict between the high-voltage circuit and the microcomputer circuit, thereby assuring very high safety. Fig. 12 is a circuit diagram showing a further detailed embodiment of the fault decision circuit 51, the safety circuit 52, the indicator 53 and the control section 34. In Fig. 12, in the control section 34, a resistor 73 is supplied with an output signal of the high-voltage detection winding 50 through a diode 72. The resistor 73 is also supplied with an output signal from a current transformer 36 through a diode 74. Thus, the pulse width modulation circuit 39 functions so that a greater one between a detection output signal from the high-voltage detection winding 50 and a detection output signal from the current transformer 36 becomes equal to the reference voltage 38. At the time of the start of the heating apparatus, therefore, VAK is controlled to a value below a certain level, and, when the magnetron oscillates, the input current is controlled to take a predetermined value. The high-voltage detection winding 50, in addition to the above-mentioned function, also supplies a detection signal to the comparator 67 where the detection signal is compared with the reference signal 68 to determine whether an abnormally high voltage is generated or not. The resulting signal is supplied to the microcomputer 54 as an electrically insulated signal through photocouplers 80a and 80b. In this way, the microcomputer 54 is electrically insulated from both the high-voltage circuit and the electric power converter thereby to secure high safety. As described above, the heating control section 40, the start control section 41 and the indicator 47 are component parts involving many logical operations or time control elements. Therefore, if a portion or all of these component parts are made up of a control means including logical operation means such as a microcomputer, the whole apparatus can be greatly simplified and reduced in cost. A rise signal is not necessarily supplied from the start control section 41 to the heating control section 40. Instead, a similar signal equivalent to the electromagnetic wave output P₀ may be supplied from the control section 34 or the like. Further, the heating time control of the heating control section in the above-mentioned embodiments relates only to the maximum output of the high-frequency heating apparatus. By means of a well-known interruption operation, however, similar heating time control may be effected in a case where the average output value is controlled to be about 200 W in the case of effecting a de-freezing operation. It will thus be understood from the foregoing description that, according to the present invention, by comprising a power supply, a power converter, a radio wave radiation section and a start control section for increasing the electromagnetic wave energy in an initial stage of operation as compared with an amount thereof in a steady operation state, excessive quality may be prevented reasonably and economically, while securing safety and reliability at the same time. Further, even when the electromagnetic wave output changes with the apparatus conditions, the heating control section completely releases the operator from the trouble of being worried about it and makes it possible to operate the apparatus in the same manner as if the output remains unchanged. A very high operation efficiency of a high-frequency heating apparatus is thus realized. Furthermore, a logical operation means or a temperature detector, if inserted in the heating control section, can detect the temperature of the power supply section, the electric power converter and the radio wave radiation section at the time of the start of the operation. The optimum output determined as a result of the detection improves the efficiency of the heating operation to have a maximum value. In addition, the apparatus comprises a high voltage detector for detecting an output voltage of a step-up transformer directly or indicrectly, a fault decision section for making a comparison between a reference signal and an output signal of the high-voltage detector which is generated after the lapse of a predetermined time from the start of the operation of the apparatus, safety means for performing at least one of the indication of a fault and the stopping of the operation of the electric power converter in response to the application thereto of a fault decision signal from the fault decision section, and further a microcomputer for performing cooking sequence control and also serving to perform at least a part of the functions of the fault decision section and the safety means. Because of this construction, the generation of an abnormally high voltage that may be caused by a fault of component parts or any assembly error can be informed and/or stopped. A trouble such as a fault of component parts, therefore, can be prevented from leading to a fire, electrical shock or other serious accidents, thereby realizing a high-frequency heating apparatus which assures very high reliability and safety. These processes of fault decision or indication or the stopping of high-voltage generation can be easily accomplished at very low cost without requiring an addition of any new relay in a manner free from its conflicts with the cooking sequence control.
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A high-frequency heating apparatus comprising: electric power supply means (24) selected from at least one of a commercial power supply, a battery and an electric generator; high voltage electric power conversion means (33) having voltage step-up means (27) for converting electric power supplied from said electric power supply means (24) into high voltage electric power: electromagnetic wave radiation means (32) arranged to receive the high voltage electric power from said high voltage electric power conversion means (33) and to radiate an electromagnetic wave; and operating condition control means (34) for controlling the operating condition of said high voltage electric power conversion means (33), characterized by comprising increased output control means (41) for controlling the operation of said operating condition control means (34) so as to make the electromagnetic wave output during a limited time period have a level higher than that of a maximum electromagnetic wave output in a steady operation state of said heating apparatus under a continuously operable condition. A high-frequency heating apparatus according to claim 1, wherein said increased output control means (41) includes timer means (45, 46) for controlling the limited time period during which the electromagnetic wave output has a level higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 2, wherein said timer means (45, 46) is constructed to enable adjustable time setting, thereby making it possible to adjust the limited time period during which the electromagnetic wave output has a level higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 1, wherein said increased output control means (41) includes stop state detection means (42, 45) for detecting a stop state of said heating apparatus so that an output signal of said stop state detection means (42, 45) is used to adjust the limited time period during which the electromagnetic wave output has a level higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 4, wherein said stop state detection means (42, 45) includes temperature detection means (42) for detecting the temperature of at least one of said electromagnetic wave radiation means (32), heat dissipating parts of said high voltage electric power conversion means (33) and the ambient air thereof so that a detection output signal of said temperature detection means (42) is used to adjust the limited time period during which the electromagnetic wave output has a level higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 4, wherein said stop state detection means (42, 45) includes stop time timer means (45) for measuring a time period during which said heating apparatus has substantially stopped the heating operation so that an output signal of said stop timer means is used to adjust the limited time period during which the electromagnetic wave output has a level higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 1, further comprising increased output indication means (47) for indicating that said electromagnetic wave radiation means (32) is radiating an electromagnetic wave whose output level is higher than that of the maximum electromagnetic wave output in the steady operation state of said heating apparatus under the continuously operable condition. A high-frequency heating apparatus according to claim 1, wherein said electromagnetic wave radiation means (32) is composed of a magnetron, and said high voltage electric power conversion means (33) is composed of an inverter circuit having one or more semiconductor switching elements (28). A high-frequency heating apparatus according to claim 1, wherein said increased output control means (41) comprises temperature determining means (42, 43, 44) arranged so that said increased output control means (41) is operable to control the operation of said operating condition control means (34) so as to make the electromagnetic wave output have a level higher than that of a maximum electromagnetic wave output in a steady operation state of said heating apparatus under a continuously operable condition during a limited time period in which said temperature determining means (42, 43, 44) determines that the temperature of at least one of said electromagnetic wave radiation means (32), heat dissipating parts of said high voltage electric power conversion means (33) and the surrounding air of each thereof is lower than a predetermined temperature. A high-frequency heating apparatus according to claim 9, wherein said temperature determining means (42, 43, 44) includes temperature detection means (42) for detecting the temperature of at least one of said electromagnetic wave radiation means (32), the heat dissipating parts of said high voltage electric power conversion means (33) and the surrounding air of each thereof.
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MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
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BESSHO DAISUKE; MAEHARA NAOYOSHI; MATSUMOTO TAKAHIRO; NIWA TAKASHI; SAKAMOTO KAZUHO; SUENAGA HARUO; YAMAGUCHI KIMIAKI; YOSHINO KOUJI; BESSHO, DAISUKE; MAEHARA, NAOYOSHI; MATSUMOTO, TAKAHIRO; NIWA, TAKASHI; SAKAMOTO, KAZUHO; SUENAGA, HARUO; YAMAGUCHI, KIMIAKI; YOSHINO, KOUJI
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EP-0489912-B1
| 489,912 |
EP
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B1
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EN
| 19,960,918 | 1,992 | 20,100,220 |
new
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C08L67
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C08L25, C08L55
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C08L67, C08L51
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C08L 51/04+B, C08L 67/02+B
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THERMOPLASTIC RESIN COMPOSITION
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A thermoplastic resin composition excellent in the resistance to chemicals and impact, which comprises specified proportions of: (A) a saturated polyester resin, (B) a rubber-reinforced styrenic resin comprising a copolymer of a vinylic monomer, a vinylcyanide monomer and, if necessary, another copolymerizable vinylic monomer, (C) an epoxy-modified copolymer comprising an aromatic vinylic monomer, a vinyl cyanide monomer, an ethylenically unsaturated epoxide monomer and, if necessary, another copolymerizable vinylic monomer, and (D) a styrenic copolymer comprising an aromatic vinylic monomer, a vinyl cyanide monomer and, if necessary, another copolymerizable vinylic monomer, wherein the content of the rubbery copolymer is 5 to 40 % by weight and that of the ethylenically unsaturated epoxide monomer is at least 0.001 % by weight, each based on the whole composition.
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The present invention relates to a thermoplastic resin composition which comprises a polyester resin, a rubber-reinforced styrene base resin and an epoxy-modified copolymer and is excellent in chemical resistance and impact resistance (namely notched Izod impact resistance). Styrene base resins such as polystyrene, styreneacrylonitrile copolymers, ABS resins, and AES or AAS resins comprising EPDM rubber or acryl rubber as a rubber component have good property balance and dimensional stability and are used in various fields. In particular, they are used in the automobile industries. In this application, they should have chemical resistance such as resistance to gasoline and brake fluids, and improvement of such resistance is important. As a polymer having good chemical resistance, a saturated polyester resin is known. Since the saturated polyester resin has poor impact strength, it is proposed to compound the ABS resin therein (see Japanese Patent Publication Nos. 30421/1972 and 25261/1976). However, such resin composition does not have sufficient impact resistance. As a result of the extensive study on the improvement of the above properties of the composition comprising the saturated polyester resin and the styrene base resins, it has been found that a thermoplastic resin composition having good chemical resistance and (notched Izod) impact strength is obtained by blending a saturated polyester, a styrene base resin and a specific epoxy-modified copolymer in a specific ratio. Accordingly, the present invention provides a thermoplastic resin composition comprising: (A) a saturated polyester resin, (B) a graft polymerized or a rubbery polymer of a rubber-reinforced styrene base resin which is obtainable by polymerizing 50 to 90 % by weight of an aromatic vinyl monomer, 10 to 50 % by weight of a cyanated vinyl monomer and 0 to 40 % by weight other copolymerizable vinyl monomer in the presence of a rubbery polymer, (C) an epoxy-modified copolymer which comprises 50 to 89.9 % by weight of an aromatic vinyl monomer, 10 to 49.9 % by weight of a cyanated vinyl monomer, 0.1 to 20 % by weight of an ethylenically unsaturated epoxy group-containing monomer and 0 to 39.9 % by weight of other copolymerizable vinyl monomer, and (D) a styrene base copolymer which comprises 60 to 85% by weight of α-methylstyrene, 0 to 20% by weight of styrene, 15 to 40% by weight of a cyanated vinyl monomer and 0 to 25% by weight of at least one other copolymerizable vinyl monomer selected from the group consisting of alkyl unsaturated carboxylates and imide monomers, wherein a content of said saturated polyester resin (A) is from 90 to 10 parts by weight, a total content of said rubber-reinforced styrene base resin (B) and said epoxy-modified copolymer (C) is from 90 to 10 parts by weight and a content of said styrene base copolymer (D) is from 5 to 60 parts by weight based on 100 parts by weight of the total weight of the polymers (A), (B), (C) and (D), and a content of said rubbery polymer is from 5 to 40 % by weight and a content of said ethylenically unsaturated epoxy group-containing monomer is at least 0.001 % by weight based on the whole weight of the composition. The present invention will be explained in detail. As the saturated polyester resin (A) to be used in the present invention, polyethylene terephthalate, polybutylene terephthalate, a polyester-ether block polymer comprising a hard segment of polyester and a soft segment of polyether and the like are exemplified. The saturated polyester resin (A) can be prepared from 1,4-butanediol and terephthalic acid, or dimethyl terephthalate and ethylene glycol. They may be used independently or as a mixture of two or more of them. The rubber-reinforced styrene base resin (B) is prepared by graft polymerizing 50 to 90 % by weight of an aromatic vinyl monomer, 10 to 50 % by weight of a cyanated vinyl monomer and 0 to 40 % by weight other copolymerizable vinyl monomer in the presence of a rubbery polymer. Examples of the rubbery polymer are polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, acrylate base copolymer and chlorinated polyethylene, each having a glass transition temperature of 0°C or lower. They may be used independently or as a mixture of two or more of them. They may be prepared by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like. In case of the emulsion polymerization, there is no specific limitation on a particle size and a gel content of the rubbery copolymer. Preferably, an average particle size is from 0.1 to 1 µm and a gel content is from 0 to 95 %. Examples of the aromatic vinyl monomer are styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert.-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene and the like, and examples of the cyanated vinyl monomer are acrylonitrile, methacrylonitrile, fumaronitrile and the like. They may be used independently or as a mixture of two or more of them. Among them, styrene, α-methylstyrene and acrylonitrile are preferred. As the other copolymerizable monomer, are exemplified alkyl unsaturated carboxylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate and the like; and imide monomers such as maleimide, N-phenylmaleimide, N-methylmale-imide, N-cyclohexylmaleimide and the like. They may be used independently or as a mixture of two or more of them. When the monomer contents are outside the above ranges, compatibility between the rubber-reinforced styrene base resin (B) and the epoxy-modified copolymer (C) is deteriorated, so that the composition comprising them and the saturated polyester resin (A) has decreased impact strength. There is no specific limitation on a ratio of the rubbery polymer to the monomers. Preferably, 20 to 80 % by weight of the rubbery polymer and 80 to 20 % by weight of the monomers are used. Also there is no specific limitation on a graft degree. Preferably, the graft degree is from 20 to 100 %. The graft polymerization can be carried out by conventional emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or combinations thereof. The epoxy-modified copolymer (C) may be prepared by polymerizing 50 to 89.9 % by weight of an aromatic vinyl monomer, 10 to 39.9 % by weight of a cyanated vinyl monomer, 0.1 to 20 % by weight of an ethylenically unsaturated epoxy group-containing monomer and 0 to 39.9 % by weight of other copolymerizable vinyl monomer. Preferably, 59.9 to 80 % by weight of the aromatic vinyl monomer, 19.9 to 40 % by weight of the cyanated vinyl monomer and 0.1 to 15 % by weight of the ethylenically unsaturated epoxy group-containing monomer are polymerized. When the monomer contents are outside the above ranges, the copolymer (C) has decreased compatibility with the rubber-reinforced styrene base resin (B). Examples of the aromatic vinyl monomer, the cyanated vinyl monomer and the other copolymerizable vinyl monomer are the same as exemplified in connection with the rubber-reinforced styrene base resin (B). They may be used independently or as a mixture of two or more of them. Among them, styrene, α-methylstyrene and acrylonitrile are preferred. In particular, α-methylstyrene and acrylonitrile are preferred. The unsaturated epoxy monomer is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in a molecule. It includes an unsaturated glycidyl ester of the formula: wherein R is a hydrocarbon group having a polymerizable ethylenically unsaturated bond, an unsaturated glycidyl ether of the formula: wherein R is the same as defined in the formula (I), and X is a divalent group: -CH2-O- or and an epoxyalkene of the formula: wherein R is the same as defined in the formula (I), and R' is hydrogen or methyl. Specific examples of these epoxide monomers are glycidyl acrylate, glycidyl methacrylate, mono- and di-glycidyl ester of itaconic acid, mono-, di- and tri-glycidyl ester of butenetricarboxylic acid, mono- and di-glycidyl ester of citraconic acid, mono- and di-glycidyl ester of endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (trade name: Nadic acid), mono- and di-glycidyl ester of endo-cis-bicyclo[2.2,1]hept-5-ene-2-methyl-2,3-dicarboxylic acid (trade name: Methylnadic acid), mono- and di-glycidyl ester of allylsuccinic acid, glycidyl ester of p-styrene-carboxylic acid, allylglycidyl ether, 2-methylallylglycidyl ether, styrene-p-glycidyl ether or p-glycidylstyrene, 3,4-epoxy-l-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and the like. The epoxy-modified copolymer (C) may be prepared by conventional emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or combinations thereof. The ethylenically unsaturated epoxy group-containing monomer may be added in any suitable manner. It can be added to a polymerization system as a mixture with other monomer(s), or in the form of an aqueous solution. There is no limitation on a molecular weight of the epoxy-modified copolymer (C). Preferably, it has a weight average molecular weight of from 10,000 to 1,000,000. The styrene base copolymer (D) is prepared by copolymerizing 60 to 85% by weight of α-methylstyrene, 0 to 20% by weight of styrene, 15 to 40% by weight of a cyanated vinyl monomer and 0 to 25% by weight of at least one other copolymerizable vinyl monomer selected from the group consisting of alkyl unsaturated carboxylates and imide monomers. Examples of the cyanated vinyl monomer are the same as exemplified in connection with the rubber-reinforced styrene base resin (B). They may be used independently or as a mixture of two or more of them. Specific examples of the copolymer (C) are styrene-acrylonitrile copolymer, a-methylstyrene-acrylonitrile copolymer, styrene-a-methylstyrene-acrylonitrile copolymer, styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methyl-styrene-acrylonitrile-N-phenhylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide-methyl methacrylate copolymer, a-methylstyrene-acrylonitrile-N-phenylmaleimide-methyl methacrylate copolymer and the like. Contents of the saturated polyester resin (A), the rubber-reinforced styrene base resin (B), the epoxy-modified copolymer (C) and the styrene base copolymer (D) are from 90 to 10 parts of (A), from 90 to 10 parts of (B) + (C), and from 5 to 60 parts by weight of (D) based on 100 parts by weight of the total weight of the polymers (A), (B), (C) and (D). Outside these ranges, good balance between the chemical resistance and impact strength which is one of the characteristics of the thermoplastic resin composition is not achieved. Preferably, the composition comprises 15 to 70 parts by weight of (A), 85 to 30 parts by weight of (B) + (C) and up to 60 parts by weight of (D). In view of impact strength and heat resistance, the composition comprises the styrene base copolymer (D) comprising 60 to 85 % by weight of α-methylstyrene, 0 to 20 % by weight of styrene, 15 to 40 % by weight of the cyanated vinyl monomer and 0 to 25 % by weight of the other copolymerizable vinyl monomer. Also, in view of heat resistance, preferably the composition comprises the styrene base copolymer (D) comprising 20 to 60 % by weight of the aromatic vinyl monomer, 10 to 40 % by weight of the cyanated vinyl monomer, 5 to 65 % by weight of of the imide monomer and 0 to 50 % by weight of the other copolymerizable vinyl monomer (except the imide monomer). In the present invention, contents of the rubbery polymer and the ethylenically unsaturated epoxy group-containing monomer in the composition are important. When the content of the rubbery polymer is less than 5 % by weight of the whole composition, the impact resistance is deteriorated, while it is larger than 40 % by weight, moldability of the composition is deteriorated. Preferably, the content of the rubbery polymer is from 5 to 30 % by weight. When the content of the ethylenically unsaturated epoxy group-containing monomer is less than 0.001 % by weight, the epoxy-modified copolymer (C) has decreased compatibility with the saturated polyester (A). Preferably, this content is at least 0.1 % by weight. There is no specific limitation on a mixing sequence and states of the saturated polyester resin (A), the rubber-reinforced styrene base resin (B), the epoxy-modified copolymer (C) and the styrene base copolymer (D). For example, these four components may be mixed simultaneously in the form of pellets, beads or powder, or specific components are premixed and then other component(s) are mixed. As mixing means, any of conventional mixing apparatuses such as a Banbury mixer, rolls or an extruder may be used. If desired, the thermoplastic resin composition of the present invention may contain additives, reinforcing materials or fillers such as an antioxidant, an ultraviolet light absorbing agent, a light stabilizer, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant, a mold release agent, glass fibers, metal fibers, carbon fibers, metal flakes and the like. In addition, the composition of the present invention may contain other thermoplastic resins such as polyacetal, polycarbonate, polyamide, polyphenyleneoxide, polymethyl methacrylate, polyvinyl chloride, etc. The present invention will be illustrated by following Reference Examples, Examples and Comparative Examples, which will not limit the scope of the present invention. In Examples, parts and % are by weight. Reference Example 1 Polyester resin (A)A-1: Polyethylene terephthalate (PET) RY-560 (manufactured by Toyo Boseki). A-2: Polybutylene terephthalate (PBT) N-1000 (manufactured by Mitsubishi Rayon). A-3: Polybutylene terephthalate (PBT) N-1200 (manufactured by Mitsubishi Rayon). Reference Example 2 Rubber-reinforced styrene base resin (B)B-1: Acrylonitrile (12 parts) and styrene (28 parts) are copolymerized in the presence of a polybutadiene latex having an average particle size of 0.45 µm and a gel content of 83 % (60 parts of solid content) to obtain an ABS graft polymer latex (graft degree: 35 %, an intrinsic viscosity of free acrylonitrile-styrene copolymer: 0.33). The intrinsic viscosity was measured in dimethylformamide at 30°C. (unit: 100 ml/g). B-2: In the same manner as in B-1, an ABS graft copolymer latex comprising polybutadiene (50 parts), acrylonitrile (15 parts) and styrene (35 parts) was prepared (graft degree: 55 %, an intrinsic viscosity of free acrylonitrile-styrene copolymer: 0.58). B-3: Acrylonitrile (15 parts) and styrene (35 parts) are emulsion copolymerized in the presence of a polybutyl acrylate latex having an average particle size of 0.3 µm (50 parts of solid content) to obtain an AAS graft polymer latex (graft degree: 50 %, an intrinsic viscosity of free acrylonitrile-styrene copolymer: 0.63). B-4: An AES graft copolymer (graft degree: 52 %, an intrinsic viscosity of free acrylonitrile-styrene copolymer: 0.60) was prepared by solution polymerizing ethylene-propylene-ethyllidenenorbornene copolymer (EPDM) (iodine value: 21, Mooney viscosity: 75, propylene content: 50 %) (50 parts), acrylonitrile (15 parts) and styrene (35 parts). Each of the graft copolymers B-1, B-2 and B-3 was separated and recovered by adding one part of Sumilizer NW (1 part) as an antioxidant and two parts of trisnonylphenyl phosphite per 100 parts of the solid content in the latex and salting out the copolymer with magnesium sulfate to recover the copolymers. The graft copolymer B-4 was precipitated in methanol followed by separation and recovering. Reference Example 3 Epoxy-modified copolymer (C)C-1: In a reactor which had been replaced with nitrogen, pure water (120 parts) and potassium persulfate (0.3 part) were charged and heated up to 65°C while stirring. Then, a monomer mixture solution of acrylonitrile (30 parts), styrene (65 parts), glycidyl methacrylate (5 parts) and tert.-dodecylmercaptan (0.3 parts) and an aqueous solution of emulsifier (30 parts) containing sodium dodecylsulfonate (2 parts) were continuously poured over 5 hours, respectively. Thereafter, the polymerization system was heated up to 70°C and aged for 3 hours to complete polymerization to obtain a copolymer having an intrinsic viscosity of 0.56 (in dimethylformamide at 30°C). C-2: In the same manner as in C-1, a copolymer comprising acrylonitrile (30 parts), α-methylstyrene (65 parts) and glycidyl methacrylate (5 parts) and having an intrinsic viscosity of 0.53 was prepared. C-3: In the same manner as in C-1, a copolymer comprising acrylonitrile (23 parts), α-methylstyrene (52 parts) and glycidyl methacrylate (25 parts) and having an intrinsic viscosity of 0.68 was prepared. Each epoxy-modified copolymer was salted out with calcium chloride and then recovered. Reference Example 4 Styrene base copolymer (D)In the same manner as in C-1, copolymers D-1 to D-5 having the following compositions were prepared: D-1 D-2 D-3 D-4 D-5 STY705540 AMS7060 ACN3030202020 N-PMI252010 MMA30 Intrinsic viscosity0.550.530.600.490.51 STY: Styrene AMS: α-Methylstyrene ACN: Acrylonitrile N-PMI: N-Phenylmaleimide MMA: Methyl methacrylate. Each of the styrene base copolymer D-1 to D-5 was salted out with magnesium sulfate and then recovered. Examples and Comparative ExamplesThe saturated polyester (A), the rubber-reinforced styrene base resin (B), the epoxy-modified polymer (C) and the styrene base copolymer (D) shown in Reference Examples were compounded in a ratio shown in Table 1 and granulated with a twin screw extruder of 40 mm. The granulating temperature was 250°C. The physical properties of each resin composition were measured as follows and the results are shown in Table 2: Notched Izod impact strengthAccording to ASTM D-256 (23°C). Chemical resistanceFlexural stress of 30 mm was applied on a molded article of 150 mm X 20 mm X 3mm which was fixed to a cantilever beam jig. Thereafter, the article was dipped in a chemical for 24 hours and the presence of cracked was observed. A test piece used in the above tests was molded with a 3.5 ounce injection molding machine at a cylinder temperature of 250°C. Examples 1-6, 17 and 18 and Comparative Examples1-3 These Examples show the effect of the epoxy-modified copolymer (C), and also the effect of the use of the α-methylstyrene base copolymer as the component (D). Examples 7 and 8 and Comparative Example 4 These Examples show the effect of the use of various saturated polyesters (A). Examples 9-11 and Comparative Examples 4 and 5These Examples show the effect of amounts of the saturated polyester (A). Examples 12, 13 and 14These Examples show the effect of the use of various rubber-reinforced styrene base resins. Examples 15 and 16 and Comparative Example 6These Examples show the effect of amounts of the rubber in the whole composition. Examples 19 and 20These Examples show the effect of the use of the maleimide base copolymer as the component (D). Example No. Chemical resistance Impact strength at 23°C (kg.cm/cm) Heat resistance (°C) DOP Brake fluid Salaid oil 1OOO33.185 2OOO54.285 3OOO52.786 4OOO45.387 5OOO58.593 6OOO56.193 C. 1OOO12.384 C. 2OOO13.592 C. 3OOO8.286 7OOO48.385 8OOO57.987 C. 4XXΔ23.182 9OOO42.386 10OOO59.283 1100063.181 C. 5OOO4.568 12OOO65.983 13OOO43.782 14OOO61.385 15OOO17.387 16OOO14.787 C. 6OOO4.888 17OOO48.386 18OOO53.192 19OOO58.592 20OOO69.098 21OOO55.385
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A thermoplastic resin composition comprising: (A) a saturated polyester resin, (B) a rubber-reinforced styrene base resin which is obtainable by graft polymerizing 50 to 90 % by weight of an aromatic vinyl monomer, 10 to 50 % by weight of a cyanated vinyl monomer and 0 to 40 % by weight of other copolymerizable vinyl monomers in the presence of a rubbery polymer; (C) an epoxy-modified copolymer which comprises 50 to 89.9 % by weight of an aromatic vinyl monomer, 10 to 49.9 % by weight of a cyanated vinyl monomer, 0.1 to 20 % by weight of an ethylenically unsaturated epoxy group-containing monomer and 0 to 39.9 % by weight of other copolymerizable vinyl monomers, and (D) a styrene base copolymer which comprises 60 to 85 % by weight of α-methylstyrene, 0 to 20 % by weight of styrene, 15 to 40 % by weight of a cyanated vinyl monomer and 0 to 25 % by weight of at least one other copolymerizable vinyl monomer selected from the group consisting of alkyl unsaturated carboxylates and imide monomers, wherein a content of said saturated polyester resin (A) is from 90 to 10 parts by weight, a total content of said rubber-reinforced styrene base resin (B) and said epoxy-modified copolymer (C) is from 90 to 10 parts by weight and a content of said styrene base copolymer (D) is from 5 to 60 parts by weight based on 100 parts by weight of the total weight of the polymers (A), (B), (C) and (D), and a content of said rubbery polymer is from 5 to 40 % by weight and a content polymer is from 5 to 40 % by weight and a content of said ethylenically unsaturated epoxy group-containing monomer is at least 0.001 % by weight based on the whole weight of the composition.
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SUMITOMO DOW LTD; SUMITOMO DOW LIMITED
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HIRAI HIKOICHI; HIRAI MIKIO; HIRAI, HIKOICHI; HIRAI, MIKIO
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EP-0489913-B1
| 489,913 |
EP
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B1
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EN
| 19,970,312 | 1,992 | 20,100,220 |
new
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G05B13
| null |
G06N7, G06N5, G05B13
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G06N 7/02T, G05B 13/02C2, G06N 7/04A, G06N 5/04G
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FUZZY CONTROL APPARATUS CAPABLE OF CHANGING RULE AND ITS OPERATION METHOD, AND CONTROL SYSTEM SWITCH-CONTROLLED BY FUZZY INFERENCE AND ITS CONTROL METHOD
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In a fuzzy control apparatus capable of changing the rule during its operation, a sample-and-hold circuit (13) stores the fuzzy inference output of a fuzzy control circuit (10) immediately before the rule change; and an output switching circuit (20) synthesizes a fuzzy control output from the fuzzy inference output stored immediately before the rule change and the fuzzy inference output after the rule change so that the ratio of the fuzzy inference output immediately before the rule change to the fuzzy control output may decrease with the lapse of time from the rule change, in other words, the ratio of the fuzzy inference output after the rule change to the fuzzy control output may increase, and outputs only the fuzzy inference output after the rule change as the fuzzy control output after a predetermined period of time from the rule change. In this manner, the drastic change of the output at the time of the rule change can be prevented and smooth switching can be made.
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Technical FieldThis invention relates to a fuzzy control apparatus, and to a method of operating the same, in which rules are capable of being changed during execution (operation) of fuzzy reasoning. Background ArtA fuzzy control apparatus is provided with an input of a controlled variable from a controlled object, executes so-called modus ponens reasoning, and outputs a manipulated variable (a fuzzy-control output) to be applied to the controlled object. Fuzzy reasoning often is expressed by control rules ( If..., then... rules) in an If..., then... format. A fuzzy control apparatus is available in which the control rules can be changed by a manual or remote operation during execution (operation) of fuzzy reasoning. In a fuzzy control apparatus of this kind, there is the possibility that the fuzzy-control output will vary suddenly according to the content of a changed rule. When a fuzzy-control output undergoes a sudden change, there is the danger that the controlled object will be adversely affected. From GB-A-2 211 324 a recurrent type inference apparatus is known in which a synthesized membership function is synthesized by combining weighted membership functions with a previously-synthesized membership function synthesized in a previous iteration cycle. From EP-A-0 268 182 a fuzzy computer including a fuzzy inference engine having a fuzzy membership-function generating circuit using a switch matrix is known. Disclosure of the InventionAn object of the present invention is to provide a fuzzy control apparatus, and a method of operating the same, in which a fuzzy-control output can be varied smoothly even in a case where a rule is changed during operation. Another object of the present invention is to provide a fuzzy control apparatus and a method of operating the same, in which a rule is capable of being changed only under a condition that a control output may not be suddenlv varied. A control apparatus according to the invention is as defined in claims 1 and 5. A corresponding method of operating a control apparatus is as defined in claims 3 and 7. In accordance with the present invention as defined in claims 1 and 3, when a rule in the fuzzy control apparatus is changed, the fuzzy reasoning output prevailing just prior to the rule change and the fuzzy reasoning output prevailing following the rule change are combined. In the resulting combination, the percentage of the fuzzy reasoning output prevailing following the rule change gradually increases, while the percentage of the fuzzy reasoning output prevailing just prior to the rule change gradually decreases. As a result, the fuzzy-control output varies smoothly from the value immediately preceding the rule change to the value following the rule change, and therefore a sudden variation is avoided. Accordingly, the controlled object is not adversely affected. Further, since the output of fuzzy reasoning is processed, the foregoing can be accomplished irrespective of the number of rules and the number of inputs. Accordingly, it is unnecessary to modify the construction of the fuzzy reasoning means and therefore the fuzzy control apparatus does not become more complicated in construction. In accordance with the present invention as defined in claims 5 and 7, when a command for changing a rule in the fuzzy control apparatus is applied, it is determined whether the suitability of an input signal with respect to the membership function of an antecedent falls within allowable limits for a rule change. The rule change is carried out only if the suitability falls within the allowable limit, i.e., only when it is determined that the fuzzy reasoning output will not vary suddenly even if the rule change is made. As a consequence, the controlled object is prevented from being adversely affected by a sudden variation in the control output due to the rule change. If a new rule to be changed is set, it is determined automatically whether a sudden variation will not be produced in the fuzzy reasoning output even when the rule is changed. If this condition is satisfied, the rule change is executed. As a result, troublesome monitoring and checking are no longer necessary, and the time required for a rule change can be shortened. Brief Description of the DrawingsFigs. 1 through 3 illustrate a first embodiment of a fuzzy control apparatus, in accordance with the present invention, in which a rule is capable of being changed, wherein ; Fig. 1 is a block diagram illustrating the electrical construction of the fuzzy control apparatus ; Fig. 2 is a timing chart illustrating the operation of each circuit in Fig. 1 ; and Fig. 3 is a flowchart, which illustrates an embodiment wherein the present invention is realized by software, showing the processing procedure of operation control of the fuzzy control apparatus ; Figs. 4 through 10 illustrate a second embodiment of a fuzzy control apparatus, in accordance with the present invention, in which a rule is capable of being changed, wherein : Fig. 4 is a block diagram illustrating the electrical construction of the fuzzy control apparatus ; Fig. 5 is a circuit diagram illustrating some of the circuits contained in an inference unit, shown in Fig. 4, as well as the mutual relationship among these circuits ; Fig. 6 is a circuit diagram showing the concrete construction of a membership-function circuit ; Fig. 7 is a graph showing input/output characteristics of the membership-function circuit ; Fig. 8 is a circuit diagram showing a fuzzy membership-function generating circuit realized using a switch matrix ; Fig. 9 illustrates the concrete construction of a symbol in Fig. 8; and Fig. 10 is a flowchart, which illustrates an embodiment wherein the present invention is realized by software, showing the processing procedure of operation control of the fuzzy control apparatus; Best Mode for Carrying Out the InventionFirst EmbodimentFig. 1, which illustrates an embodiment of a fuzzy control apparatus, in accordance with the present invention, in which a rule is capable of being changed, is a block diagram sowing the electrical construction of the fuzzy control apparatus. Fig. 2 is a timing chart for describing the operation of each circuit in Fig. 1. A fuzzy control circuit 10, which is referred to also as a fuzzy controller or fuzzy reasoning unit, etc., executes fuzzy reasoning in accordance with a predetermined rule ( If..., then... rule). The fuzzy control circuit 10 includes not only special-purpose devices (either of analog or digital type) for fuzzy reasoning (for example, see Nikkei Electronics , July 27, 1987, pp. 148 - 152, published by Nikkei McGraw-Hill), but also binary-type computers and processors programmed so as to execute fuzzy reasoning. The fuzzy control circuit 10 performs fuzzy reasoning, in accordance with a set rule, in dependence upon a given control input (a controlled variable or an offset between a target value and a controlled variable), and generates a fuzzy reasoning output which is the result of this reasoning. The fuzzy reasoning output is applied to a sample/hold circuit 13 and to a coefficient unit (or amplifier circuit) 22 of an output changeover circuit 20, described below. The sample/hold circuit 13 comprises a switch circuit 14, a capacitor 15 and a buffer amplifier 16. The input terminal of the buffer amplifier 16 is connected to the output terminal of the fuzzy control circuit 10 via a switch circuit 14, and to the capacitor 15, one end of which is grounded. The switch circuit 14 is on/off controlled by a control signal provided by a timing control circuit 12, described later. The output of the sample/hold circuit 13 is applied to a coefficient unit (or amplifier circuit) 21 of the output changeover circuit 20. A control rule for fuzzy reasoning in the fuzzy control circuit 10 is set by a rule-setting switch unit 11. The rule set by the rule-setting switch unit 11 is read in the fuzzy control circuit 10 when a switch Sw is turned on. Changing the control rule also is possible as by switch changeover within the rule-setting switch unit 11. The switch Sw is turned on by a setting read-in signal outputted by the timing control circuit 12. The output changeover circuit 20 comprises a function generating circuit 23, the aforementioned coefficient units 21, 22, and an adder 25 which adds the outputs of the coefficient units 21, 22. The function generating circuit 23 outputs a function signal which rises sharply in synchronism with a trigger signal provided by the timing control circuit 12, and which then gradually diminishes in level with the passage of time (e.g., a signal which declines linearly, exponentially or in a step-like manner). The function signal outputted by the function generating circuit 23 is applied to the coefficient units 21 and 22, whose coefficients (or gains) α and 1-α are changed by the function signal, and also applied to the timing control circuit 12. The coefficient α takes on values range from 1 to 0 and varies in the same manner as the above-mentioned function signal. The function generating circuit 23 is provided with a variable resistor 24 for adjusting the time constant of the outputted function signal. As a result, the rate of the decrease in the function value with respect to elapsed time can be determined in suitable fashion. The output of the adder 25 is the control output (manipulated variable) applied to the controlled object. When the control rule is changed during the operation of the fuzzy control circuit 10, the operator changes over the switch in the rule-setting switch unit 11 in such a manner that the desired rule is set. A modification trigger signal is applied to the timing control circuit 12 at the moment the rule is to be changed. The timing control circuit 12 applies a control signal to the switch circuit 14 of the sample/hold circuit 13 in synchronism with the leading edge of the modification trigger signal. As a result, the switch circuit 14 is turned off. Accordingly, the fuzzy reasoning output (voltage) of the fuzzy control circuit 10 prevailing just prior to turn-off of the switch circuit 14 (i.e., just prior to the rule change) is held in the capacitor 15. Next, the setting read-in signal is applied to the switch Sw in synchronism with the trailing edge of the modification trigger signal. As a result, the switch Sw is turned on temporarily and the new rule set in the rule-setting switch unit 11 is accepted by the fuzzy control circuit 10. From this point onward, the fuzzy control circuit 10 executes fuzzy reasoning in accordance with the newly set rule. Further, the timing control circuit 12 applies a trigger signal to the function generating circuit 23 at the trailing edge of the modification trigger signal. The circuit 23 generates the function signal, which rises instantaneously (at which time the coefficient α becomes 1) and then gradually decays. The fuzzy-control output which prevailed just prior to the rule change, and which is being held in the sample/hold circuit 13, is applied to the coefficient unit 21. The fuzzy reasoning output (the output following the rule change) of the fuzzy control circuit 10 is applied to the coefficient unit 22. The coefficient unit 21 delivers the fuzzy reasoning output, which prevailed just prior to the rule change, upon multiplying it by the coefficient α. The coefficient unit 22 delivers the fuzzy reasoning output, which prevails following the rule change, upon multiplying it by the coefficient (1-α). The outputs of the coefficient units 21 and 22 are applied to the adder 25, which adds these outputs and delivers the sum as the fuzzy-control output. The coefficient α decreases monotonously with the passage of time, as shown in Fig. 2. Consequently, when a rule is changed, the percentage of the control output from the output changeover circuit 20 that is occupied by the fuzzy reasoning output prevailing just prior to the rule change gradually diminishes with the passage of time, while the percentage of the control output that is occupied by the fuzzy reasoning output following the rule change gradually increases with the passage of time. Accordingly, the control output does not vary suddenly with a change in the rule but instead varies smoothly from the value just prior to the rule change to the value following the rule change. When the function signal (coefficient α) falls below a predetermined threshold level at elapse of a fixed time from the moment of the rule change, the control signal which the timing control circuit 12 is applying to the switch circuit 14 of the sample/hold circuit 13 is terminated, and therefore the switch 14 is turned on. As a result, the fuzzy reasoning output of the fuzzy control circuit 10 is applied to the sample/hold circuit 13 at all times. Further, since the coefficient α becomes zero or almost zero, the fuzzy reasoning output of the fuzzy control circuit 10 which prevails following the rule change is delivered as the fuzzy-control output through the coefficient unit 22 and adder 25. Fig. 3 is a flowchart illustrating an example of the procedure of the operation of the fuzzy control apparatus in a case where the present invention is realized by software in a computer system. In this case, the fuzzy reasoning also is realized by the software of the computer system. First, a parameter α, which decides the combining ratio (the percentage or weighting for adding of the fuzzy reasoning output just prior to the rule change to the fuzzy reasoning output following the rule change, is cleared (step 31). Next, it is determined (step 32) whether the rule of fuzzy reasoning is to be changed (i.e., whether there is an input of a rule-change command). When the rule is to be changed (YES at step 32), the parameter α is set at 1 and a fuzzy reasoning value OH prevailing just prior to the rule change is stored (steps 33, 34). The rule is then changed (step 35). In a case where there is no rule-change command (inclusive also of a case where a rule change has already been made) (NO at step 32), fuzzy reasoning is carried out in dependence upon the input value, and this reasoning value OF is stored (step 36). Next, the value of the fuzzy-control output is calculated in accordance with the equation α·OH + (1-α)·OF using the parameter α, the stored reasoning value OH prevailing just prior to the rule change, and the current reasoning value OF, and the calculated value is delivered as the control output (step 37). Next, it is determined whether the parameter α is 0 (step 38). If the parameter α is not 0 (NO at step 38), then minute quantity Δα a (0<Δα<1) is subtracted from the current parameter α and the result of the subtraction operation is set as a new parameter α (step 39). It is then determined whether the new parameter α is negative (step 40). If the parameter α is positive (NO at step 40), the program returns to step 32 and the processing of steps 36 - 39 is repeated. As a result, the parameter α gradually decreases with the passage of time. Therefore, in the fuzzy-control output, there is a decrease in the percentage of the fuzzy reasoning output prevailing just prior to the rule change and an increase in the percentage of the fuzzy reasoning output which follows the rule change. When the new parameter α becomes negative, α is forcibly set to 0 (step 41). In a case where the parameter α is 0 (YES at step 38), processing for updating the parameter α is not carried out and the program returns to step 32 so that the processing of steps 36, 37 is repeated. In this case, the fuzzy reasoning value OF prevailing after the rule change becomes the fuzzy-control output, which is delivered. In accordance with the processing procedure of the flowchart shown in Fig. 3, the parameter α gradually decreases incrementally at the fixed value Δα. However, this does impose a limitation upon the invention, for it will suffice if the parameter decreases monotonously. Accordingly, it goes without saying that an arrangement may be adopted in which the parameter α gradually decreases exponentially, by way of example. Second EmbodimentAnother embodiment of a fuzzy control apparatus in which a rule is capable of being changed according to the present invention will now be described. This embodiment relates to a fuzzy controller of the type in which a membership function is expressed by a voltage distribution which appears on a plurality of signal lines. Here the invention is applied to an arrangement which performs fuzzy reasoning by a MIN/MAX operation. Fig. 4 is a block diagram illustrating the fuzzy control apparatus of this embodiment. N-number of inference units 61 -6n, which correspond to the number of set control rules, are provided. Each inference unit 6i (i = 1 - n) is equipped with membership function circuits (hereinafter referred to as MFCs) 70a, 70b, 70c, the number of which (three in this embodiment) is equal to the number of types of input variables xa, xb, xc. These MFCs 70a - 70c, which represent fuzzy sets described by the antecedent in a control rule, output membership-function values (degrees of suitability) with regard to the input variables. The outputs of the MFCs 70a - 70c enter a MIN circuit 71, which subjects these signals to a MIN operation. A circuit (hereinafter referred to as an MFG) 110, which generates a membership function representing a fuzzy set described by the consequent in a control rule, is provided. The MFG 110 outputs a membership function represented by voltages distributed on a plurality (m; for example, 25) outputs lines. The membership function is applied to a MIN circuit (a truncation circuit) 72. The MIN circuit 72 executes a MIN operation between each output value representing the membership function provided by the MFG 110, and the result of the MIN operation outputted by the MIN circuit 71, and outputs a membership function, which represents the results of reasoning, in the form of voltage signals distributed on the m-number of lines (output Ai: i = 1 - n). The results of reasoning A1 - An outputted by the inference units 61 - 6n are applied to a MAX circuit 120. After these results are subjected to a MAX operation, final results of reasoning B are obtained as voltage signals similarly distributed on m-number of lines. A center-of-gravity circuit 130 is provided in order to obtain a definite output (a non-fuzzy output) from the results of reasoning B. In each inference unit 6i, the membership functions in the MFCs 70a - 70c and MFG 110 are set to predetermined shapes and at predetermined positions in dependence upon the control rule. The shape and position of a membership function are capable of being changed. The rule change is realized by changing either the shape or position of a membership function, or both. The positions of the membership functions of the MFCs 70a - 70c are decided by a label voltage VLA, which is outputted by each of label-voltage generating circuits 90a, 90b, 90c. It is possible to change a control rule even during execution of fuzzy reasoning. The three membership functions of the antecedent are set or changed by setting in setting digital switch units 75a, 75b, 75c codes (referred to as labels) of membership functions to be set (or of new membership functions to be changed). These rule codes are latched in a latch circuit 80 at a timing allowed by a rule-change inhibiting control circuit 100, whence they are applied to corresponding label-voltage generating circuit 90a, 90b, 90c, respectively. The setting of the code of the membership function of the consequent is carried out using a digital switch unit 75d. Under the control of the control circuit 100, the code set in the digital switch unit 75d is applied to the MFG 110 after being similarly latched in the latch circuit 80, and the change in the consequent membership function for changing the control rule is carried out. Fig. 5 illustrates a concrete example of the arrangement of, as well as the relationship among, the digital switch unit 75a, the data latch circuit 80, the label-voltage generating circuit 90a, the rule-change inhibiting control circuit 100, and the MFG 110. The code of an antecedent membership function is represented by four bits, and therefore the digital switch unit 75a includes four switches Sw1 - Sw4. The same is true for the other digital switch units 75b, 75c. One ends of the switches Sw1 - Sw4 are connected together and grounded. The other ends of the switches Sw1 - Sw4 are connected to D-input terminals of respective D-type flip-flops 80a - 80d contained in the data latch circuit 80. The other ends of the switches Sw1 - Sw4 are further connected to positive voltage terminals via pull-up resistors R1 - R4, respectively. As a result, in conformity with the on/off states of the switches Sw1 - Sw4, L-, H-level input signals are applied to the D-input terminals of the D-type flip-flops 80a - 80d. The inference unit 61 includes the rule-change inhibiting control circuit 100. The rule-change inhibiting control circuit 100 applies a new rule, which has been set in the digital switch unit 75a, etc. during execution of fuzzy reasoning, to the MFCs 70a - 70c and MFG 110, etc., under conditions in which a sudden fluctuation will not be produced in the control output, and forbids a change in the rule of the MFCs and MFG in a case where the control output will experience a sudden fluctuation. The rule-change inhibiting control circuit 100 is constituted by a comparator 101 and a reference-voltage circuit 102. A voltage representing the result of the MIN operation outputted by the MIN circuit 71 is applied to a positive input terminal of the comparator 101, and a reference voltage outputted by the reference-voltage circuit 102 enters a negative input terminal of the comparator. The output of the comparator 101 is applied to a timing input terminal G of each of the D-type flip-flops 80a - 80d via an inverter 85. When the result of the MIN operation outputted by the MIN circuit 71 is higher than the reference voltage, the rule change by the digital switch unit 75a, etc., causes the fuzzy-control output to vary in a sudden manner. Therefore, in order to prevent this, the H-level output signal of the comparator 101 is applied as an L-level signal to each G input terminal of the D-type flip-flops 80a - 80d via the inverter 85. Accordingly, the flip-flops 80a - 80d will not operate. In a case where the result of the MIN operation outputted by the MIN circuit 71 is lower than the reference voltage, it is judged that the rule change by the digital switch unit 75a, etc., will not cause a sudden variation in the fuzzy-control output. At such time, the output of the comparator 101 is the L level, and therefore an H-level timing signal is applied to the flip-flops 80a - 80d. The flip-flops 80a - 80d latch the code set in the digital switch unit 75a and apply the code L1 - L4 to the label-voltage generating circuit 90a. The rule codes set in the other digital switch units 75b, 75c also are similarly applied to the corresponding label-voltage generating circuits 90b, 90c, respectively, through the latch circuit 80 only in a case where the rule change is allowed by the control circuit 100. The membership function of the consequent is represented by a code of three bits, and therefore the digital switch unit 75d includes three switches. The code that has been set in the digital switch unit 75d also is inputted to the MFG 110 as codes C1, C2, C3 through the latch circuit 80 only in a case where the rule change is allowed by the control circuit 100. The label-voltage generating circuit 90a is constructed by a decoder 91, a switch array 92 and a reference-voltage generating circuit 93. A selecting circuit is constructed by the decoder 91 and the switch array 92. The reference-voltage generating circuit 93 generates seven types of predetermined label voltages (reference voltages) -E3 through E3 and outputs these voltages on respective ones of seven different lines. These label voltages enter the switch array 92. The output voltage of an analog biasing circuit (an arbitrary-voltage generating circuit) 76 which outputs an arbitrary voltage (though a voltage between -E3 and E3) also enters the switch array 92. The four-bit digital code L3, L2, L1, L0 is applied to the decoder 91, as mentioned above. The decoder 91 decodes the code and controls the switch array 92. Specifically, among the eight types of input voltages inclusive of the output voltage of the analog biasing circuit 76 inputted to the switch array 92, that designated by the digital code L3 - L0 is outputted from the switch array 92 as the label voltage VLA. The label voltage VLA is supplied to the MFC 70a. Basically, in accordance with a triangular membership function having a peak at the position of the applied label voltage VLA, the MFC 70a generates an output voltage VOUT representing the corresponding membership-function value when an input voltage (a voltage representing an input variable) VIN is applied. A concrete example of the construction of this MFC 70a is illustrated in Fig. 6. The other MFCs 70b and 70c are similarly constructed. The MFC 70a includes a current source 59 of a current I0 and a multiple-output current mirror 53 driven by this current source 59. The multiple-output current mirror 53 includes transistors Q6, Q7, Q8, Q9 and Q10. Accordingly, a current I0 equal to the current of the current source 59 flows into the transistors Q7, Q8, Q9 and Q10 so that these transistors Q7 - Q10 act as current sources. The MFC 70a includes two differential circuits 51 and 52. The differential circuit 51 will be described first. The differential circuit 51 includes two transistors Q1 and Q2 between the emitters of which a resistor R1 is connected. An input voltage VIN, namely the input variable xa, is applied to the base of the one transistor Q1, and the label voltage VLA is applied to the base of the other transistor Q2. The current I0 is supplied to the emitters of both transistors Q1, Q2 by the transistor Q8 serving as the current source. Let I1 represent the current which flows into the transistor Q1 and I2 the current which flows into the transistor Q2. When VIN < VLA holds, a current I2 = I0 flows into the transistor Q2 and no current (I1 = 0) flows into the transistor Q2. When the input voltage VIN exceeds the label voltage VLA, the current I2 of transistor Q2 diminishes linearly with an increase in the input voltage VIN, and the current I1 which flows into the transistor Q1 increases linearly from zero. When the relation VIN = VLA + R1I0 is attained, the relations I2 = 0, I1 = I0 are established. This state is maintained in a region of VIN greater than the foregoing. A current mirror 55 is provided and is driven by the current I2 which flows into the transistor Q2. A resistor RL is connected to the output side of the current mirror 55. Let the voltage developed across the resistor RL be a voltage V1. Since the voltage V1 is given by V1 = I2RL, it is constant up to a prescribed input voltage with respect to an increase in the input voltage VIN and then changes so as to attain the zero level after decreasing in linear fashion. The slope of the portion at which the voltage V1 decreases linearly is given by -RL/R1. This slope can be changed by changing the value of the resistor R1. The other differential circuit 52 has the same construction as that of the differential circuit 51. Let R2 represent the resistor connected between the emitters of two transistors Q3 and Q4, and let I3, I4 represent the currents which flow into the transistors Q3, Q4. The differential circuit 52 is driven by the transistor Q7 serving as a current source. A current mirror 54 is driven by the current I3 which flows into the transistor Q3. Since the current I3 flows into the resistor RL connected to the output side of the current mirror 54, a voltage V2 dropped across the resistor RL is represented by V2 = I3RL. With regard to a change in the input voltage VIN, the voltage V2 is at the zero level up to a prescribed input voltage, then increases linearly and attains a constant level. The slope of the portion at which the voltage V2 increases linearly is given by RL/R2. The MFC 70a is further provided with a two-input MIN circuit. The two-input MIN circuit outputs whichever of its two input voltages is lower. The two-input MIN circuit comprises a comparator and a compensator. The comparator is constituted by transistors Q11, Q12 whose emitters are connected together, and a current mirror 56 which acts as a current source for driving these transistors. The current mirror 56 is driven by the transistor Q9. Since the aforesaid voltages V1 and V2 are applied to the bases of the transistors Q11 and Q12, respectively, the transistor having the smaller voltage (here represented by Vmin) of these voltages V1 and V2 applied to its base is rendered conductive, and the other transistor is cut off. Accordingly, a voltage (Vmin + VEB), which is obtained by adding the emitter/base voltage VEB of the conductive transistor to the voltage Vmin, appears at the emitters. This voltage is applied to the base of a transistor Q13. The compensator, which is constituted by the transistor Q13 and the transistor Q10 that is for current-driving this transistor, compensates the voltage VBE that appears as a computation error at the output of the comparator. As a result of reducing the voltage VEB at the transistor Q13, Vmin appears as the output voltage VOUT at the emitter thereof. This output voltage is shown in Fig. 7. Thus, a membership function whose peak position is the label voltage VLA is set in the MFC 70a, and an output voltage VOUT, which represents the membership-function value conforming to the input VIN, is obtained, as shown in Fig. 7. Figs. 8 and 9 illustrate an example of the membership-function generating circuit (MFG) 110 using a switch matrix as the switch array. In Fig. 8, seven types of membership functions, which are outputted from 25 output terminals, numbered 0 through 24, of the membership-function generating circuit, are illustrated below these output terminals. The values of these outputted membership functions are quantified to four levels for the sake of simplification. These four levels correspond to voltages 0, 1.7, 3.3 and 5.0, respectively. The four levels are stipulated by a voltage-distribution generating circuit 114A. The circuit 114A is provided with three fuzzy truth-value voltage sources 114a, 114b and 114c of voltages 1.7, 3.3 and 5.0 V. Five voltage lines VL drawn diagonally in Fig. 8 are led out from the circuit 114A. The central line is connected to the voltage source 114c, the lines on either side of the central line are connected to the voltage source 114b, and the two outermost lines are connected to the voltage source 114a. A decoder 116A is a 1-of-8 decoder. The three-bit (C1, C2, C3) binary signal representing a label provided by the data latch circuit 80 enters the decoder 116A. The decoder 116A outputs an H-level signal at any of its eight output terminals in conformity with the code represented by this input signal. The eight output terminals correspond to no designation and to seven types of babels. For example, an H-level signal is outputted at the no-designation output terminal when the input code signal is 000, and at an NL output terminal when the input code signal is 001. Signal lines SL indicated by the horizontal lines in Fig. 8 are led out from these output terminals, with the exception of the no-designation output terminal. In a switch matrix 115A, output lines OL are led out to the 25 output terminals from prescribed points of intersection between the voltage lines VL and the signal lines SL. A symbol 115a, which is indicated by a small square at each of these points of intersection, is a switch provided between the voltage line VL and output line OL and on/off-controlled by the voltage on the signal line SL. By way of example, the switch is constructed by a MOS FET. It is of course permissible to provide two or more of the switches 115a on one output line OL. All the output lines are grounded via a register 115b at their output terminal sides. When the three-bit binary signal (C1, C2, C3) representing the label from the data latch circuit 80 is applied to the decoder 116A in the above-described arrangement, an H-level signal appears at whichever of the signal lines SL corresponds to this label, and the switches 115a provided on this signal line are turned on. As a result, each voltage of the voltage-distribution generating circuit 114A appears at the corresponding output terminal via the output lines OL through the switches 115a that have been turned on, and therefore a voltage distribution representing the membership function is outputted. In the above-described embodiment, the rule change is carried out in accordance with the setting by the digital switch units 75a - 75d. However, it goes without saying that the present invention is applicable also to a fuzzy control apparatus in which the rule change can be performed not only by a manual operation but also by remote control. Further, the invention can be applied also to a fuzzy control apparatus realized by a binary computer. Fig. 10 is a flowchart illustrating an example of a procedure of the operation of a fuzzy control apparatus in a case where the present invention is realized by software in a computer system. In this case, fuzzy reasoning also is realized by the software of a computer system. First, the number of rule to be changed is inputted by the operator (step 120). The particulars of the rule change are inputted from rule-change input means (a keyboard or the like) (step 121). Thereafter, a counter is cleared (step 122). When the result of the MIN operation of an antecedent is outside allowable limits, the counter measures suspension standby time for temporarily suspending the rule change in order to prevent a sudden variation in the control output. When the counter is cleared, it is determined whether the value of the MIN operation indicative of the degree of suitability of the antecedent membership function is within the allowable limits (step 123). If the value is not within the allowable limits (NO at step 123), the counter is incremented and it is determined whether the suspension standby time has arrived (steps 124, 125). The processing of steps 123 through 125 continues up to attainment of the standby time so long as a NO answer is obtained at step 123. When the standby time elapses, a display to this effect is presented (step 126). If the result of the MIN operation is within the allowable limits (YES at step 123), then the control output will not change suddenly owing to a rule change. Accordingly, the contents of the rule are changed and a display to the effect that the change has been completed is presented (steps 127, 128). Industrial ApplicabilityThe fuzzy control apparatus in which a rule is capable of being changed, the method of operating the same, the control system in which changeover is controlled by fuzzy reasoning, and the control method of this system, which are in accordance with the present invention, are well suited for use in automatic control of temperature, velocity and may other quantities.
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A control apparatus for supplying a manipulated variable to a controlled object, characterized in that the control apparatus comprises: control means (10) in which a manner of control is capable of being changed during operation; storage means (13) for storing a control output which prevails immediately prior to a change of the manner of control; synthesizing output means (21, 22, 25) for combining, and outputting as a synthesized control output, the stored control output which prevailed immediately prior to the change of the manner of control and a control output which prevails following the change of the manner of control, the synthesized control output representing the manipulated variable; and means (23, 24) for altering a combining ratio of said synthesizing output means in such a manner that, with passage of time from a moment at which the manner of control is changed, there is a gradual decrease in a percentage of the control output which prevailed immediately prior to the change of the manner of control, and a gradual increase in a percentage of the control output which prevails following the change of the manner of control, in the synthesized control output of said synthesizing output means, and for outputting, as the synthesized control output, upon passage of a predetermined time from the moment at which the manner of control is changed, the control output which prevails following the change of the manner of control. The control apparatus according to claim 1 characterized in that: said control means (10) is fuzzy reasoning means in which a rule is capable of being changed during operation; said storage means (13) is storage means for storing a fuzzy reasoning output which prevails immediately prior to a rule change; said synthesizing output means (21, 22, 25) is synthesizing output means for combining, and outputting as a fuzzy-control output, the stored fuzzy reasoning output which prevailed immediately prior to the rule change and a fuzzy reasoning output which prevails following the rule change, the fuzzy-control output representing the manipulated variable; and said combining ratio altering means (23, 24) is means for altering a combining ratio of said synthesizing output means in such a manner that, with passage of time from a moment at which the rule change is made, there is a gradual decrease in a percentage of the fuzzy reasoning output which prevailed immediately prior to the rule change, and a gradual increase in a percentage of the fuzzy reasoning output which prevails following the rule change, in the fuzzy-control output of said synthesizing output means, and for outputting, as the fuzzy-control output, upon passage of a predetermined time from the moment at which the rule change is made, the fuzzy reasoning output which prevails following the rule change. A method of operating a control apparatus for supplying a manipulated variable to a controlled object and including a control means (10) for producing a control output in which a manner of control is capable of being changed during operation, characterized in that the method comprises the steps of: storing (34) a control output which prevails immediately prior to a change of a manner of control, when the manner of control is changed; generating (36, 37, 38, 39) a synthesized control output which represents the manipulated variable by combining, after the change of the manner of control, the stored control output which prevailed immediately prior to the change of the manner of control and a control output which prevails following the change of the manner of control, and altering a combining ratio in such a manner that, with passage of time from a moment at which the manner of control is changed, there is a gradual decrease in a percentage of the control output which prevailed immediately prior to the change of the manner of control, and a gradual increase in a percentage of the control output which prevails following the change of the manner of control, in the synthesized control output; and outputting (36, 37, 38, 41), as the synthesized control output, upon passage of a predetermined time from the moment at which the manner of control is changed, the control output which prevails following the change of the manner of control. The method according to claim 3 characterized in that the method is for operating a fuzzy control apparatus including fuzzy reasoning means (10) for producing a fuzzy reasoning output in which a rule is capable of being changed during operation, and comprises the steps of: storing (34) a fuzzy reasoning output which prevails immediately prior to a rule change when a rule change is made; generating (36, 37, 38, 39) a fuzzy-control output which represents the manipulated variable by combining, after the rule change, the stored fuzzy reasoning output which prevailed immediately prior to the rule change and a fuzzy reasoning output which prevails following the rule change, and altering a combining ratio in such a manner that, with passage of time from a moment at which the rule change is made, there is a gradual decrease in a percentage of the fuzzy reasoning output which prevailed immediately prior to the rule change, and a gradual increase in a percentage of the fuzzy reasoning output which prevails following the rule change, in the fuzzy-control output; and outputting (36, 37, 38, 41), as the fuzzy-control output, upon passage of a predetermined time from the moment at which the rule change is made, the fuzzy reasoning output which prevails following the rule change. A control apparatus for supplying a manipulated variable to a controlled object, characterized in that the control apparatus comprises: control means (70a, 70b, 70c, 71, 72, 110) which outputs a control output representing the manipulated variable and in which a manner of control is capable of being changed during operation; holding means (75a, 75b, 75c, 75d) for holding a code which represents a new manner of control to be changed; means (100) for determining whether a value relating to the control output falls within allowable limits for a change of a manner of control; and means (80, 100) for applying the code held in said holding means to said control means when it is determined that the value relating to the control output falls within said allowable limits, and for forbidding application of the code to said control means when it is determined that the value falls outside said allowable limits. The control apparatus according to claim 5 characterized in that: said control means (70a, 70b, 70c, 71, 72, 110) is fuzzy reasoning means in which a rule is capable of being changed during operation; said holding means (75a, 75b, 75c, 75d) is rule holding means for holding a code which represents a new rule to be changed; said determining means (100) is means for determining whether degree of membership of an input signal with respect to a membership function of an antecedent in said fuzzy reasoning means falls within allowable limits for a rule change; and said applying means (80, 100) is control means for applying the code of the new rule held in said rule holding means to said fuzzy reasoning means when it is determined that the degree of membership of the input signal falls within said allowable limits, and for forbidding application of the code of the new rule to said fuzzy reasoning means when it is determined that the degree of membership of the input signal falls outside said allowable limits. A method of operating a control apparatus for supplying a manipulated variable to a controlled object and including a control means (70a, 70b, 70c, 71, 72, 110) which outputs a control output representing the manipulated variable and in which a manner of control is capable of being changed during operation, characterized in that the method comprises the steps of: holding (120, 121) a code, which represents a new manner of control to be changed, when the code has been applied; determining (123), when a command for changing a manner of control has been applied, whether a value relating to the control output falls within allowable limits for a change of manner of control; applying (123, 127) the held code of the new manner of control to said control means when it is determined that the value relating to the control output falls within said allowable limits, and forbidding application of the code to said control means when it is determined that the value falls outside said allowable limits. The method according to claim 7 characterized in that the method is for operating a fuzzy control apparatus including fuzzy reasoning means (70a, 70b, 70c, 71, 72, 110) in which a rule is capable of being changed during operation, and comprises the steps of: holding (120, 121) a code, which represents a new rule to be changed, when the code has been applied; determining (123), when a rule-change command has been applied, whether degree of membership of an input signal with respect to a membership function of an antecedent in said fuzzy reasoning means falls within allowable limits for a rule change; applying (123, 127) the held code of the new rule to said fuzzy reasoning means when it is determined that the degree of membership of the input signal falls within said allowable limits, and forbidding application of the code of the new rule to said fuzzy reasoning means when it is determined that the degree of membership of the input signal falls outside said allowable limits.
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OMRON TATEISI ELECTRONICS CO; OMRON CORPORATION
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MATSUNAGA NOBUTOMO; NISHIDAI HAJIME; MATSUNAGA, NOBUTOMO; NISHIDAI, HAJIME; MATSUNAGA, NOBUTOMO C/O OMRON CORPORATION; NISHIDAI, HAJIME C/O OMRON CORPORATION
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EP-0489914-B1
| 489,914 |
EP
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B1
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EN
| 19,960,417 | 1,992 | 20,100,220 |
new
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A47J36
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C23C14
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C23C16, A47J36, C23C14
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C23C 14/06F, C23C 16/34, A47J 36/02, C23C 14/58B, C23C 14/58, C23C 16/56, C23C 14/58H2
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METHOD OF FORMING TITANIUM NITRIDE COATING AND PAN MADE BY THIS METHOD
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A method of forming titanium nitride coating by ion plating which has an excellent decorative effect and a method of forming titanium nitride coating by which the color tone stability can be maintained even under high-temperature conditions. The method includes: (1) one which comprises forming titanium nitride coating on the surface of a base material by physical or chemical vapor deposition; (2) one which comprises forming titanium nitride coating on the surface of a base material and heating the coated base material in an atmosphere comprising a mixture of oxygen with nitrogen to form transparent and stable titanium oxide coating on the surface of the nitride coating to thereby effect color tone stabilization; and (3) one which comprises forming titanium nitride coating on the surface of a base material and heating the coated base material in a nitrogen atmosphere to diffuse nitrogen into the titanium nitride coating to thereby effect color tone stabilization. A cooking pan is produced by forming titanium nitride coating on the surface of a base material of a pan by any of the aforementioned methods.
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The present invention relates to a method for forming a titanium nitride (TiN) film over the surface of a substrate (see document US-A-4 226 082, column 16, lines 47 to 51) and to a cooking vessel with a TiN coating manufactured using the formation method thereof. Traditionally, a cooking pan such as a frying pan or a shallow pot (hereinafter referred to as the pan ) is made simply by forming a piece of metallic material, such as steel, and coating the inner surface of the pan with a fluororesin such as Teflon. Pans coated with fluororesin have been extensively used as frying pans and the like because of their prevention of charred food during cooking and their resistance to rust. However, pans coated with fluororesin are not attractive because fluororesins are colorless, and they do not have sufficient durability because fluororesins are soft. Such fluororesin properties cause the coated layers to deteriorate or peel off after repeated use and result in reduced effectiveness in the prevention of burnt food. The present invention is designed in consideration of the reasons above, and an object of the present invention is to provide a method of forming a TiN film and the pan obtained by such a method. In a first mode of the TiN film formation method, TiN film is formed over the surface of the substrate by using a physical vapor deposition method, whereby it is possible to form, on the surface of the substrate, a TiN film with a beautiful golden color, a high hardness value, and chemical stability. A pan, which is manufactured by forming TiN film over the surface of the substrate of the pan in accordance with the above method and obtained in such a manner, provides the following effects: (1) The cosmetic properties of the pan are improved because the TiN film has a beautiful golden color. (2) The surface of the pan's resistance to wear and tear is improved because of the high hardness of TiN. (3) Food cooked in the pan will not burn or stick to the surface of the pan because TiN is chemically stable and will not react to the burned food. In a second mode of the TiN film formation method, the TiN film is first formed on the surface of the substrate, the substrate is heated in an oxygen and nitrogen atmosphere, thereby coating the surface of the TiN film with a very thin layer of titanium oxide (TiO₂) several hundred Angstroms thick. With this method, the thin TiO₂ layer over the TiN film surface is transparent and will not change the color of the golden TiN film. In addition, since the thin TiO₂ film restricts the penetration of external oxygen to areas within the film, it is possible to obtain a TiN film with a stable color which will not change even if subjected to high temperatures. By forming the TiN film over the pan's surface in accordance with the above method, it becomes possible to maintain the beautiful golden color of the TiN film on the surface of the pan's substrate, as well as to achieve those effects that can be obtained by the aforementioned method. In a third mode of the TiN film formation method, the TiN film is first formed over the surface of the substrate and the substrate is heated in a nitrogen atmosphere to diffuse the nitrogen into the TiN film, thereby fixing the residual titanium (Ti) as TiN. By this method, it is possible to obtain a TiN film with a color which is stable even if subjected to high temperatures. Furthermore, a TiN film is formed on the surface of a pan by the methods mentioned above, which restrict changes in color, and such a pan is thus provided. FIG. 1 is an embodiment of the present design showing a perspective diagram of a frying pan. FIG. 2 is cross-sectional view of the main part of the frying pan shown in FIG. 1. FIG. 3 is a conceptual diagram showing an ion plating apparatus. FIG. 4 through FIG. 7 are diagrams to illustrate examples of the experiments related to the present design. FIG. 8 is a conceptual diagram showing an example of an apparatus which implements a TiN film formation method. FIG. 9 is a conceptual diagram showing the ion plating apparatus used by the apparatus shown in FIG. 8. FIG. 10 is a conceptual diagram that shows an example of a heat treatment apparatus used in the apparatus shown in FIG. 8. FIG. 11 is a conceptual diagram that shows another example of the heat treatment apparatus used in the apparatus shown in FIG. 8. FIG. 12 is a diagram that shows the result of an X-ray diffraction. First methodFIG. 3 shows an example of an ion plating apparatus used in the manufacture of a frying pan (1) according to a first method. The inside of this ion plating apparatus (5) is maintained at a vacuum of about 10⁻⁵ to 10⁻⁷ Torr by a vacuum pump (6). Several hundred volts are applied to the body (2) of the frying pan arranged inside of the ion plating apparatus (5). Titanium (7) (a coating material) is placed on the side opposite to the body (2) of this frying pan. In the vicinity of this titanium (7) is an ion electrode (8) which uses Ar gas for Argon cleaning the surface before the film formation of the frying pan body (2), and adds nitrogen to the atmosphere for heating and evaporation during film formation followed further by ionisation. In order to form a TiN layer (4) on the frying pan body (2) by means of the ion plating apparatus (5), the inner surface (the surface to be coated) of the frying pan body (2) is first ground to a mirror finish and has removed from it any unevenness such as cutting marks from the lathe or oil sumps. Debris or oil is removed from the pan by means of the washing and degreasing of the ground surface. Once the frying pan body (2) has completed such pretreatment, it is placed inside the ion plating apparatus (5). Then, the titanium (7) is subjected to ion bombardment in an Ar atmosphere and heated by an electron beam issued from the ion electrode (8). The titanium (7) is evaporated, and the evaporated particles are ionized. The ionised particles have high kinetic energy and collide strongly with and attach to the frying pan body (2), so that a Ti layer (3) is formed over the surface of the frying pan body (2). When the thickness of the Ti layer (3) is several hundred angstroms, the voltage applied to the frying pan body (2) is lowered, and nitrogen is introduced into the ion plating apparatus (5) through a nitrogen supply passage (9) in order to maintain the pressure inside the apparatus (5) at about 10⁻⁵ Torr. The aforementioned ionized titanium particles and the nitrogen are caused to react by the above operation so as to attach TiN to the Ti layer (3) on the surface of the frying pan body (2), and a uniform TiN layer (4) 2 to 3 micron thick is formed thereon. A frying pan (1) is thus manufactured by the above operation. FIG. 1 shows the frying pan manufactured by such a method, wherein the numeral 1 denotes the frying pan. This frying pan is, as shown in FIG. 2, composed by providing a 2 to 3 micron thick TiN layer (4) on the inside of the frying pan body (2), which is made from a metallic material such as steel by means of a Ti layer (3) several hundred angstroms thick. The above Ti layer (3) is formed directly over the surface of the frying pan body (2) and is very firmly attached thereto. The TiN layer (4) is firmly formed in close contact with the Ti layer (3), so that the TiN layer (4) is securely joined to the frying pan body (2). The frying pan (1) manufactured by this method is provided on the surface of the body (2) thereof, with the TiN layer (4) producing a beautiful golden color, thereby improving the cosmetic properties of the pan, and conferring a feeling of high quality thereto. Further, because the TiN layer has high hardness (about Hv2000 in Vickers' hardness), it is possible to improve the durability of the pan's surface. Moreover, because the TiN layer (4) is chemically stable, it does not react to burnt food and is excellent in its resistance to adhesion of burnt food, and thus the frying pan will almost never allow burnt food to stick thereto during cooking. Furthermore, even if burnt food does stick to the frying pan, it can be easily removed therefrom. In the method stated above, the frying pan is given as an example, but a relatively shallow pan can be produced instead of a frying pan. In the method stated above, the TiN layer is formed only on the inside surface of the frying pan body, but the TiN layer can also be formed over the entire surface, including the handle, or only a part of the inside surface. [Experiment 1]The apparatus shown in FIG. 3 was used to form at 2 to 3 micron TiN layer over the surface of a steel frying pan by means of an approximately 200 Å Ti layer, and a frying pan having the same composition as the one shown in FIG. 1 (hereinafter referred to as the TiN-coated frying pan) was thus manufactured. Three types of frying pans, a TiN coated frying pan, a traditional steel frying pan (uncoated) and a Teflon coated frying pan, were used to conduct the following experiments. Fish (sole) of almost the same size were prepared, and each sole was placed on the center of the cooking plane of each frying pan (previously unused). The three frying pans each placed with a sole thereon were heated simultaneously with strong flames of the same intensity for about five minutes. The soles were removed, and the weight of the burnt sole remaining on the cooking plane of the frying pan was measured. Then, three other frying pans identical to those above were used for repeated heating and cooking (100 times), and the weight of the burnt sole remaining on the cooking plane of the frying pan was measured again. The results of this experiment are shown in FIG. 4 and FIG. 5. The burning levels shown in these diagrams are expressed as an absolute value of the weight of the burned portion of the fish, where the amount of burned fish cooked on an uncoated frying pan is taken to be 100. As shown in FIG. 4 and FIG. 5, when a traditional steel frying pan (uncoated one) was used, the burn was considerable after both the first and the 100th cooking. When a Teflon-coated frying pan was used, little burn was observed after the first cooking (a burning degree is 3.). However, after the 100th cooking, the burning degree was as large as 40, which indicates a deterioration of the teflon's ability to prevent burning after the repeated use of the frying pan. When a TiN-coated frying pan was used, little burn was observed (the burning degree is 3) after the first cooking, as in the case of the Teflon-coated frying pan. After the 100th cooking, the burning degree was 20, which is about half that of the Teflon-coated frying pan. It was thus confirmed that after repeated cooking the TiN-coated frying pan is effective in preventing food from burning. [Experiment 2]In the second experiment, kiao-tz (dumplings stuffed with minced pork) were used, as they are one of the most easily burned of foods. Fifty dumplings of almost the same size were prepared for one frying pan; three types of unused frying pans similar to those used in the first experiment were prepared; and the fifty dumplings were placed on their cooking planes. The three types of frying pans with the dumplings were placed on household gas burners and were heated simultaneously for about five minutes with a strong flame of the same intensity. Afterwards, the number of burned dumplings was counted. Then, each of the three types of frying pans repeated the above operations 100 times, and the number of burned dumplings was counted again. The results of this experiment are shown in FIG. 6 and FIG. 7. As is apparent from these diagrams, when a traditional, uncoated steel frying pan was used, the number of burned dumplings was notable both after the first cooking and after the 100th cooking. When a Teflon-coated frying pan was used, no dumpling was burned after the first cooking. However, after the 100th cooking, six dumplings were found burned, indicating the deterioration of the Teflon's ability to prevent burning after repeated cooking. When a TiN-coated frying pan was used, there were no dumplings burned after the first cooking. There were also no burned dumplings found after the 100th cooking, thus confirming that the TiN-coated frying pan has an excellent ability to prevent burns after repeated cooking. [Experiment 3]Three types of frying pans, which are the same as those used in the first and second experiments, were used in the third experiment. The cooking plane of each frying pan was scrubbed with wire brushes for five minutes with the same degree of force. As a result of the scrubbing, countless scratches were marked over the cooking plane of the uncoated steel frying pan. Countless white scratches also appeared on the cooking plane of the Teflon-coated frying pan, and part of the Teflon coating peeled off. On the other hand, the TiN-coated frying pan had no scratches and maintained a lustrous shine. Second methodFIG. 8 is a diagram to explain a second method, in which the numeral 11 denotes a substrate of the frying pan, 12 a frying pan formed with TiN film thereon, 13 a frying pan processed for color stabilization, 14 a grinding and washing apparatus, 15 an ion plating apparatus, and 16 denotes a heat treatment apparatus which accomplishes the color tone stabilization process. In order to form a TiN film over the surface of the substrate (11) of the frying pan using this apparatus, the surface of the frying pan substrate (11) is first ground and cleaned by the grinding and washing apparatus (14). The frying pan substrate (11) is composed of a metallic material such as steel. Because the frying pan substrate (11) may be uneven or have dust, oils, or fats attached to the surface where the film is to be formed (which could cause reduced adhesion of the TiN film to the substrate during the formation process thereof), the surface is ground, degreased and washed clean with demineralized water, acid, alkali and the like within the grinding and washing apparatus (14). The TiN film is formed on the surface of the frying pan substrate (11), which has been pretreated in such a manner, by the ion plating apparatus (15). The ion plating apparatus (15) comprising the body (15A) of the apparatus as shown in FIG. 9, a crucible (18) in which the film-formation material titanium (17) is to be placed, a power source for a substrate of an integrated circuit (19), a gas (Ar, N₂) supply regulator (20), an ionization electrode (21), an electron beam apparatus (22), a vacuum apparatus (23), a heater (24), and a gas (Ar, N₂) supply opening (25). Several hundred volts are applied to the frying pan substrate (11), which is arranged on the side opposite to the crucible (18) containing the titanium (17), by the printed circuit substrate power source (19). The interior of the body of the ion plating apparatus (15A) is maintained at a vacuum of about 10⁻⁵ to 10⁻⁷ Torr by the vacuum apparatus (23). Under such conditions, Ar gas is injected into the apparatus by the gas supply regulator (20) to accomplish ion bombardment in the Ar atmosphere over the surface of the frying pan substrate (11). Then, the titanium (17) placed in the crucible (18) is heated and evaporated by the electron beam apparatus (22) to produce Ti particles. The Ti particles are ionized by the ionization electrode (21) to cause the ionised Ti particle to collide with the surface of the frying pan substrate (11), thereby forming the Ti film. When the thickness of the Ti film has grown to several hundred angstroms, the applied voltage of the frying pan substrate (11) is lowered, and N₂ is introduced from the gas supply opening (25) into the body of the ion plating apparatus (15A). The internal pressure of the ion plating apparatus (15) is then adjusted to about 10⁻⁵ Torr by the gas (Ar, N₂) supply regulator (20). In such a manner, the ionised Ti particles above and the N₂ that was also ionised are caused to react by the ionization electrode (21) and form a 2 to 3 micron TiN film over the Ti film formed on the surface of the frying pan substrate (11), thereby manufacturing a frying pan (12). The frying pan (12) is then placed in the heat treatment apparatus (16). As shown in FIG. 10, the heat treatment apparatus (16) comprising the body (16A) of the heat treatment apparatus, a nitrogen (N₂) cylinder (26), an oxygen (O₂) cylinder (27), a purifier (28, 29), a heater (30), a shelf (31), and a pump (32). A TiN-formed frying pan (12) is placed on the shelf (31) in the heat treatment apparatus body (16A) and heated. While heating, N₂ and O₂ are supplied from the N₂ cylinder (26) and the O₂ cylinder into the heat treatment apparatus body (16A) through the purifier (28, 29), so that the inside of the heat treatment apparatus body (16A) is maintained at an atmosphere of O₂:N₂ = 1:20 to 1:5. Under the above conditions, the heater (30) is used to heat the TiN-formed frying pan (12) to 350 to 500°C to form a uniform TiO₂ film of about several hundred angstroms over the TiN film surface, thereby obtaining a frying pan (13) with a TiN film of stabilized color tone. Here, the temperature conditions (350 to 500°C) used for the above operation are set to a level which is close to the upper limit where the frying pan is used at high temperatures, and yet the golden color of TiN is not lost. In the formation method of the TiN film, the color tone of the heat-treated TiN film can be changed to various tones by changing the composition ratio of Ti:N while forming TiN film by the ion plating method. For example, if the condition of the ion plating apparatus used in this experiment is set to about Ti/N = 2.0, the color tone will be light gold during the TiN film formation and turn to a gold color after the heat treatment. If the condition of the ion plating is set to about Ti/N =1.0, the color tone will be gold during the TiN film formation and turn to a deep gold after the heat treatment. It is therefore possible to obtain a frying pan with a stabilized color tone. In a method as described above, a frying pan (13) can be obtained in which the surface of the frying pan substrate (11) is provided with a TiN film having excellent color tone stability during high temperature cooking. According to this method of forming TiN film, it is possible to stabilize the TiN film color tone while heating by forming a very thin TiO₂ film over the TiN surface, which is produced by heating Ti in the TiN film in a mixed atmosphere of oxygen and nitrogen. In addition, by properly adjusting the Ti/N ratio, which is among the conditions used for film formation with the ion plating apparatus, it becomes possible to form a TiN film of various color tones. The frying pan obtained by the aforementioned method will have an improved appearance and will acquire a feeling of high quality because the TiN film is a beautiful gold color. Because the TiN film has a stable color tone, it will not change color when heated during cooking, and its beautiful gold color can be maintained over a long period of time. Third methodNow, a third TiN film formation method will be described. In this third method, an apparatus similar to that used in the above methods is used and a frying pan (12) is obtained by forming a TiN film over the surface of the frying pan substrate (11) through operations similar to the ones above. The frying pan (12) obtained in such manner is placed in a heat treatment apparatus (33) shown in FIG. 11. The heat treatment apparatus (33) comprising the body (33A) of the heat treatment apparatus, a nitrogen (N₂) cylinder (34), a purifier (35), a heater (36), a shelf (37), and a pump (38). The frying pan (12) is placed on the shelf (37), and N₂ is supplied from the N₂ cylinder (34) into the heat treatment apparatus body (33A) through the purifier (35). The inside of the heat treatment body (33A) is maintained in an N₂ atmosphere (760 to 765 Torr). In such a manner, the frying pan (12) is heated to 350 to 600°C by the heater (36) under the above conditions so as to diffuse the nitrogen into the TiN film, and the Ti remaining in the TiN during film formation becomes TiN. Most of the Ti remaining in the TiN film that can react to N₂ at the temperature conditions above will be turned into TiN, and a change in color tone of the TiN film will not occur because there is no longer any Ti in the TiN film that can be oxidized by the air, even if the TiN film is heated later at a temperature lower than the above (350 to 600°C). In the manner stated above, it is thus possible to obtain a frying pan with stabilized color tone by coating the surface of the frying pan substrate body (11) with a TiN film with excellent color tone stability at high temperatures. With this method of TiN film formation, it is possible to heat the residual Ti in the TiN film in an individual nitrogen atmosphere to obtain TiN, thereby stabilizing the color tone of the TiN film. In addition, because most of the residual Ti in the TiN film is turned into TiN due to color tone stabilization treatment, It is possible to obtain a TiN film with excellent color tone, closer in color to pure gold than TiN film before color tone stabilization treatment. In each of the above experiments, the TiN film is formed using the ion plating method, but other film forming methods such as the sputtering, metalization or the chemical vapor deposition method may be used to form the TiN film. In each of the above experiments, the method is applied when manufacturing frying pans, but this method can also be applied to various cooking utensils for heating other than frying pans such as a pan with a relatively shallow bottom or a spatula. [Experiment 4]The apparatus shown in FIG. 8 through FIG. 11 was used to manufacture a frying pan which has a color tone stabilized TiN film on its surface. The frying pan substrate body (11) was placed in the grinding and washing apparatus (14), the surface thereof is ground, washed first with water then with demineralized water, acid, base, again with water and finally with alcohol. Afterwards, this substrate (11) was then placed in the ion plating apparatus body (15A). The inside of the ion plating apparatus body (15A) was maintained in a vacuum, about 10⁻⁵ to 10⁻⁷ Torr in the vacuum apparatus (23), and several hundred volts were applied to the installed frying pan substrate (11). Then, the argon gas was injected into the apparatus which bombarded the frying pan substrate (11) with ions in an argon gas atmosphere, and a 200 Å thick layer of Ti was formed over the surface of the frying pan substrate (11). Next, the applied voltage of the frying pan substrate (11) was lowered, N₂ was injected into the ion plating apparatus body (15A) by the gas supply regulator (20), the internal pressure of the ion plating apparatus body (15A) is maintained at about 10⁻⁵ Torr, and a 2 to 3 micron TiN layer was formed. The frying pan (12) obtained by the aforementioned method was placed on the shelf inside the heat treatment apparatus body (16A), N₂ and O₂ were supplied into the heat treatment apparatus body (16A) from the N₂ cylinder (26) and the O₂ cylinder (27), respectively, through the purifier (28, 29). The inside of the heat treatment apparatus body (16A) was maintained at an atmosphere of O₂:N₂ = 1:20 to 1:5 in the above manner, and the frying pan was heated to 350°C by the heater under such conditions. As a result, a frying pan (called embodiment A) with a TiN-film surface and a gold color tone was obtained. Similarly, the frying pan (12) was placed on the shelf (37) in the heat treatment apparatus (33), N₂ was supplied from the nitrogen cylinder (34) into the heat treatment apparatus body (33A) through the N₂ purifier (35). The inside of the heat treatment apparatus body (33A) was maintained in an N₂ atmosphere (760 to 765 Torr) in the manner stated above, and the frying pan was heated to 350°C by the heater (36) under such conditions. As a result, a frying pan (called embodiment D) formed with a TiN-film surface and a pure gold color tone was obtained. With respect to the frying pans of embodiment A and embodiment D obtained through the above operations, tests were conducted on the change in the TiN-film color tone as a result of heating, resistance to burning, and resistance to wear. To test discoloration due to heating, the frying pan of embodiment A and a frying pan (called the compared sample) coated with TiN that was not provided with color tone stabilization treatment were heated to 300°C. As a result of heating, no discoloration was observed in the frying pan of embodiment A, but the frying pan of the compared sample changed color to yellow with a tinge of black. X-ray diffraction tests were carried out on each of the heated frying pans. The results of the X-ray diffraction tests are shown in FIG. 12. The symbol A shown in FIG. 12 denotes a frying pan of embodiment A provided with the TiN coating and heated to 300°C, the symbol B denotes a frying pan of the compared sample uncoated and heated to 300°C, and the symbol C denotes a frying pan of the compared sample provided with the TiN coating. A 300°C heating test was also conducted on the frying pan of embodiment D, but no discoloration was observed. With respect to the burning of food, the frying pans of embodiment A and embodiment D were used for long-term tests in which fish and rice cakes were baked, but both frying pans burned no food at all. With respect to wear resistance, a wire brush was used to scrub forcibly the surfaces of the frying pans of embodiment A and embodiment D, but both frying pans showed no damage to their film surfaces and no peeled film. It was therefore confirmed that these frying pans have excellent wear resistance. As described above, the method of forming the TiN film and the pan according to the present invention has the following effects: The TiN film formation method according to Claim 1 is a method for forming TiN film over the surface of the substrate by a physical metalization method or a chemical metalization method. The pans obtained by such methods have a TiN film with an attractive gold color formed on their surfaces, so that the cosmetic properties of the pan are improved and a look of high quality is conferred to the pan. In addition, because the TiN film has high hardness, it is possible to improve the resistance to wear of the surface of the pan. Further, because the TiN film is chemically stable and free from reactions to burning food and has excellent resistance to burning, the pan will not cause food to burn while cooking, and even if burning should occur, it can be removed easily. With the TiN film formation method according to Claim 1, it is possible to obtain a TiN film with a stable color tone by heating the Ti remaining in the TiN film in a mixed atmosphere of oxygen and nitrogen to produce a transparent and stable TiO₂ film. The pans obtained by such a method have a TiN-film surface with an attractive gold color tone, thereby improving the cosmetic appeal thereof and producing a look of high quality. Because this pan has a transparent and stable TiO₂ film over the TiN film produced on the substrate surface, the beautiful gold color tone of the pan can be maintained over a long time, and the gloss of the pan will not change during heating. It is possible to obtain a TiN film with a stable color tone by heating the Ti remaining in the TiN film in an individual nitrogen atmosphere to produce TiN. The pan resulting from this method has a TiN film with a beautiful gold color tone on its surface. As a result, it is possible to improve its decorative properties and to provide a high quality impression. Because most of the Ti remaining in the TiN film formed on the substrate surface becomes TiN, the beautiful gold color tone of the pan can be maintained over a long time, and the gloss of the pan will not change during heating.
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A method for forming a titanium nitride film, wherein the method is characterized in that a titanium nitride film is formed on the surface of an object by means of physical vapor deposition or chemical vapor deposition, and then the object having the titanium nitride film is heat-treated in an atmosphere consisting of oxygen and nitrogen wherein the ratio of O₂:N₂ is in a range between 1:20 and 1:5, thereby effecting a color-tone stabilizing treatment by forming a transparent and stable titanium oxide film over the surface of the titanium nitride film. A method for forming a titanium nitride film in accordance with claim 1, wherein a titanium film is formed on the surface of an object by means of physical vapor deposition or chemical vapor deposition, before the formation of said titanium nitride film. A method for forming a titanium nitride film in accordance with claim 2, wherein said formation of said titanium film is continued until the thickness of said titanium film reaches several hundred angstroms, and thereafter, said formation of said titanium nitride film is continued until the thickness of said titanium nitride film reaches 2 to 3 µm. A method for forming a titanium nitride film in accordance with claim 3, wherein when said thickness of said titanium film reaches several hundred angstroms, a voltage applied to said object is lowered, and then nitrogen gas is supplied for said formation of said titanium nitride film. A method for forming a titanium nitride film in accordance with claim 2, wherein said formation of said titanium film is continued until the thickness of said titanium film reaches 200 angstroms, and thereafter, said formation of said titanium nitride film is continued until the thickness of said titanium nitride film reaches 2 to 3 µm. A method for forming a titanium nitride film in accordance with claim 5, wherein when said thickness of said titanium film reaches 200 angstroms, a voltage applied to said object is lowered, and then nitrogen gas is supplied for said formation of said titanium nitride film. A method for forming a titanium nitride film in accordance with one of claims 1-6, wherein the temperature of said atmosphere of said heat-treatment ranges between 350°C and 500°C. A vessel having a titanium nitride film formed on the surface thereof which is manufactured according to a method as claimed in one of claims 1-7.
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NIIGATA ENGINEERING CO LTD; NIIGATA ENGINEERING CO., LTD.
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KANNO HIROSHI; NAGAOKA HITOSHI; KANNO, HIROSHI,; NAGAOKA, HITOSHI,; KANNO, HIROSHI, KAIHATSU CENTER; NAGAOKA, HITOSHI, NIIGATA ENGINEERING CO., LTD.
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EP-0489915-B2
| 489,915 |
EP
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B2
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EN
| 20,000,209 | 1,992 | 20,100,220 |
new
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G01C21
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G01C21
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G01C21, G08G1
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G08G 1/0969, G01C 21/34
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NAVIGATION APPARATUS AND METHOD
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A navigation apparatus and method designed chiefly for the drivers and also for pedestrians when no such instrument as a distance sensor or a bearing sensor is used. Upon receipt of data related to the passage along which one is now traveling, such as signals from transmitters installed along the passage, electromagnetic waves from an artificial satellite, or based on the distance sensor and bearing sensor, or upon receipt of information input by the user, the apparatus displays what would happen if one proceeds the passage without turning right or left or what would happen if one proceeds a predetermined lane. When a target is set, the apparatus displays both the target and the lane to travel, and further displays the passage leading to the target as well as a proper and suitable passage that leads from a major passage to the target. The data of passage are retrieved by attaching group code and common code to the links.
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Technical FieldThe present invention relates to a navigation system which is mainly used by a driver of an automobile and a method therefor, and which is known from IEEE PLANS '88 POSITION LOCATION AND NAVIGATION SYMPOSIUM RECORD NAVIGATION INTO THE 21ST CENTURY , Kissemmee, Florida, 29.11. - 02.12.88; C.B. Harris et al.: DIGITAL MAP DEPENDENT FUNCTIONS CF AUTOMATIC VEHICLE LOCATION SYSTEMS , pp. 79 - 87, for example.Background ArtA conventional navigation system having a storage device, a processing device, an input device, a display device, sensors and the like and a navigation method to be executed in the system may be classified into the following two types on the basis of the contents displayed on the display device as driving information provided for a user.One of the two types is a map display system which is arranged in such a manner that a map is displayed on the screen of the display device and a travelling locus, a present position, a moving direction, a target, a target direction, an instructed course or the like are indicated in the map. Another one is an arrow display system which is arranged in such a manner that no map is displayed but arrows respectively showing the target direction and the course instruction at each intersection are indicated. The map display system and the arrow display system respectively have encountered the following problems:According to the map display system, a driver must look at the displayed map while driving a vehicle. Therefore, the driver must pay attention to many factors and thereby the driver will be exhausted, causing a load to be applied to the driver. Furthermore, a risk will arise as the case may be. Therefore, in the conventional map display system, the display device has been disposed in a lower position so that the driver cannot look at it during driving, or only main roads are indicated during driving. However, these devices could not satisfactorily overcome the problems and thereby a risk in terms of the traffic safety remains. Because of the risk, the European countries have had a denial view on the map display system and therefore they have not employed the map display system.The arrow display system encounters the following two typical problems: In a case where the target direction is shown by an arrow as one of the display modes of the display device, the driver psychologically tends to earlier turn to the right or left in accordance with the shown arrow, causing a problem to arise, for example, the vehicle strays in a residential area. Furthermore, in a case where the course is instructed at an intersection as another display mode, timing at which traffic information collected in a real time is indicated and acceptability for the drivers, which becomes a serious problem for the aged drivers, remain as unsolved problems, because there is a course instruction as the assumption.According to a basic system design concept used for developing the conventional navigation system, the most important factor for the navigation system lies in that the present position of the user's vehicle, which is moving, is accurately recognized in a map (road map) which has been previously prepared. This system design concept is similarly applied to both the map display system and the arrow display system.However, the conventional navigation system developed in accordance with the basic system design concept has been restricted by the system design concept and thereby it is of no practical use at present.That is, since the vehicle such as an automobile moves at considerably high speed, it is not so practical for the driver even if the driver recognizes the present position of the vehicle as a point of low accuracy on the road map displayed on the display device. That is, it is rather acceptable for the driver who is driving the vehicle, in the aspects of the speed sensibility and the sense about the positional relationship and the directional relationship with respect to his target, that the driver recognizes the state of the vehicle's movement as a line while making the positional relationship with respect to the target clear than recognizing the present position indicated as a point, on the screen of the display device. It is easier and more natural for the driver to recognize the state of the vehicle's movement as the line than to recognize the state of the movement as the point. Furthermore, information about the state of the movement as the line is more valuable as available drive information. In addition, since the user's vehicle such as an automobile must move while being restricted by a road in a different manner from an airplane and a ship, it is more practical to recognize the road along which the user's vehicle is currently moving while making the positional relationship with the target for the use's vehicle clear than obtaining the present position of the user's vehicle as a point.Furthermore, if the present position of the user's vehicle is intended to be accurately obtained, the load of realizing the high accuracy becomes too heavy for the navigation system. As a result, the cost for manufacturing the navigation system cannot be reduced and thereby wide using of the navigation system will be interrupted. Therefore, the primary ideal of preventing the traffic snarl and realizing the safety traffic cannot be achieved. It is very dangerous for the driver to drive his vehicle while actually looking for a road. Therefore, there has been a desire of a practical navigation system to be developed as a system of aiding the driver to easily reach the position of the target. According to the conventional navigation system arranged in accordance with the map display system, the driver must watch the driving course set on the road map displayed on the display device. Therefore, the dangerous factor cannot be eliminated and thereby its practicality is insufficient.Since the driver must pay attention to many things during driving the vehicle, the load of the driver must be reduced for the purpose of safely driving the vehicle. Therefore, it is preferable that a navigation system be arranged in such a manner that information necessary to select the course can be obtained at first sight.According to the conventional navigation system arranged in accordance with a route guide system in which the driving course through which the vehicle reaches the target is indicated on the display device, an optimum driving course is set in accordance with the relationship between the start position and the target position at the time of start of driving. According to the above-described navigation system arranged in accordance with the route guide system, it is actually difficult to drive the vehicle while keeping the driving course in the actual road state even if the driving course is indicated on the display device. Furthermore, the degree of the danger can be increased due to stress given to the driver when the determined driving course is instructed for the driver.However, if the instruction by means of indicating the driving course is not made but only the present position of the user's vehicle is indicated, the value of information is insufficient. It is more dangerous to look for the course in accordance with the present position shown on the road map displayed on the display device than to instruct the driving course.It is important for the navigation system to, via the display device, show the drive information which is valuable to reach the target in a state in which the safety cannot be deteriorated. In particular, intense stress is given to the driver if the optimum driving course to reach the target is determined before the start of driving and the one fixed driving course is shown to the driver. In order to prevent the state in which the stress is given to the driver, it is preferable that the navigation system be constituted in such a manner that the driver is able to select a course to reach the target and the driver's determination about the selected course is given priority. As a result, the driver is able to drive the vehicle with composure.Furthermore, the current background in which the aged drivers increase must be taken into consideration. In addition, the mental state and recognition of the driver in a specific situation must be considered.Therefore, it is insufficient for the display device to indicate the present position of the user's vehicle on the road map. In addition, it is an excessive function to indicate the driving course on the map.An object of the present invention is to provide a significantly practical navigation system and a method therefor capable of overcoming the above-described problems and meeting the above-described requirements by regarding information about the movement state of a moving object as a line as important and employing a concept of a line representing a route segment along which the moving object is currently moving, that is a travelling line , whereby necessary and minimum practical information is supplied to a user such as a driver to cause the user to independently select the course.Another object of the present invention is to provide a navigation system and a method therefor in which a novel and practical navigation display system is employed which is completely different from the conventional map display system and the arrow display system in terms of the display method and which is arranged completely different from the course guide system in terms of a navigation principle such that the driving course is not set previously but a user is able to independently make the driving course while selecting a course in accordance with the determination about driving made by the user.Disclosure of the InventionAccording to the present invention, there is provided a navigation system and a method therefor arranged in such a manner that coordinates and various data items about positions are stored in a storage device at need, a processing device performs a predetermined process when predetermined information is supplied via an input device and a display device indicates the result of the process, wherein, when information about a route segment along which a moving object is currently moving is supplied by means of any one or some of a receipt of a signal transmitted from a transmitter, a receipt of satellite electric waves, detections of a distance sensor and an azimuth sensor and an operation of a user, a line (hereinafter referred to as a travelling line at need) representing the route segment along which the moving object is currently moving is, together with information about a target such as a target position, indicated on the screen of the display device while always making the positional relationship with the target clear.The route segment along which the moving object is currently moving means a route segment along which the moving object , on which the main unit of the navigation system is mounted, is currently moving. For example, the route segment is a route segment the start point of which is defined by a point at which turning to the right/left is performed at an intersection and end point defined by a final point to which the moving object is able to reach in a case where the moving object moves without performing turning to the right/left after turning to the right/left at the intersection. The route segment along which the moving object is currently moving is changed in accordance with the movement of the moving object while repeating turning to the right/left. Therefore, in principle, information about a novel route segment along which the moving object is currently moving is obtained whenever the route segment along which the moving object is currently moving is changed, and when obtaining the information about the novel route segment, a line representing the route segment along which the moving object is currently moving is generated. Thus, the line representing the route segment along which the moving object is currently moving shown on the screen of the display device is updated. The information about the route segment along which the moving object is currently moving means information from which data about the shape and the position of the route segment along which the moving object is currently moving can be finally obtained. The meaning of the line representing the route segment along which the moving object is currently moving, that is, the travelling line will be concretely described later.The navigation system and the navigation method according to the present invention are characterized in that the travelling line (the line representing the route segment along which the moving object is currently moving) and the target for the moving object to reach are always indicated on the screen of the display device, and a driver or the like can move to reach the target by selecting freely at the driver's will a route segment along which the driver or the like wants to pass on the basis of the recognition of the positional relationship between the travelling line and the target on the screen. The travelling line indicated on the screen of the display device is updated whenever the driver selects another route segment due to turning to the right/left. As described above, the travelling line is updated with the movement of the moving object in accordance with a selection of the driving course at the driver's will or the like. Therefore, the travelling line is completely different in terms of its concept from the driving course which is described in the background art and which is previously determined before the start of driving between the start point and the target.The present position of the moving object is at need indicated on the screen of the display device. Since the present position of the moving object can be ascertained from the conditions when making the travelling line indicated or the positional relationship with the target, the particular necessity of clearly indicating the present position is not required. Furthermore, it is not necessary to, on the screen of the display device, display the road map about a region in which the moving object is currently moving.As will be described below, the present invention has a plurality of embodiments so as to select a proper embodiment in accordance with the purpose and way of use of the present invention. According to these embodiments, a variety of configurations for variously generating the travelling line and states of indication mode on the screen of the display device are explained. A preferred aspect of the present invention lies in a navigation system and a method therefor arranged in such a manner that transmitters are disposed in the route segments and a signal to be transmitted from the transmitter is given data about the shape and the position of the route segment in which the transmitter is disposed, whereby, when a main unit of the navigation system mounted on the moving object and having a signal receiving function receives the signal, a travelling line representing the route segment along which the moving object is currently moving is indicated on the display device. Furthermore, a configuration may be constituted in such a manner that a code is given to the signal to be transmitted from the transmitter, data about the shape and the position of the route segment is stored in a data storage device of the main unit, data about the shape and the position of the route segment which corresponds to the code read from the signal is retrieved from the data stored in the storage device on the basis of the code read from the signal and the travelling line is indicated on the basis of the retrieved data.A preferred aspect of the present invention lies in a navigation system and a method therefor arranged in such a manner that data about the shape and the position of a route segment is stored in the data storage device, data corresponding to the route segment along which the moving object is currently moving is retrieved from data stored in the data storage device when information which can be recognized by a user when the user moves through the route segment and with which the route segment along which the moving object is currently moving can be specified and the travelling line is indicated.A preferred aspect of the invention lies in a navigation system and a method therefor arranged in such a manner that the present place (present position) is estimated on the basis of satellite electric waves, or a distance sensor and an azimuth sensor, a route segment which is nearest to the estimated present position is discriminated, data about the shape and the position of the route segment is retrieved from data stored in a data storage device and it is indicated as a travelling line. A configuration may be employed which is arranged in such a manner that a locus of a route segment which can be considered that the moving object has passed along is obtained on the basis of the estimated present position, the route segment along which the moving object has passed is discriminated on the basis of a result of a comparison made between the locus and the shape of the route segment, data about the shape and the position of the route segment which is positioned in front of the route segment along which the moving object has passed and through which the moving object will pass through if it does not turn to the right/left is retrieved from data stored in the data storage device and it is indicated as a travelling line.A preferred aspect of the present invention lies in a navigation system and a method therefor arranged in such a manner that it comprises a distance sensor and an azimuth sensor, the route segments which intersect each passage are, together with the state of advancement into the intersection, stored, the distance between the intersections is stored, the distance from the initial movement position is detected by the distance sensor, the distance from the initial movement position to each intersection is obtained, the stored distance and said quantity of detection are subjected to a collation, the intersection which is passed at the time of the detection is estimated on the basis of the collation, the route segment into which the moving object has been advanced is estimated on the basis of the detected state when the state of the advancement into the intersection is detected, data about the shape and the position of the route segment into which the moving object has been advanced is retrieved from data stored in the data storage device and a travelling line representing the shape and the position of the route segment is indicated on the display device. Another configuration may be employed in which the state of advancement of the user into the intersection is supplied in place of the detection of the azimuth performed by the azimuth sensor to estimate the route segment into which the user has advanced, data about the shape and the position of the route segment into which the user has advanced is retrieved from data stored in the data storage device and the passage is indicated as the travelling line.As described above, according to the present invention, generating and indicating of the travelling line can be realized by a variety of configurations. In the configuration according to the present invention, a route segment to the end point of the route segment which can be selected if the moving object moves without performing turning to the right/left or along a course in which the driving is regulated is, as information necessary and sufficient for a driver or the like to select a course and in the form of information called the travelling line , indicated on the screen of the display device. The concept of the display information called the travelling line has not been disclosed according to the conventional navigation systems.The navigation system and the method therefor according to the present invention treat the target for the moving object to reach as follows:The configuration is constituted in such a manner that the coordinate position of the target is supplied so that codes about name of the target, the number given to the target and the name are supplied to retrieve data about the target on the basis of the supplied information and information about the target such as the target position is indicated on the screen of the display device.In a case where information supplied to the main unit or information supplied for the purpose of retrieving data about the route segment to indicate the travelling line includes information about the present position, an area to which both the present position and the target position belongs is retrieved and the area is displayed on the display screen and as well as the target position and the travelling line on which the present position or an equivalent position in place of the present position are positioned are indicated on the display screen. The supplied information including information about the present position is exemplified by a case in which a signal transmitted from the transmitter includes information about the position at which the transmitter is disposed, a case in which inputting is performed in accordance with the name of the intersection, the name of a place, the lot number and the name of the roadside facility, a case in which a specific coordinate position is supplied, a case in which the code numbers which correspond to elements showing the above-described positions substantially show the equivalent place in place of the present position and a case in which information about the estimated present position is supplied.As described above, information about the target (for example, the target position) and the line (travelling line) representing the route segment along which the user's vehicle is currently moving are always indicated on one common display screen. Therefore, the user is, at first sight of the display screen, able to determine the selection of the course through which the user is able to reach the target on the basis of the relationship with the actual driving situation.That is, when the driver or the like, who is a user, looks the travelling line indicated on the display screen, the user is able to quickly, easily, extemporaneously and at free will determine to go straight along the route segment along which the user's vehicles is currently moving, or turn to the right or left into another route segment in accordance with the positional relationship with the target.The travelling line serving as information with which the moving object is able to reach the target is superior information with which the determination is made to conventional information used in the conventional navigation technology such as the locus, the present position, the target direction and the moving direction. Furthermore, the configuration according to the present invention is arranged in a manner different from the configuration in which a previously set optimum driving course is instructed but the same is arranged in such a manner that the determination made by a driver or the like is given priority. Therefore, the load and danger of the driver can be eliminated from the psychological viewpoint and a significantly preferable effect can be obtained in terms of the traffic safety.In addition, information, that is, the present position of the moving object is not obtained but only the line representing the route segment along which the moving object is currently moving must be grasped. Therefore, the restriction involved in the conventional system in which the driving course and the moving object must be continuously aligned with each other on the road map displayed on the display screen can be eliminated. As a result, the load in terms of the accuracy applied to the navigation system can be reduced.If information for specifying the route segment is once supplied, in accordance with the most simple configuration, the travelling line can be generated and indicated. Therefore, the ensuing necessity of estimating the present position by means of the navigation system can be eliminated to make it serve as the navigation system.In each mode of the present invention, the configuration is constituted in such a manner that the present position of the user's vehicle or an equivalent place in place of the present position, an intersection line representing the route segment which intersects the route segment along which the user's vehicles is currently moving at this very moment, the intersection of the travelling line and the intersection line, the moving direction and the locus are, as secondary determination information, indicated. As a result, a variety of requests made in each mode can be met while making the indication of the travelling line to be the basic function.Furthermore, a preferred aspect of the present invention can be constituted in such a manner that data about the shape and the position of the route segment at which the target confronts is stored in the data storage device, data about the target position and data about the route segment which confronts the target are retrieved when a target is set, the target position is indicated on the display device and as well as a line representing the route segment which confronts the target is indicated on the display device. Another configuration example may be arranged in such a manner that data about the shape and the position of a route segment which constitutes a course through which the moving object is able to properly correctly reach the target from a main route segment positioned near the target is, together with data about the shape and the position of the route segment at which the target confronts, stored in the data storage device. Thus, when a target is set, data about the target position and data about the shape and the position of the route segment at which the target confronts are retrieved and as well as data about the shape and the position of the route segment which constitutes the course through which the moving object is able to reach the target is retrieved and the target position and the line representing the route segment at which the target confront are indicated on the display device and as well as the line representing the route segment which constitutes the course through which the moving object is able to reach the target is indicated on the display device.As a result of the thus-made configuration, the route segment and the travelling line with which an access to the target can be made are clearly shown on the display screen. Furthermore, by arranging the configuration in such a manner that the route segment which is able to be adapted to the directional regulation is formed into data and the above-described route segment is indicated or the regulation is clearly indicated, the moving object is significantly easily able to reach the target.Furthermore, the present invention can be constituted in such a manner that the target and the travelling line are not indicated on one display screen. According to this example of display, the configuration is constituted in such a manner that the target direction is retrieved while making the central point or arbitrary points of an area displayed on the display screen in which the travelling line is indicated to be a start point and the target direction is, together with the travelling line, indicated by an arrow or the like,As a result of the thus-arranged configuration, in a case of a mode of the present invention in which the present position and an equivalent position in place of the present position is not used as the assumption, for example, in a case where the travelling line is indicated when a user supplies the name or the code of the route segment as information, in a case where it is difficult to display the target and the travelling line in one area due to the restriction caused from data, or in a case where the present position cannot be detected due to some trouble, the system according to this mode is able to serve as a supplementary function to aid the driver or the like to select the course. Furthermore, since the travelling line is indicated, the arrow representing the target direction does not trouble the user. Therefore, this mode of the present invention is able to serve as a satisfactory effective navigation system.Furthermore, according to the mode of the present invention in which the distance sensor and the azimuth sensor are not required, the navigation system and the method therefor according to the present invention can be utilized as a portable apparatus adaptable to a pedestrian. Also according to this mode, the travelling line and the target are indicated in a manner different from the conventional configuration in which the map is displayed. Therefore, the user is able to recognize the direction of movement to reach the target.Since an effect as a navigation system and a method is obtained because the target and the travelling line are indicated on the display screen, the contents of display can be simplified, causing a plurality of advantages to be realized.In a case where the arrow display system, the size of the display screen can be reduced. However, a predetermined size of the display is required in the map display system. In a case where the present position is shown, it must be collated with the circumferential state after it has been confirmed in the map. Therefore, background information must be sufficiently shown in the map, causing a necessity to arise in that the size of the display screen must be enlarged.On the other hand, since background information is an indispensable factor according to the present invention, the size of the screen can be reduced and as well as a wide area can be displayed as practical and meaningful information.By combining the navigation system and the method therefor according to the present invention with information about traffic snarl, the user is able to previously detour the snarl. Furthermore, an aid system can be provided with which driving can be performed in such a manner that a driver is able to select a route segment to detour the snarl after the driver has confirmed the actual degree of the traffic snarl.According to the present invention, by combining with a navigation system of another course guide system, it can be provided as information source to freely select the course which is deviated from the instructed course in a case where although the optimum course has been instructed, the moving object is deviated from the optimum course during driving or in a case where the instructed course is not accepted by the aged driver because the traffic volume is too large in the instructed course or the traffic speed is too high in the above-described course.Brief Description of DrawingsFig. 1 is a block diagram which illustrates an embodiment of a navigation system according to the present invention;Fig. 2 is a flow chart which corresponds to embodiments 1 and 2;Fig. 3 is a flow chart which corresponds to embodiment 4;Fig. 4 is a flow chart which corresponds to embodiment 6;Fig. 5 is a flow chart which corresponds to embodiment 8;Fig. 6 is a flow chart which corresponds to embodiment 10;Fig. 7 is a flow chart which corresponds to embodiment 12;Fig. 8 is a flow chart which corresponds to embodiment 24; andFigs. 9, 10 and 11 illustrate typical examples of indication made on the screen of the display device in a case where the navigation method according to the present invention is carried out.Best Mode for Carrying Out the InventionEmbodiments of the present invention will now be described hereinafter with reference to the drawings.Fig. 1 illustrates the configuration of a navigation system according to the present invention. The illustrated navigation system collectively includes all of the components. It is preferable that the elements of the system may be selectively employed at the time of a practical use as described later. The sequence illustrated by each of the illustrated flow charts partially shows the characteristic sequence of the navigation method according to the present invention. Therefore, they may be combined with one another as desired at a practical use.The navigation system shown in Fig. 1 is composed of two sections. A first section comprises a main unit with an auxiliary device, which is mounted on a moving object such as an automobile or a human body. The main unit has a function of receiving a signal given from the outside, a function of generating data by utilizing its internal device and the auxiliary device and a function of making the obtained signal or data. A second section is an external unit disposed externally of the main unit, the second section being a unit for supplying a signal including required information to the main unit. Then, the description will be made hereinafter on the assumption that the moving object is an automobile. The automobile provided with the main unit is defined as a user's vehicle .Referring to Fig. 1, a signal 2 emitted from a transmitter 1 disposed on a route segment includes data showing the shape and the position of the route segment on which the transmitter 1 is disposed, or a code for retrieving the data relating to the route segment, or other information about an intersection and a crossing or the like. An orbit satellite 4 irradiates electric waves 5 including information for estimating the position of the user's vehicle. The signal 2 is received by a receiver 3, while the electric waves 5 are received by a receiver 6.The transmitter 1 and the orbit satellite 4 correspond to the above-described external unit.It is preferable that the transmitting section of the transmitter 1 and the receiving section of the receiver 3 are respectively housed in chambers each having members for shielding signals on its side and rear portions and arranged in such a manner that an opening is formed in its front portion. As a result, a directivity in the transmission and the receipt of the signal 2 is given.An azimuth sensor 7 and a distance sensor 8 are devices for use to estimate the present position of the user's vehicle after a travel, the azimuth sensor 7 and the distance sensor 8 being arranged to respectively detect the azimuth and the distance.A touch panel 9 having a touch panel controller 12, a manipulating section 10 and a voice input section 11 which respectively receive an input operation of an operator such as a driver. A data storage section 14, as described in each embodiment of the present invention to be described later, stores any one of required data about the shape and the position of the route segment, information about the intersections and crossings, data about the target and the shape and the position of the route segment through which the moving object is able to reach to the target, coordinates and other map data in a manner corresponding to each embodiment of the present invention. A processing section 23 makes a variety of data items to be described later in accordance with a program stored in a storage device (not shown in Fig. 1). Means for realizing a variety of functions as to the variety of data items are defined in the processing section 23. The function means will be described with reference to Fig. 1 in each of the embodiments of the present invention.In addition, reference numeral 13 designates a display section, 24 designates an input section, and 25 designates a reading means. The processing section 23, the data storage section 14, the display section 13, the input section 24, the receivers 3 and 6, the reading means 25, the azimuth sensor 7, the distance sensor 8, the touch panel controller 12, the touch panel 9, the manipulating section 10 and the voice input section 11 constitute the above-described main unit and the auxiliary device. The azimuth sensor 7, the distance sensor 8 and the like are, in actual fact, the auxiliary devices provided for the main unit.Figs. 9, 10 and 11 illustrate examples of indication on the screen of the display section 13. Referring to these figures, reference numeral 27 designates a target for the user's vehicle to reach, 28 designates the above-described travelling line, 29, 30 and 31 designate the crossings, 32 designates a route segment confronting the target, 33 designates a route segment with which the route segment confronting the target is able to access a main route segment 34 and 35 designate the intersections.Then, various embodiments realized by the navigation system thus-constituted will now be described, while assuming a circuit element block having a predetermined processing function in the processing section 23.Embodiment 1:When information about the route segment along which the user's vehicle is currently moving is supplied to the processing section 23 via the input section 24, data about the shape and the position of the route segment is read from the data storage section 14 via a retrieval means 15. A display processing means 22 generates a travelling line which represents the route segment on the basis of data about the shape and the position of the route segment. The travelling line, that is, a line representing the shape and the position of the route segment along which the user's vehicles is currently moving, is indicated on the display section 13.A variety of ways of supplying information about the route segment along which the user's vehicle is currently moving to the input section 24 and the sources of information of this type to be supplied to the input section 24 will be described in each of the embodiments to be described later.When information about the route segment along which the user's vehicle is currently moving is obtained and this route segment is indicated, as the travelling line, on the screen of the display section 13, the screen, in principle, always indicates information about the target for the user's vehicle to reach. In a case where the position of the target can be indicated on the display screen, it is preferable that the position of the target should be indicated as information about the target. There have been known the configuration and the method of the conventional navigation system for indicating the position of the target on its display device at need. An embodiment 24 will be described as an example relating to the configuration for always indicating the travelling line and the position of the target on the display screen. In a case where the position of the target cannot clearly be indicated on the display screen, another information about target is indicated. This case will be described in an embodiment 28.According to the above-described configuration, the contents indicated on the display section 13, that is, at least the displayed travelling line and the target, enable the driver to instantaneously, easily and clearly recognize the positional relationship between the target and the travelling line. As a result, the driver is able to independently judge and select the preferable course to approach or reach the target while taking the actual state of the travel into consideration.Furthermore, the present position of the user's vehicle is, at need, indicated on the display screen.In general, the route segment along which the vehicle travels is formed into data as a segment between two points given coordinate positions. A data base of the navigation system according to the present invention relating to the route segment is made as follows.First, the route segments are sectioned so as to be formed into data.The forming of the route segments into data is performed in such a manner that data is constituted in units of links which can be obtained by sectioning the route segments at the intersections. Furthermore, a code is given to each link so as to make it to be a subject of a retrieval. If there is a characteristic in the shape of the route segment, for example, if there is a sharp curve, the shape sometimes is utilized to express the route segment.Data about the link is, for example, formed into groups to constitute link groups. The link groups are classified as follows so as to be given codes so that data is made.As to the route segments (it is preferable that each of the route segments be formed into the same route segment for the impression of the driver) which can be respectively considered as one continuous route segment in a general rule data is made in such a manner that the start to the end of the route segment is made to be one route segment and links which constitute this route segment are made to be one group to which a code is given.A point of advancement from another route segment is made to be a start point and links which constitute a route segment from this start point to the end point are formed into one group which constitutes one link group to which a code is given to make data.A split point of an exclusive right-turn lane or an exclusive left-turn lane, or that of an exclusive movement lane (or a route segment), in which vehicles must move, is arranged to be a start point. Furthermore, a course from this start point to the end point of the route segment in which the vehicle moves in this lane is arranged to be one route segment and links which constitute this route segment are formed into one group so as to be given a code as a link group so that data is made.In each of the cases, it is preferable that a specific code is given to each link and furthermore a common code is given to each of the links which constitute one group in order to perform a data retrieval on the basis of these codes.The arrangements are the basic one for making the data base. However, it is preferable that the data base about the route segment be varied as described in each of the following embodiments.Embodiment 2:The transmitter 1 disposed in a route segment transmits the signal 2 including data about the shape and the position of the route segment. The signal 2 is received by the receiver 3 of the main unit. The signal 2 is supplied to the input section 24 via the reading means 25. At this time, the area of a plane coordinates in which the route segment is positioned is read from the data storage section 14 by the retrieval means 15 in accordance with the coordinate position of the route segment or the like. The coordinate data and data about the shape and the position of the route segment are indicated on the display section 13 by the displays processing means 22. It is preferable at this time that sound be generated to inform the user of the receipt of the signal 2 when the same is received. It is preferable that data included in the signal 2 be data about the shape and the position of the route segment from the start point to the end point of the route segment, assuming that the start point is the point at which the transmitter 1 is disposed, and thereby the coming portion of the travelling line (the distance from the present position of the user's vehicle in the travelling line) be indicated.Embodiment 3:In the embodiment 2, data about the position of the transmitter 1 is included in the signal 2. As a result, the position of the transmitter 1 is indicated on the screen of the display section 13 in addition to the travelling line. Embodiment 4 :A code is included in the signal 2 transmitted from the transmitter 1 disposed in the route segment. On the other hand, data about the shape and the position of the route segment which corresponds to the code is stored in the data storage section 14 of the main unit. When the code is, by means of the signal 2, supplied to the processing section 23 via the reading means 25 and the input section 24, data about the shape and the position of the route segment is read out from the data storage section 14 by the operation of the retrieval means 15. In accordance wich retrieved data, the travelling line representing the shape and the position of the route segment is then indicated on the display section 13 by the display processing means 22.Also in this embodiment, it is preferable that the receipt of the signal 2 be informed to a user when the same is received by the sound.Embodiment 5 :In the embodiment 4, data about the position of the transmitter 1 is included in data to be stored in the data storage section 14 so that the position of the transmitter 1 is indicated on the display section 13 in addition to indicating the travelling line. Embodiment 6:Data about the shape and the position of all of the route segments are stored in the data storage section 14. Therefore, when a user (a driver or another occupant) supplies any one of the name of the route segment, that of the intersection, the name of a place, the lot number, the name of a facility positioned on the roadside, the coordinate position or a code number given to it by the key of the manipulating section 10, the touch panel 9, the voice input section 11 or the like, data about the shape and the position of the route segment is read from the data storage section 14 by the operations of the input sections 24 and the retrieval means 15. As a result, the travelling line is indicated on the display section 13 on the basis of the function of the display processing means 22.Embodiment 7 :As the equivalent position to be treated in place of the present position of the user's vehicle, position data of a region which is expressed by the intersection and the name of a place or the lot number, that of the point which is indicated by the facility positioned on the roadside or the coordinates are stored in the data storage section 14 so that the equivalent position is indicated on the display section 13 together with the travelling line. Embodiment 8 :Information about the route segment along which the user's vehicle is currently moving is supplied via the input section 24 connected to the receiver 6 for receiving the electric waves 5, the receiving 3 for receiving the signal 2, the reading means 25, the distance sensor 7 and the azimuth sensor 8. Information thus-supplied is made in the processing means 16 so that the present place (present position) at which the user's vehicle moves is estimated by a present place estimating means 17. In accordance with the estimated present position, the route segment is estimated and discriminated by a route segment estimating means 18. After the route segment has been discriminated, data about the shape and the position of the route segment is read from the data storage section 14 by the retrieval means 15. Furthermore, it is supplied to the display processing means 22 so that the travelling line representing the shape of the route segment is indicated on the display section 13.As a method for discriminating the route segment along which the user's vehicle is currently moving in accordance with the estimated present position of the user's vehicle, it is preferable that, for example, an arbitrary points set on the route segments are, as data, stored in the data storage section 14 to perform the nearest point retrieval while making the arbitrary points to be the subject. As a method of setting the arbitrary point, it is preferable that plural points should be set at long intervals in one route segment in a case where there is no adjacent route segment to the one route segment, and that the arbitrary point in another route segment should be set at a position corresponding to the point set in one route segment in a case where there are two route segments to be adjacent mutually. As a result of the retrieval performed in such a manner that the arbitrary points are respectively treated as the nearest point to the position of the vehicle, the route segment is discriminated by utilizing the nearest points.According to the above-described embodiment, data is retrieved in accordance with the arbitrary point set in the route segment, or a link constituting the discriminated route segment to which the arbitrary point belongs. It is preferable that a specific code to a link which constitutes the route segment is given in addition to the specific link code to each link to retrieve data about the links. As an alternative to this, it is preferable that a group code for each link group, which is constituted by the links, is given to retrieve data formed into a group by the group code. As an alternative to this, a common code is given to the specific code to the link which constitutes the route segment is given to perform retrieval by the common code. Embodiment 9:In the above-described embodiment 8, a point on the route segment nearest to the estimated present position may be, together with the travelling line, indicated on the display section 13.Embodiment 10:When a passed route segment is discriminated upon a comparison made between the shape of a locus (passed route segments or route segments along which the vehicle has already passed) and the shape of the route segment based on the stored data, a route segment present in front of the passed route segment and along which the vehicle will run if the user's vehicle does not turn right or left is discriminated by a route segment discriminating means 18 on the basis of the discriminated passed route segment. Then, data about the shape and the position of the discriminated route segment is read from the data storage section 14 by the retrieval means 15. As a result, the travelling line is indicated on the display section 13 by means of the display processing means 22.According to the above-described embodiment, it is preferable that data be retrieved on the basis of the final link which constitutes the passed route segment.It is preferable that a specific code is given to a link which constitutes the route segment from the link to the end point of the same to retrieve data about it, in addition to the specific link code to each link. As an alternative to this, it is preferable that a group code for each link group, which is constituted by the links, is given to retrieve data formed into a group by the group code. As an alternative to this, a common code is given to the specific code to the link which constitutes the route segment to the end point of the same to perform retrieval by the common code.Embodiment 11:When the travelling line is indicated on the display section 13, the estimated present position is, as the end point of the locus or the start point of the travelling line, indicated on the display section 13 by means of the display processing means 22.Embodiment 12:The data storage section 14 stores data about the shape and the position of the route segments and as well as, together with the state of advancement at the intersection, stores the distance between intersections and the route segments which intersect each route segment. When information about the start point is, as the initial positional information, supplied through the input section 24, each intersection is discriminated by an intersection discriminating means 19 on the basis of both of the distance from the start point to each intersection calculated in accordance with the stored data, and the actual running distance measured by the distance sensor 8. In accordance with azimuth information detected by the azimuth sensor 7, the route segment into which the vehicle has been advanced at the intersection is discriminated by the route segment discriminating means 18. In accordance with information about the result of the discriminations, data about the shape and the position of the route segment into which the vehicle has been advanced is read from the data storage section 14 by the retrieval means 15.According to the above-described embodiment, data constituting the discriminated route segment is retrieved. It is preferable that a specific code to a link which constitutes the route segment from the most forward link to the end point of the route segment is given in addition to the specific link code to the most forward link of the route segment into which the vehicle has been advanced to retrieve data about them. As an alternative to this, it is preferable that a group code for each link group, which is constituted by the links, is given to retrieve data formed into a group by the group code. As an alternative to this, a common code is given to a specific code to a link which constitutes the route segment to its end point is given to perform retrieval by the common code. Embodiment 13:It is preferable that the position of the estimated passed-intersection is stored in a storage means 20 to indicate, together with the travelling line, the estimated passed intersection on the display section 13.Embodiment 14:Although the configuration in the embodiment 12 is arranged in such a manner that the state of the user's vehicle to turn to the right/left is detected by the azimuth sensor 7, this configuration is arranged in such a manner that a user inputs the state of turning to the right/left by any one of the voice input section 11, the touch panel 9, and the key or the switch disposed in the manipulating section 10.Embodiment 15 :The position of the estimated passed-route segment is scored in a storage means 20 to display, together with the travelling line, this intersection on the display section 13.The above-described embodiments 12 and 14 may be modified as follows:As for the initial movement position, it is preferable that a point is previously set, the position of this point is stored in the data storage section 14 and it is then supplied by means of the code given to the point to set the initial movement position.When the initial movement position is supplied as the coordinate position of an arbitrary point, the distance from the initial movement position to an intersection at which the vehicle first turns right or left is detected by the distance sensor 8. The detected distance is stored in the storage means 20 and the same is as well as collated with the distance obtained from a means provided in the intersection discriminating means 19 and arranged to calculate the distance from the initial movement position to each intersection. Thus, the intersection at which the user's vehicle has turned right or left is discriminated by the intersection discriminating means 19.It is preferable that the configuration be arranged in such a manner that, when the user's vehicle has once turned to the right or left at an intersection, this intersection is, as the initial movement position, stored in the storage means 20 so as to discriminate the intersection at which the vehicle will then turn to the right or left on the basis of the stored data.It is preferable that the distance from a point, which can be set as the initial movement position, to an intersection on a route segment near the point is, together with the initial movement position, stored in the data storage section 14 and make it to be collated with the distance detected by the distance sensor 8. It is preferable that a code for the route segment to which the point is set is given to data about the point so as to retrieve data about the route segment when the point is set as the initial movement position and it is then indicated as the travelling line on the display section 13.It is preferable that the point, which is previously set as the initial movement position, be a facility which can easily be made to be a mark such as a gasoline station or a roadside restaurant and which relates the travel of the vehicle. In this case, it is supplied as a code given to the facility.As the point which is previously set as the initial movement position, it is also preferable that a plate or the like which is disposed at the intersection or the route segment and given a code number or the like be used.In a case where the initial movement position is an arbitrary position, it can be set on the screen of the display section 13 by using a cursor or it can be set by means of the latitude and the longitude. In order to calculate the distance, it is preferable that the position be converted into coordinate position.In a case where the azimuth sensor 7 detects the right turn or the left turn of the user's vehicle, a collation is made between the travelled distance and the detected data about the right turn or the left turn. If there is not subject intersection, it is preferable that the discrimination of the intersection be cancelled. The case takes place when the lane is changed, the vehicle drops in a parking area or a roadside restaurant, or the right turn or the left turn due to a sharp curve route segment or the like is detected. When the user inputs the state of the right or the left turn or when azimuth sensor 7 detects it and an effective discrimination of the intersection is thereby made, it is preferable that the cumulative quantity detected by the distance sensor 8 is cancelled and counting is again commenced from zero.In a case where the user inputs the state of the right turn or the left turn of the user's vehicle, it is preferable that the travelling line is indicated on the display section 13, the nearest intersection positioned forward is shown by an exaggerated enlarged view. Therefore, when the number given to the route segment in this enlarged view is input by a key or voice or by directly touching the display screen, the route segment to which the user's vehicle will be advanced is discriminated.As another modification, it is preferable that the state of the advancement be input by voice in such a manner that it is expressed as right , upper right , lower right and left . In this case, a configuration can be employed in which each advancement state is given so as to be input by the given number or the same is input in another language such as English.Another modification may be employed which is constituted in such a manner that keys or switches are disposed at the top end section, the intermediate portion and the lower portion of the right side of the screen frame of the display section 13, the top end portion, the intermediate portion and the lower potion of the left side of the same and the right portion and the left portion of the lower side of the same to correspond to the state of the advancement, that is, the upper right, right, lower right, upper left, left, lower left and U-turn. Embodiment 16 :In a case where information about the route segment along which the use's vehicle is currently moving includes information about the present position of the vehicle, data about the shape and the position of the subject route segment from the present position to the end point of the route segment is retrieved from data stored in the data storage section 14 to indicate the forward portion of the route segment along which the vehicle is currently moving, as the travelling line, on the display section 13 on the basis of the retrieved data. Embodiment 17:When the travelling line and the locus are indicated on the display section 13, the travelling line and the locus are indicated by different kinds of lines or different colors.Embodiment 18:The display mode on the display section 13 may be arranged in such a manner that the shape and the position of the route segment along which the user's vehicle is currently moving are indicated as the travelling line, and furthermore, the shape and the position of another route segment which intersects the route segment along which the user's vehicle is currently moving are indicated as intersection lines 29, 30 and 31.In this case, it is preferable that the travelling line and the intersection line be indicated in different colors or different kinds of lines.Embodiment 19:As a display mode on the display section 13, the position of the intersection may be, together with the travelling line and the intersection line, indicated or the same may be indicated in place of the travelling line and the intersection line. Embodiment 20:As a display mode on the display section 13, the direction of the travel or the direction in which the vehicle must travel may be indicated by using an arrow or the like in addition to the travelling line.Embodiment 21:The travelling direction can be indicated on the display section 13 on the basis of the detection of the travelling direction obtained by the azimuth sensor 7.Furthermore when the present position is estimated in accordance with the satellite electric waves 5, a means for storing the estimated point and indicating this point on the screen of the display section 13 is provided, wherein the travelling direction is indicated by continuous points, or a direction in the direction of extension of a line connecting two or more continuous points including the final point is defined as the travelling direction, whereby the travelling direction discriminating means 21 discriminates the travelling direction in accordance with the above-made definition so as to indicate the travelling direction on the display section 13 by an arrow or the like. Embodiment 22:It is preferable that the locus be indicated together with the travelling line on the screen of the display section 12.Embodiment 23:As a display mode to be made on the display section 13, the present position or the equivalent position in place of the present position can be indicated on the display section 13. Furthermore, it is preferable that the present position or the equivalent position in place of the present position be stored in the storage means 20 and a sequential plurality of stored points are indicated together with the travelling line.Embodiment 24:The configuration can be formed in such a manner that, in a case where input information for retrieving data about the shape and the position of the route segment to be indicated as the travelling line includes information about the present position of the user's vehicle, an area to which both the present position and the target position for the user's vehicle belong is retrieved so as to indicate the area on the display section 13, and in addition, the target position, a travelling line having the present position or the equivalent position in place of the present position thereon may be indicated on the display section 13. It is preferable that the area to which both the coordinate position of the present position or that of the equivalent position in place of the present position and that of the target coordinate position belong be retrieved. As an alternative to this, it is preferable that codes for a small area and a large area set to several stages as being a different reduced scale to meet a desire are given to a signal transmitted by the transmitter 1, data to be retrieved in response to this signal, data to be retrieved by the name of the intersection, the name of a place, a lot number, the roadside facility or the like which is supplied by the user, data to be retrieved by the present position or the passed route segment estimated in accordance with the result of the satellite electric wave or the detection made by each sensor or data to be recrieved by the intersection at which the user's vehicle has been advanced into a different route segment. Also data about the target position is given the similar area code, whereby a code which is common to them is retrieved.It is preferable that the area codes for them be retrieved in such a manner that the sequential collation is started form a small area code to retrieve a code which is common to them. As an alternative to this, the sequential collation is started from a large area code until the area becomes different in a small area, and then a restoration to the common area is made.As an alternative to this, a configuration can be employed which is arranged in such a manner that a large area to which both the target and the travelling line belong is displayed, a frame which can be moved and the size of which can be changed is provided in the display screen and an area to which both the target and the travelling line belong is determined and selected by the user's operation of the frame so as to display this area. As an alternative to this, either of the target or the travelling line is first indicated on the display screen and the area is sequentially changed to a large area by the user until they belong to the same area.Embodiment 25:The configuration is constituted in such a manner that the position of a target for the user's vehicle is stored in the data storage section 14 together with data about the shape and the position of the route segment at which the target confronts. It is preferable that data about the position of the target be retrieved by the retrieval means 15 when the target is set and as well as data of the shape and the position of the route segment which confronts the target be retrieved to indicate the position of the target, the shape and the position of the route segment on the display section 13. If a variety of regulations are applied to the route segment, for example, if there is a directional regulation, it may be shown by an arrow or the like or the sections through which the vehicle can or cannot pass in the route segment at which the target confronts it may be expressed by different colors or different kinds of lines, on the screen of the display section 13.It is preferable that the vehicle type regulation, the hour regulation and weight regulation be indicated on the display section 13 on the basis of the selection made by the user.Embodiment 26:The configuration is constituted in such a manner that data about the shape and the position of the route segment which constitutes a course through which the vehicle is able to properly and correctly reach from a main route segment adjacent to the target is stored in the data storage section 14. It is preferable that, when a target is set, the target and the shape and the position of the route segment along which the vehicle reaches this target be indicated on the screen of the display section 13.It is preferable that route segments constituting a course to be practically advantageous should be indicated on the display screen in accordance with the regulation of the law together with the target, and furthermore the passed intersections and their names, marks for them or the like should be indicated similarly.It is preferable that the main route segment which is connected to the route segment indicated together with the target and another route segment which is connected to the main route segment when the main route segment is indicated together with the target are stored in the data storage section 14, whereby, when the above-described another route segment is retrieved as the route segment for the user's vehicle, a message target accessed is informed to the user by voice or image.Embodiment 27:it is preferable that, when a target is set, a target direction, the start point of which is made to be the present position or an equivalent position in place of the present position, be discriminated by a target direction discriminating means 26 and as well as the discriminated target direction be indicated by an arrow or the like together with the travelling line on the display section 13.In a case where the travelling line is indicated while being given a priority on the display screen, for example, in a case where the target cannot be indicated on the display screen because an enlarged view is displayed on the screen of the display section 13 as a result of passing along a route segment which puzzles the user or a complicated passage, it is preferable that the target direction should be indicated.Embodiment 28:The configuration can be constituted in such a manner that, when a target is set, the target direction, the start point of which is a central point or an arbitrary point in the area displayed on the display section 13 which indicates the travelling line, is discriminated by the target direction discriminating means 26. The discriminated target direction is, together with the travelling line, indicated by an arrow or the like on the display section 13.it is preferable that, in a case where the travelling line is indicated while being given a priority on the display screen, for example, in a case where the target cannot be clearly indicated on the display screen because an enlarged view is displayed on the display screen as a result of passing along a route segment which puzzles the user or a complicated passage, or in a case where information about the present position cannot be obtained, the target direction should be indicated. Embodiment 29:It is preferable that, when a novel information item as to the route segment along which the user's vehicle is currently moving, which is different from information which has been previously supplied, is supplied, data about the novel route segment along which the user's vehicle is currently moving is retrieved in accordance with the novel information item and a corresponding travelling line is indicated on the display screen, both the travelling line to be indicated in accordance with the previous input information and the travelling line to be indicated in accordance with the novel input information should be indicated and they should be indicated by different lines or different colors so as to distinguish them.Then, the contents of the processing operation to be performed by the processing section 23 will now be described with reference to flow charts shown in Figs. 2 to 8. The processing operation to be executed by the processing section 23 is the navigation method to be executed by the navigation systems shown in Fig. 1. The operations for respectively performing the navigation methods shown by the above-described flow charts have basically been described in the above-described respective embodiments. Therefore, each navigation operation will now be described while describing the correspondence with the embodiments.Basically, the navigation method according to the present invention is, as can be seen from the description as to the navigation systems, constituted in such a manner that, when information about the route segment along which the user's vehicle is currently moving is supplied to the main unit including the processing section 23, the main unit generates data concerning the travelling line representing the shape and the position of the route segment along which the user's vehicle is currently moving in accordance with the reformation. Then, the travelling line thus-obtained is indicated on the screen of the display section 13 while showing clearly the positional relationship with the target.Specifically, the navigation method according to the present invention is executed as follows:First, the signal 2 is, as shown in Fig. 2, received by the receiver 3 (step 51). Then, data about the shape and the position of the route segment along which the user's vehicle is currently moving is read (step 52) so as to retrieve an area which corresponds to the read route segment (step 53). Then, the area and the travelling line are indicated on the screen of the display section 13 (step 54). For example, the signal to be supplied to the receiver 3 is, as described in the embodiment 2, the signal transmitted from the transmitter 1. The above-described navigation method corresponds to, for example, the embodiments 1 and 2.As shown in Fig, 3, the signal including the code is received by the receiver 3 (step 61). Then, the code included in the signal is read (step 62) so as to retrieve data about the route segment which corresponds to the above-described code from the data storage section 14 (step 63). Then, the travelling line is indicated on the screen of the display section 13 (step 64). The above-described navigation method corresponds to the embodiment 4.Another navigation method is, as shown in Fig. 4, constituted in such a manner that information about the route segment along which the user's vehicle is currently moving is supplied by the user by operating the manipulating section 10 or the like (step 71). Then, data about the route segment which corresponds to supplied information is retrieved from the data storage section 14 (step 72) so as to indicate the travelling line representing the shape and the position of the retrieved route segment on the screen of the display section 13 (step 73). The above-described navigation method corresponds to the embodiment 6.Another navigation method is arranged in such a manner that, when information obtained from the satellite electric waves 5 or the sensors 8 and 10 is, as shown in Fig. 5, supplied (step 81), the present position of the user's vehicle is estimated in accordance with supplied information (step 82) . Then, the route segment corresponding to the estimated present position is discriminated (step 83) so as to data for indicating the travelling line which corresponds to the above-described route segment is retrieved from the data storage section 14 (step 84). Then, the travelling line is indicaced on the screen of the display section 13 (step 85). The above-described navigation method corresponds to the embodiment 8.A further navigation method is, as shown in Fig. 6, constituted in such a manner that, when information of the satellite electric wave 5 or that obtained as a result of the detection performed by the sensors 8 and 10 is supplied (step 91), the present position of the user's vehicle is estimated in accordance with the supplied information and a locus for the user's vehicle is obtained in accordance with a plurality of estimated present positions (step 92). Then, the locus thus-obtained and a route segment stored in the data storage section 14 are subjected to a comparison (step 93). As a result of this comparison, the passed route segment is discriminated (step 94) so as to retrieve data about the forward route segment from the data storage section 14 in accordance with the passed route segment (step 95). Then, a travelling line representing the shape and the position of the retrieved route segment is indicated on the screen of the display section 13 (step 96). The above-described navigation method corresponds to the embodiment 10.Another navigation method is, as shown in Fig. 7, arranged in such a manner that the initial movement position is set (step 101). Then, the travelled distance from the initial movement position is detected (step 102) so as to store the detected travelled distance (step 103). Furthermore, the distance from the initial movement position to each intersection is obtained in accordance with data (step 104). Then, the intersection which is passed is estimated from the result of a comparison made between the above-described distance and the above-described detected travelled distance (step 105). Then, the state of the advancement into the intersection is detected (step 106) to estimate the advanced route segment (step 107), retrieve data about the advanced route segment (step 108) and indicate the travelling line on the screen of the display section 13 in accordance with the retrieved data (step 109). The above-described navigation method corresponds to the embodiment 12.The navigation method shown in Fig. 7 may be arranged in such a manner that the travelling line is indicated by a user by inputting the state of the advancement into the intersection by operating the manipulating section 10 in step 106.Another navigation method is, as shown in Fig. 8, arranged in such a manner that, when the name or the code of a target is supplied (step 111), data about the target is retrieved (step 112) and the target is indicated on the screen of the display section 13 in accordance with the data (step 113). If information about the route segment along which the user's vehicle is currently moving is supplied at this time (step 114), a signal concerning the information is read or data concerning the passage is retrieved (step 115). Then, an area to which both the present position or an equivalent position in place of the present position and the target belong is retrieved (step 116) so that the above-described area is displayed on the screen of the display section 13. Thus, the target and the travelling line are indicated on the display screen (step 117). The above-described navigation method corresponds to the embodiment 24,Industrial ApplicabilityAs described above, the navigation system and the method therefor according to the present invention are optimum to be mounted on a vehicle while making a driver to be the subject. Furthermore, it can be used as a portable navigation system for a pedestrian.
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A navigation system comprising a main unit having a storage device (14), a central processing device (23), an input device (24) and a display device (13), said main unit accompanying a moving object, wherein said central processing device (23) has display processing means (22) for always indicating information about a target for said moving object to reach and information about the position of said object and for displaying said information on a screen of said display device (13), wherein said input device (24) has a function of receiving information about the shape and the position of a route segment along which said object is currently moving from an external device (1, 4) positioned externally to said main unit and/or an auxiliary device (7, 8, 10, 11) provided for said main unit; andas indication of the position of said object, said central processing device (23) is adapted to generate a line (28) representing said route segment along which said object is currently moving on the basis of said information whenever said input device (24) receives said information about the shape and the position of said route segment while clearly indicating the positional relationship with said target, and wherein an end point of said line (28) corresponds to a final point of said route segment which can be reached if said moving object moves without performing turnings to the right or left which are not prescribed by traffic regulations.A navigation system according to claim 1, wherein said external device is a transmitting device (1) disposed in each route segment, said transmitting device (1) having data supplying means for supplying data about the shape and the position of said route segment in which said transmitting device is disposed;said storage device (14) stores data about plane coordinates of areas;said main unit has, in a stage before said input device (24), receiving means (3) for receiving said signal (2) transmitted from said transmitting device (1) and reading means (25) for reading said signal (2) received by said receiving means (3) and said central processing device (23) has retrieval means (15) for retrieving said area on said plane coordinates in which said route segment exists ,from said storage devices (14), on the basis of said information obtained by said reading means (25); andsaid input device (24) fetches said data about the shape and the position of said route segment from an output signal from said reading means (25) and said display processing means (22) generates said line (28) representing said route segment on the basis of said area obtained by said retrieval means (15) and said data about the shape and the position of said route segment obtained by said input device (24) and indicates said line (28) on said display device (13).A navigation system according to claim 1, wherein said external device is a transmitting device (1) disposed in each route segment;said transmitting device (1) has code supplying means for supplying a specific code for said transmitting device (1) to a signal (2) transmitted from said transmitting device (1);said storage device (14) stores data about the shape and the position of each route segment;said main unit has, in a stage before said input device (24), receiving means (3) for receiving said signal (2) transmitted from said transmitting device and reading means (25) for reading said signal (2) received by said receiving means (3) and said central processing device has retrieval means (15) for, from data stored in said storage device (14), retrieving data about the shape and the position of said route segment in which said transmitting device (1) is disposed on the basis of said code obtained by said reading means (25); andsaid display processing means (22) generates said line (28) representing said route segment on the basis of said data about the shape and the position of said passage obtained by said retrieval means (15) and indicates said line (28) on said display device (13).A navigation system according to claim 1, wherein said auxiliary device is an input manipulating device (10) for inputting various information items, with which said route segment, which is recognized by an operator at the time of travelling said route segment, can be specified, to said input device (24);said storage device (14) stores data about the shape and the position of each route segment;said central processing device (23) has retrieval means (15) for retrieving data about the shape and the position of a corresponding route segment from said storage device (14) on the basis of said information when said operator inputs said various information items into said input device by operating said input manipulating device (10); andsaid display processing means (22) generates said line (28) representing said route segment on the basis of said data obtained by said retrieval means (15) and indicates said line (28) on said display device(13).A navigation system according to claim 4, wherein said various information items are any one of the name of a route segment, the name of an intersection, the name of a place, a lot number, the name of a facility on the roadside and the coordinate position, or a code number given to each of these information items.A navigation system according to claim 1, wherein said external device is a satellite (4) for emitting electric waves including positional information;said storage device (14) stores data about the shape and the position of each route passage;said central processing device (23) has present position estimating means (17) for estimating the present position of said moving object on the basis of said positional information supplied by said satellite (4), route segment discriminating means (18) for discriminating a route segment nearest to said present position when said present position is obtained by said present position estimating means (17) and retrieving means (15) for retrieving data about the shape and the position of said route segment from data stored in said storage device (14); andsaid display processing means (22) generates said line (28) representing said route segment on the basis of said data about the shape and the position of said route segment obtained by said retrieval means (15) and indicates said line (28) on said display device(13).A navigation system according to claim 6, wherein said central processing device (23) has retrieval means (15) for retrieving data about a point near said estimated present position and said display processing means (22) indicates said retrieved point on said line (28) indicated on said display device (13).A navigation system according to claim 1, wherein said external device is a satellite (4) for emitting electric waves including positional information;said storage device (14) stores data about the shape and the position of each route segment;said central processing device (23) has a present position estimating means (17) for estimating the present position on the basis of said electric waves emitted from said satellite, a route segment discriminating means (18) for discriminating a passed route segment by comparing a locus obtained on the basis of said estimated present position and said shape of said route segment stored in said storage device (14) and retrieval means (15) for, from data stored in said storage device (14), retrieving data about the shape and the position of a route segment which is in front of said passed route segment and will be a route segment when no turning to right/left is made, when said passed route segment is discriminated as a result of the comparison; andsaid display processing means (22) generates said line (28) representing a route segment along which said moving object is currently moving on the basis of said retrieved data and indicates said line (28) on said display device (13).A navigation system according to claim 8, wherein said line (28) is indicated in such a manner that said estimated present position is made to be the start point of said line (28).A navigation system according to claim 1, wherein said auxiliary device includes a distance sensor (8) for detecting a travelled distance and an azimuth sensor (7) for detecting a direction of a travel;said storage device (14) stores data about the shape and the position of each route segment, route segments intersecting each route segment, a state of advancement at each intersection and the distance between intersections in each route segment;said central processing device (23) has means for setting an initial movement position, means for storing the detected quantity of the distance from said initial movement position detected by said distance sensor (8), means for obtaining the distance from said initial movement position to each intersection, means for collating said distance and said detected quantity, means for estimating intersections passed at the time of said detection when said collation has been made, means for, when said azimuth sensor (7) detects the state of advancement into an intersection, estimating a route segment into which an advancement is made on the basis of said detected state and means for retrieving data about the shape and the position of said route segment into which said advancement is made from data stored in said storage device (14); and said display processing means (22) generates said line (23) representing said route segment on the basis of said retrieved data and indicates said line (23) on said display device (13)A navigation system according to claim 1, wherein said auxiliary device includes a distance sensor (3) for detecting a travelled distance and input manipulating means (10) for inputting, by an operator, a state of advancement at an intersection from a route segment along which a moving object is currently moving to another route segment;said storage device (14) stores data about the shape and the position of each route segment, route segments intersecting each route segment, a state of advancement at an intersection and distance between intersections in each route segment;said central processing device (23) has means for setting an initial movement position, means for storing the detected quantity of the distance from said initial movement position detected by said distance sensor (8), means for obtaining the distance from said initial movement position to each intersection, means for collating said distance and said detected quantity, means for estimating intersections passed at the time of said detection when said collation has been made, means for estimating a route segment into which an advancement is made on the basis of said state of advancement into another route segment at said intersection supplied by said operator and means for retrieving data about the shape and the position of said route segment into which said advancement is made from data stored in said storage device (14); andsaid display processing means (22) generates said line (28) representing said route segment on the basis of said retrieved data and indicates said line (28) on said display device (13).A navigation system according to claim 1, wherein said central processing device (23) has retrieval means (15) for retrieving data about the shape and the position of said route segment from the present position of said moving object to the end point of said route segment through which said moving object is moving at this very moment in a case where information about the present position is obtained on the basis of said information about the shape and the position of said route section along which said moving object is currently moving; andsaid display processing means (22) indicates the forward portion of said route section along which said moving object is currently moving as said line (28) representing said route section on the screen of said display device (13) on the basis of said retrieved data.A navigation system according to claim 2, wherein said data supplied from said transmitting device (1) includes data about the shape and the position of another route section which intersects said route section along which said moving object is currently moving and a line (29, 30, 31) representing said another route section is, together with said line (28) representing said route section along which said moving object is currently moving, indicated on the screen of said display device (13) as an intersection line.A navigation system according to claim 3, wherein said storage device (14) stores data about the shape and the position of each route section and data about the shape and the position of a route section which intersects each of said route sections, said retrieval means (15) as well as retrieves data about the shape and the position of said which intersects said route segment when said retrieval means (15) retrieves data about the shape and the position of said route segment in which said transmitting device (1) is disposed from data stored in said storage device and a line (28) representing said route segment along which said moving object is currently moving and a line (29, 30, 31) representing said other route segment are indicated on the screen of said display device (13) as an intersection line.A navigation system according to claim 1, wherein in a case where information about the present position of said moving object is included in said information obtained by said input device (24) about the shape and the position of said route segment along which said moving object is currently moving, an area to which both said present position and the position of said target belong is retrieved and said target and said line (28) on which said present position or an equivalent position in place of said present position is present are indicated on the screen of said display device (13).A navigation system according to claim 15, wherein said storage device (14) stores said position of said target by means of the coordinate position and data about the shape and the position of a route segment which confronts said target, said data about said position of said target is retrieved when a target is set, also data about the shape and the position of said passage which confronts said target is retrieved and said target and a line (32) representing said passage which confronts said target are indicated on the screen of said display device.A navigation system according to claim 16, wherein said storage device further stores data about the shape and the position of a route segment which constitutes a course which properly correctly reaches said target from a main route segment near said target, data about said target and data about the shape and the position of said route segment which confronts said target are retrieved when a target is set, also data about the shape and the position of said route segment which constitutes said course is retrieved and said position of said target, a line (32) representing said route segment which confronts said target and a line (33) representing said route segment which constitutes said course are indicated on the screen of said display device (13).A navigation system according to claim 1, wherein said central processing device (23) has means (26) for retrieving a direction of said target while making an arbitrary point of an area displayed on the screen of said display device (13) to be a start point when said target is set and said display processing means (22) indicates said (28) representing said route segment and an arrow representing said direction of said target on the screen of said display device (13).A navigation system according to claim 1, wherein when as to said route segment along which said moving object is currently moving novel information different from said information which has been supplied is supplied, said data is retrieved on the basis of said novel information and a line corresponding to said novel information is indicated on said display device on the basis of said retrieved data, said line (28) generated by said previous information and said line generated by said novel information are indicated together on the screen of said display device (13) in such a manner that said two lines are indicated by different kinds of lines or different colors. A navigation method of generating information about a moving state of a moving object and indicating said information on a display device, said navigation method comprising the steps of: in a main unit accompanying said object, setting a target for said moving object to reach, generating information about the position of said object and always indicating information about said target, and about the position of said object on a screen of said display device (13), whereinsaid information about the position of said object is the shape and the position of a route segment along which said moving object is currently moving,said indication of the position of said object includes a line (28) representing said route segment generated on the basis of said information about the shape and the position of said route segment,said line (28) is updated on said screen whenever said route segment is changed, andan end point of said line (28) corresponds to a final point of said route segment which can be reached if said moving object moves without performing turnings to the right or left which are not prescribed by traffic regulations.A navigation method according to claim 20, wherein a signal including data about the shape and the position of said route segment along which said moving object is currently moving is transmitted from a transmitting device (1) disposed in each route segment and said main unit uses said data obtained by receiving said signal as said information about the shape and the position of said route segment.A navigation method according to claim 20, wherein a signal including a code for specifying said route segment along which said moving object is currently moving is transmitted from a transmitting device (1) disposed in each route segment and said main unit generates said information about the shape and the position of said passage on the basis of said data obtained by receiving said signal and data stored in said storage device.A navigation method according to claim 20, wherein an operator inputs, into said main unit, various information items with which said route segment, which is recognized at the time of a movement along a route segment, can be specified and said information about the shape and the position of said route segment is generated on the basis of said various information items.A navigation method according to claim 23, wherein said various information items are any one of the name of a route segment, the name of an intersection, the name of a place, a lot number, the name of a facility on a roadside, a coordinate position or a code number given to these information items.A navigation method according to claim 20, wherein electric waves including positional information and emitted from a satellite (4) are received, the present position of said moving object is estimated on the basis of said positional information supplied from said satellite (4), a route segment which is nearest to said present position is discriminated when said present position is obtained and said information about the shape and the position of said route segment is generated on the basis of said nearest route segment.A navigation method according to claim 25, wherein data about a point near said estimated present position is retrieved and said retrieved point is indicated on said line (28) indicated on said display device.A navigation method according to claim 20, wherein the present position of said moving object is estimated, the traveling locus of said moving object is obtained on the basis of said estimated present position, said locus thus-obtained is subjected to a comparison with previously-prepared data about the shape and the position of a route segment, a route segment in which the latest present position is included is obtained by making a retrieval and a line (28) representing said retrieved route segment is indicated on said screen of said display device.A navigation method according to claim 27, wherein the indication is performed in such a manner that said estimated present position is made to be the initial end portion of said line (28).A navigation method according to claim 20, wherein data about the shape and the position of each route segment, route segments intersecting each route segment, the state of advancement at each intersection and the distance between intersections in each route segment are previously prepared in a storage device, the distance from an initial movement position is detected by a distance sensor (8) to store it in a case where said initial movement position is set, the distance from said initial movement position to each intersection is obtained, said distance and said detected quantity are compared with each other, an intersection which is passed at the time of detection is estimated, a route segment into which said moving object has been advanced is estimated on the basis of the detected state of said advancement into said intersection when the same is detected, data about the shape and the position of said route section in which said moving object has been advanced is retrieved from data stored in said storage device (14), a line (28) representing said route section is generated on the basis of said retrieved data and said line (28) is indicated on said display device (13).A navigation method according to claim 20, wherein a distance sensor (8) for detecting the travelled distance and input manipulating means (10) for, by an operator, inputting the state of an advancement from a route section along which said moving object is currently moving into another route section at an intersection are utilized;data about the shape and the position of each route section, route sections intersecting each route section, the state of advancement at each intersection and the distance between intersections in each route section are previously prepared in a storage device (14);when an initial movement position is set, the distance from said initial movement position is detected by said distance sensor (8) to store it, the distance from said initial movement position to each intersection is obtained, said distance and said detected quantity are compared, an intersection which is passed at the time of detection is estimated, said route section into which said moving object has been advanced is estimated from the state of advancement into another route section at said intersection supplied by said operator, data about the shape and the position of said route section into which said moving object has been advanced is retrieved from data stored in said storage device (14), a line (28) representing said route section is generated on the basis of said retrieved data and said line (28) is indicated on said display device (13).A navigation method according to claim 20, wherein in a case where information about the present position of said moving object is obtained on the basis of said information about the shape and the position of said route section along which said moving object is currently moving, data about the shape and the position of said route section from said present position to the end position of said route section along which said moving object is currently moving is retrieved from data stored in said storage device (14) and the forward portion of said route section along which said moving object is currently moving is, as a line (28) representing said route section, indicated on said display device (13) on the basis of said retrieved data. A navigation method according to claim 20, wherein another route segment intersecting said route segment along which said moving object is currently moving is, as a line (29,30,31) intersecting said line (28), indicated on said display device (13).A navigation method according to claim 20, wherein in a case where information about the present position of said moving object is included in information about the shape and the position of said route segment along which said moving object is currently moving, said present position or an equivalent position in place of said present position is indicated on said line (28).A navigation method according to claim 20, wherein a line (32) representing a route segment confronting said target is indicated on the screen of said display device (13).A navigation method according to claim 34, wherein said line (32) representing said route segment confronting said target, a line (33) representing a main route segment near said target and a line representing a route segment which constitutes a course through which said moving object is able to properly correctly reach said target from said main route segment are indicated on the screen of said display device (13).A navigation method according to claim 20, wherein when a target is set, a direction of said target is retrieved while making an arbitrary point in an area displayed on the screen of said display device (13) to be a start point and said line (28) representing said route segment and an arrow representing said direction of said target are indicated on the screen of said display device.A navigation method according to claim 20, wherein when novel information about said route segment along which said moving object is currently moving different from previous information which has been supplied is supplied, said data is retrieved on the basis of said novel information and a line corresponding to said novel information is indicated on said display device on the basis of said retrieved data, said line (28) generated by said previous information and said line generated by said novel information are indicated together on the screen of said display device (13) in such a manner that said two lines are indicated by different kinds of lines or different colors.A navigation system according to claim 1, wherein said auxiliary device is a distance sensor (8) for detecting a travelled distance and an azimuth sensor (7) for detecting a travelling direction;said storage device (14) stores data about the shape and the position of each passage;said central processing device (23) has present position estimating means (17) for estimating the present position of said moving object on the basis of positional information detected by said distance sensor (8) and said azimuth sensor (7), route segment discriminating means (18) for discriminating, when said present position is obtained by said present position estimating means (18), a route segment which is nearest to said present position and retrieval mean (15) for retrieving data about the shape and the position of said route segment from data stored in said storage device (14); andsaid display processing means (22) generates said line (28) representing said route segment on the basis of said data about the shape and the position of said route segment obtained by said retrieval means (15) and indicates said line (28) on said display device(13).A navigation system according to claim 1, wherein said auxiliary device is a distance sensor (8) for detecting the travelled distance and an azimuth sensor (7) for detecting a travelling direction;said storage device (14) stores data about the shape and the position of each route segment;said central processing device (23) has present position estimating means (17) for estimating the present position detected by said distance sensor (8) and said azimuth sensor (7), route segment discriminating means (18) for obtaining a locus on the basis of said estimated present position, comparing said locus and the shape of said route segment stored in said storage device and discriminating a passed route segment and retrieval mean (15) for, when said passed route segment has been discriminated after said comparison between said locus and said shape of said route segment has been performed, retrieving data about the shape and the position of a route segment in front of said route segment and through which said moving object travels if the same does not turn right or left from data stored in said storage device; andsaid display processing means (22) generates said line (28) representing said route segment along which said moving object is currently moving on the basis of said retrieved data to indicate said line (23) on said display device (13).
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TSUYUKI TOSHIO; TSUYUKI, TOSHIO
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TSUYUKI TOSHIO; TSUYUKI, TOSHIO
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EP-0489916-B1
| 489,916 |
EP
|
B1
|
EN
| 19,950,809 | 1,992 | 20,100,220 |
new
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B01D59
| null |
B01D59
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B01D 59/34
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METHOD OF CONCENTRATING OXYGEN 18 WITH LASER
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A method of concentrating oxygen 18 with laser which comprises adding optionally a hydrocarbon to a saturated acyclic ether (except dimethyl ether) or a saturated cyclic ether as a starting material containing oxygen 18 and laser beams are applied thereto for causing selective photolysis of oxygen 18, and separating a product containing oxygen 18 from the products of said photolysis. The concentrated oxygen 18 can be used as a tracer or the like.
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The present invention relates to a method for separation and enrichment of oxygen 18 with a laser, and more particularly to a method for enrichment of oxygen 18 utilizing infrared multiple-photon decomposition of a saturated aliphatic ether other than dimethyl ether and perfluorodimethyl ether or a saturated cyclic ether with a TEA-CO₂ laser. There exist naturally three isotopes of oxygen, oxygen 16, oxygen 17 and oxygen 18, which account for 99.8%, 0.037% and 0.204% of the Earth's oxygen, respectively. Enriched oxygen 18 isotope is widely used as a tracer and is in strong demand. Therefore, an economical method of enrichment of oxygen 18 capable of supplying large amounts of oxygen 18 would profit a society and promote scientific progress. Methods for enrichment of oxygen 18 able to produce more than 1g/day that have been studied up to now include the distillation method, the electrolytic method and the chemical exchange method. Actual enrichment of oxygen 18 is currently being conducted using the NO low temperature distillation method at a production rate of 3kg/year of oxygen 18 having at least 90% purity. However, the enrichment factor ( α ₁₈ ) of ¹⁸O (1.037) is low, the operation temperature is low (- 151. 8°C ), and two large plant systems (a low enrichment distillation column (42 m) and a high distillation column (90m)) are required. The inventors therefore studied the laser isotope enrichment method for its potential to enable reduction of plant size, highly selective single-step enrichment, and shortening of the processing time. When a gaseous substance is irradiated with strong pulsed infrared laser light, it dissociates after absorption of several tens of infrared photons per single molecule. This is known as infrared multiple-photon decomposition. By properly selecting the starting materials and irradiation conditions, it is possible to dissociate isotopes with high selectivity. Thus, the infrared multiple-photon decomposition can be applied for enrichment and separation of isotopes. Laser isotope separation and enrichment with a TEA-CO₂ laser, which posesses relatively high laser power and is one of the easiest to operate among commercially available pulsed infrared lasers, has been studied in detail. Chemical compounds already studied for enrichment of oxygen 18 utilizing oxygen 18 selective infrared multiple-photon decomposition with a TEA-CO₂ laser include dimethyl ether1 ○ [V.V. Vizhn, Y. N. Molin, A. K. Petrov, and A. R. Sorokin, Appl. Phys., 17, 385 (1978) ] , 2 ○ [ K. O. Kutschke, C. Willis, P. A. Hackett, J. Photochem., 21, 207 (1983)] , perfluorodimethyl ether 3 ○ [ Tetsuro. Majima, Takashi. Igarashi, and Shigeyoshi. Arai, Nippon Kagaku kaishi, 1490 (1984) ] , perfluoroacetone [ P. A. Hackett, C. Willis, and M. Gauthier, J. Chem. Phys., 71 , 2682 (1982) ] , and UO₂ (hexafluoroacetyl acetone)₂ (tetrahydrofuran) [ D. M. Cox, R. B. Hall, J. A. Horsley, G. M. Kremer, P. Rabinowitz, and A. Kaldor, Science, 205, 390 (1979) ] . One object of laser isotope separation and enrichment is to enable high selectivity and to increase decomposition and product yields. Generally, higher decomposition and product yields decrease selectivity. Laser isotope separation and enrichment are generally optimized by optimum selection of starting materials and irradiation conditions. In the laser enrichment of oxygen 18, ethers whose C-O bonds dissociate initially are some of the most suitable raw materials. Dimethyl ether absorbs infrared energy by the inverse symmetric stretching vibration of C-O-C bond and fluoro-substituted carbonyl compounds absorb infrared energy by the stretching vibration of C-F bond in the oscillation region of a TEA-CO₂ laser. The selective laser multiple-photon decomposition of oxygen 18 can be initiated by irradiation with TEA-CO₂ laser light on the lower wavenumber side of the absorption. The enrichment of oxygen 18 by the prior art methods using demethyl ether or perfluorodimethyl ether as a raw material generally involves the use of relatively expensive raw materials, high decomposition threshold of dimethyl ether, which lowers decomposition and product yields and likelihood of reduced selectivity in the enrichment of oxygen 18 from the carbon monoxide (CO) obtained as the final oxygen-containing product owing to the fact that the CO is obtained through the secondary decomposition of aldehyde. Additionally, the selective multiple-photon decomposition of oxygen 18 in a single step using a saturated aliphatic ether other than demethyl ether and perfluorodimethyl ether or a saturated cyclic ether can enrich the concentration of oxgen 18 in the product up to 40%, but markedly reduces the product yield to 1%. On the other hand, when the product yield is increased, the degree of enrichment of oxygen 18 in the product considerably decreases. Therefore, it is difficult to achieve high enrichment and high yield of oxygen 18 at the same time by single step infrared multiple-photon decomposition. Accordingly, an object of the present invention is to provide an economical method for enrichment of oxygen 18 in a high concentration by laser isotope enrichment of a saturated aliphatic ether and/or a saturated cyclic ether as a starting material. Another object of the present invention is to provide a method for enrichment of oxygen 18 achieving higher concentration and yield than can be attained by single step infrared multiple-photon decomposition. These objects have been solved by the methods according to claims 1-10. Oxygen 18-containing starting materials used in the present invention include saturated aliphatic ethers such as, for example, diisopropyl ether, diethyl ether, and t-butyl methyl ether, and saturated cyclic ethers such as, for example, propylene oxide, tetrahydropyran, dioxane, and tetrahydrofuran. Among these, diisopropyl ether and t-butyl methyl ether are preferred and can be readily obtained commercially. The oxygen 18-containing starting materials are preferably reacted under pressure of from 0.1 to 30.0 Torr. Higher reaction pressure than the above range may lower the selectivity of oxygen 18 enrichment. On the other hand, lower reaction pressure than the above range may raise another problem of decreasing the yield of photodecomposed products containing oxygen 18. A more preferred pressure range is from 0.1 to 2.0 Torr. Hydrocarbons used in the present invention include saturated and/or unsaturated hydrocarbons having from 3 to 6 carbon atoms. Isobutane, propane, and 2-methylbutane are preferred. The preferred molar ratio of the oxygen 18-containing ether to the hydrocarbon is in the range of from 1:0.1 to 1:30 in the present invention. A higher molar ratio of the hydrocarbons than the above may lower the decomposition and product yields. A lower molar ratio of the hydrocarbons may complicate the product distribution because of the low trapping efficiency of radical species containing oxygen 18. A molar ratio of from 1:1 to 1:3 is more preferred. The ether or mixture of the ether and hydrocarbon as starting material(s) is charged into an irradiation chamber through a vacuum system by operating valves, in a prescribed amount for a batch-wise method, or is passed into the irradiation chamber at a constant flow rate (10-100ml/min) for a continuous method. Further, the starting material(s) can be introduced as a molecular beam or be introduced into a vacuum cell as a supersonic beam which is formed by expansion from a nozzle. The lasers used in the present invention may be selected from those having an ocillation wavelength which selectively photodecomposes oxygen 18-containing ethers. Examples include the TEA-CO₂ laser, the hydrogen halide laser, the Raman laser, the CO laser and the CF₄ laser. These lasers can be used individually or in combinations. The TEA-CO₂ laser is preferred. The term oxygen 18 selective herein is used to mean that the C-O bond of oxygen 18-containing ethers is selectively decomposed, and the C-O bond of oxygen 16-containing ethers is not decomposed. The laser used in the present invention may be employed under continuous oscillation, but preferably employed under pulsed oscillation. In the case of pulsed oscillation, the preferred pulse number is from 10 to 10,000 pulses. A pulse number below this range may lower the efficiency of the oxygen 18 selective photodecomposition, and a higher pulse number may reduce the selectivity of the oxygen 18 enrichment. The more preferred pulse number range is from 10 to 100 pulses. In addition, the preferred duration of the pulses is from 50 to 1000 ns. A shorter duration sometimes reduces the decomposition and product yields, and a longer duration may reduce the selectivity of oxygen 18 enrichment. The more preferred duration of the pulses is from 80 to 120 ns. The preferred laser wavelength employed in the present invention is from 950 cm ⁻ ¹ to 1160 cm ⁻ ¹. The absorption strength of the ethers usually becomes weaker at laser wavelengths above the above range. On the other hand, the decomposition yield may be lowered at shorter laser wavelengths. The more preferred wavelength is from 975 cm ⁻¹ to 1060 cm⁻¹. The preferred laser fluence employed in the present invention is from 1 to 50 J · cm ⁻ ² . A higher fluence may decrease the selectivity of oxygen 18, and a lower fluence may decrease the yield of photodecomposed products containing oxygen 18. The more preferred range of the laser fluence is from 2 to 10J · cm ⁻ ² . The laser irradiation is preferably performed at a temperature of from - 80 to 150 °C . When the temperature is higher than this range, thermal decomposition of the starting material ether may occur. On the other hand, when the temperature is lower than this range, the desired pressure may not be obtained because the vapor pressure of the starting material ether is lowered. The more preferred temperature range is from - 40°C to 50 °C . The oxygen 18-containing products formed by the present invention include aldehydes₁ ketones, alcohols, and/or carbon monoxide. Other products such as hydrocarbons and hydrogen may be formed as secondary products. Methods for separation of desired products containing oxygen 18 from the mixture of the photodecomposed products include a separation method by a Toepler pump, a column chromatography method, and a fractional distillation method. Preferred separation methods are the separation method by a Toepler pump and the column chromatography method. The efficiency of oxygen 18 enrichment can be increased by converting the products containing oxygen 18 into ethers, inducing the oxygen 18 selective photodecomposition by the laser light using said ethers as a part or all of the starting materials, and separating oxygen 18-containing products from the photodecomposed products. The oxygen 18-containing products may converted into ethers by known chemical processes. For example, when the products containing oxygen 18 are aldehydes, they can be converted into ethers by dehydration condensation after reduction into alcohols. When the products containing oxygen 18 are alcohols, they can be converted into ethers by dehydration condensation. Reduction of aldehydes into alcohols may be conducted by a catalytic reduction method or a method using reducing agents such as LiAlH₄ and the like. The reduction methods by NaBH₄ and LiAlH₄ are preferred because of their convenience. The dehydration condensation reaction of alcohols into ethers can he conducted by a method which comprises heating the alcohols in the presence of a catalyst such as sulfuric acid and a method which comprises reacting the alcohols with metallic sodium to form sodium alkoxide and then reacting the sodium alkoxide with alkyl halides to form ethers. From the point of convenience it is preferred that symmetric ethers be synthesized by the heating dehydration using an acidic catalyst, and both symmetric and asymmetric ethers be synthesized by reaction with alkyl halides. The ethers thus obtained may be used in the second photodecomposition reaction by the laser irradiation after or without purification. In the second photodecomposition by the laser irradiation, fresh ether can be added as a starting material to the ethers thus obtained. Methods for purification of ethers include a column chromatography method and a fractional distillation method. The preferred method is the column chromatography method. The process for enrichment of the present invention can be operated batch-wise or continuously, using, for example, the apparatus shown in Fig. 1, which will now be briefly explained. The reaction chamber 15 spherical in shape and made of transparent and pressure-resistant PYREX glass. It is equipped with cylinders on both sides and has windows made of NaCl 17. Its internal volume is 2420 cm³ . The raw material ether can be introduced into the reaction chamber at a desired pressure amount (batch-wise method) or can be passed at a desired pressure and constant flow rate (continuous method) through a gas handling system 20. The laser light 12 from a TEA-CO₂ laser 11 is controlled to a desired diameter by an iris plate 13 and then focused by an optional lens 14 made of BaF₂ to irradiate the center of reaction chamber. After irradiation by the TEA-CO₂ laser, the sample is separated by the gas handling system 20 and a sample separating system 18, and a part of the sample is analyzed by a gas chromatograph-mass spectrometer 19. The reactions in one embodiment of the present invention are shown in the following reaction schemes. These schemes are employed for explanation and do not restrict the scope of the present invention. Scheme 1 shows the reactions where diisopropyl ether is used as the ether starting material and hydrocarbons are not added. Scheme 2 shows the reactions where isobutane is added to diisopropyl ether and the resulting mixture is irradiated with a laser. Fig. 1 shows a schematic diagram of an apparatus which can be used to carry out the present invention. (EXPLANATION OF THE SYMBOLS)11TEA-CO₂ laser oscillator, 12laser light, 13iris plate 14lens for infrared light, 15irradiation reaction chamber, 16gaseous sample, 17NaCl window plate 18sample separation system, 19gaschromatograph-mass spectrometer 20gas handling system, 21raw material ether, 22vacuum apparatus. The present invention will now be described in detail with reference to examples. Except as otherwise indicated, the following examples were carried out at room temperature. EXAMPLE 1Diethyl ether, diisopropyl ether, t-butyl methyl ether, propylene oxide and tetrahydropyran (products of Tokyo Kasei) were used as starting materials after one distillation cycle for purification. Isobutane (product of Takachiho Chemicals) was used as an additive after one vacuum distillation cycle. Fig. 1 is a schematic diagram of the apparatus used for carrying out the present invention. A beam 12 from a pulse-oscillated TEA-CO₂ laser (Type 103-2, manufactured by Lumonics) 11 was passed through the iris plate 13, focused by the lens 14 having a focal length of 20 cm or 170 cm for infrared light and then directed into the irradiation chamber 15, which was located around the focal point, for irradiating saturated ether gas (0.3-20 Torr) 16. The oscillation line of the TEA-CO₂ laser was about 10-30 cm ⁻¹ toward the lower wavenumber side from the absorption band of the ethers. Absorption by oxygen 18-containing ethers can be expected in this wavenumber region. The beam diameters at the focal points were 0.0007 cm² and 0.33 cm² for lenses having a focal length of 20 cm and 170 cm, respectively. Accordingly, the laser fluence at the focal point ranged from 1 to 20 J · cm ⁻ ² . A repetition rate of the laser pulses was 0.7 Hz. The irradiation chamber was a sphere shaped glass bulb having a diameter of 17 cm with glass cylinders measuring 9.5 cm in length and 2 cm in inner diameter at its opposite sides. Each glass cylinder had a NaCl window plates 17 at its outer end. The chamber had an irradiation path length of 36 cm and an internal space of 2,420 cm³ . The sample after the irradiation with laser light was first separated into trapped components (ethers and the products) and untrapped components (mainly CO) at liquid nitrogen temperature using the separation system 18 such as Toepler pump, and in a instance was further separated into trapped components and untrapped components (mainly aldehyde) at -95°C . Each component was measured by the gaschromatograph-mass spectrometer 19 (gaschromatograph GC-7A, manufactured by Shimazu, mass spectrometer TE-150, manufactured by NEVA) to quantify the decomposition amount of the raw material, the production amount of each product, and the concentration of oxygen 18 in CO and aldehydes. Table 1 and Table 2 below show the kinds of ethers used as raw materials, the laser irradiation conditions, the oxygen 18 content of the products [ oxygen 18/(oxygen 18+oxygen 16) ] and selectivity of oxygen 18 enrichment [ selectivity= (oxygen 18/oxygen 16 in the products)/(oxygen 18/oxygen 16 in the raw material) ] . Laser irradiation conditions for the infrared multiple-photon decomposition of ethers in oxygen 18 enrichment. No. Starting Material Pressure Torr Laser Wavenumber cm⁻¹ Laser Fluence J · cm⁻² Pulse Number 1Diethyl ether1.0983.251.23000 2Diethyl ether1.0982.101.83000 3Diisopropyl ether3.0978.471510000 4Diisopropyl ether1.0978.472.81000 5Diisopropyl ether1.0978.471.23000 6Diisopropyl ether0.3978.47 2.71000 7Diisopropyl ether 1.0 975.93 1.9 1000 8t-Butyl methyl ether3.01055.631710000 9t-Butyl methyl ether1.0982.251.92000 10Propylene oxide1.01057.301.82000 11Tetrahydrofuran1.0982.101.73000 12Tetrahydrofuran1.0982.101.93000 13Diisopropyl ether + isobutane1.0 1.0978.471.23000 Enrichment of oxygen 18 by the infrared multiple-photon decomposition of ethers No. Product Oxygen 18 Content of Product/% Selectivity of Oxygen 18 Enrichment 1CH₃ CHO3.015 2CH₃ CHO1.89.2 3CO0.281.4 4CH₃ CHO1.78.6 5CH₃ CHO1270 6CH₃ CHO1478 7CH₃ CHO41350 8CO0.321.6 9CH₃ COCH₃1.36.6 10CH₃ CHO0.301.5 11CH₃ CHO1.57.4 12CH₃ CHO6.233 13(CH₃ )₂ CHOH3.015 For example, in sample No.7, 1.0-Torr of diisopropyl ether was irradiated by 1000 pulses of TEA-CO₂ laser light having a wavenumber of 975.93cm ⁻¹ and a fluence at the focal point of 1.9J · cm⁻² . As a result, oxygen 18 was enriched up to 41% in CH₃ CHO as an oxygen containing main product as listed in sample No.7 of Table 2, which value is 350 times greater than the natural abundance of oxygen 18. The results of the above examples show that a relatively high selectivity of oxygen 18 enrichment and improvement of the yield of production were achieved. In particular, sufficiently high selectivity was attained when the pressure of the starting materials and the laser fluence were low. EXAMPLE 2The mixture of components separated at -196 °C according to the method of Example 1, No.7, was applied to a column choromatograph to obtain oxygen 18 enriched acetaldehyde at a yield of 10%. One gram of the acetaldehyde thus obtained was reduced with LiAlH₄ to obtain ethyl alcohol at a yield of 90%. Then the ethyl alcohol was dehydrated by heating in the presence of H₂SO₄ to obtain diethyl ether at a yield of 70%. The oxygen 18 content of the obtained diethyl ether was 41% and was the same as that in the acetaldehyde obtained in Example 1, No.7 (41%). The method of Example 1, No. 1 was repeated using the diethyl ether thus obtained to obtain acetaldehyde which contained 91.5% of oxygen 18 at a yield of 10%. In this case, the selectivity of oxygen 18 enrichment was 15, the same as that of Example 1. EXAMPLE 3The acetaldehyde of Example 2 was converted in accordance with the method of Example 2 into diethyl ether to obtain acetaldehyde which contained 99.4% of oxygen 18 at a yield of 10%. The yield of acetaldehyde was 0.1% based on the diisopropyl ether used as the primary raw material. The selectivity of oxygen 18 enrichment was 15, the same as that of Example 1. EXAMPLE 4The mixture of components separated at -95°C according to the method of Example 1, No. 13, was applied to a column chromatograph to obtain oxygen 18 enriched isopropyl alcohol at a yield of 20%. One gram of the isopropyl alcohol thus obtained was reacted with metallic sodium to form sodium isopropoxide and then reacted with isopropyl iodide to obtain diisopropyl ether at a yield of 75%. The oxygen 18 content of the diisopropyl ether thus obtained was 3% and was the same as that in the isopropyl alcohol obtained in Example 1, No. 13. The method of Example 1, No. 13 was repeated using the diisopropyl ether thus obtained to obtain isopropyl alcohol which contained 32% of oxygen 18 at a yield of 20%. In this case, the selectivity of oxygen 18 enrichment was 15, the same as that of Example 1. EXAMPLE 5The method of Example 4 was repeated using as a raw material the isopropyl alcohol which was obtained in Example 4 and contained 32 % of oxygen 18 to obtain diisopropyl ether. The method of Example 1, No. 13 was repeated using the diisopropyl ether thus obtained to obtain isopropyl alcohol which contained 87% of oxygen 18 at a yield of 20%. The yield of isopropyl alcohol was 0.2% based on the diisopropyl ether used as the primary raw material. In this case, the selectivity of oxygen 18 enrichment was 15, the same as that of Example 1. EXAMPLE 6The method of Example 5 was repeated using the isopropyl alcohol which was obtained in Example 5 and contained 87 % of oxygen 18 to obtain diisopropyl alcohol containing 99% of oxygen 18 at a yield of 20%. The yield of isopropyl alcohol was 0.04% based on the diisopropyl ether used as the primary raw material. In this case, the selectivity of oxygen 18 enrichment was 15, the same as that of Example 1. As described above, the laser enrichment method of the present invention enables oxygen 18 to be enriched economically and provided in large quantities. The laser enrichment method of the present invention also makes it possible to reduce the size of the apparatus and the processing time required for the enrichment. The present invention provides oxygen 18 enriched aldehydes, carbon monoxide, alcohols, ethers, and others, which can be used as tracers and so on.
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A method for enrichment of oxygen 18, which comprises the steps of (a) irradiating a saturated aliphatic ether and/or a saturated cyclic ether as an oxygen 18-containing starting material with laser light to induce oxygen 18 selective photodecomposition, with the proviso that the saturated aliphatic ether is not dimethyl ether or perfluorodimethyl ether; and (b) separating oxygen 18-containing products from the photodissociated products. A method for enrichment of oxygen 18, which comprises the steps of (a) adding a hydrocarbon to a saturated aliphatic ether and/or a saturated cyclic ether as an oxygen 18-containing starting material, and irradiating the material(s) with laser light to induce oxygen 18 selective photodecomposition; and (b) separating oxygen 18-containing products from the photodissociated products. A method for enrichment of oxygen 18, which comprises the steps of (a) irradiating a saturated aliphatic ether and/or a saturated cyclic ether as an oxygen 18-containing starting material with laser light to induce oxygen 18 selective photodecomposition, with the proviso that the saturated aliphatic ether is not dimethyl ether or perfluorodimethyl ether; (b) separating oxygen 18-containing products from the photodecomposed products; and (c) converting the obtained oxygen 18-containing products into ethers and applying the ethers as the starting materials to the process (a). A method for enrichment of oxygen 18, which comprises the steps of (a) adding a hydrocarbon to a saturated aliphatic ether and/or a saturated cyclic ether as an oxygen 18-containing starting material, and irradiating the material(s) with laser light to induce oxygen 18 selective photodecomposition; (b) separating oxygen 18-containing products from the photodecomposed products; and (c) converting the obtained oxygen 18-containing products into ethers and applying the ethers as the starting materials to the process (a). The method in accordance with Claim 3 or 4, wherein the step (c) comprises the steps of (f) reducing aldehydes as the products containing oxygen 18 into alcohols; and (g) dehydrating the resulting alcohols to form ethers. The method in accordance with Claim 3 or 4, wherein the step (c) comprises the step of dehydrating the alcohols as the products containing oxygen 18 to form ethers. A method in accordance with Claim 1, 2, 3 or 4 for preparation of oxygen 18-containing aldehydes. A method in accordance with Claim 3 or 4 for preparation of oxygen 18-containing ethers. A method in accordance with Claim 1, 2, 3, 4 or 5 for preparation of oxygen 18-containing alcohols. A method in accordance with Claim 1, 2, 3 or 4 for preparation of oxygen 18-containing carbon monoxide.
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RIKAGAKU KENKYUSHO
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ARAI SHIGEYOSHI FUSHIMI-GODOSY; MAJIMA TETSURO RIKAGAKU KENKYU; SUGITA KYOKO RIKAGAKU KENKYUSH; ARAI, SHIGEYOSHI 821, FUSHIMI-GODOSYUKUSYA; MAJIMA, TETSURO RIKAGAKU KENKYUSHO; SUGITA, KYOKO RIKAGAKU KENKYUSHO
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EP-0489917-B1
| 489,917 |
EP
|
B1
|
EN
| 19,960,124 | 1,992 | 20,100,220 |
new
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H04M1
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H04M11, H04N1
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H04M11, H04M1, H04N1
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T04N201:327C2C, H04M 11/06D, H04N 1/327C, T04M1:57, H04M 1/654, T04N201:327C3E, H04M 1/663, T04N201:327C2B
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COMPOSITE TELEPHONE SET
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A composite telephone set comprising an information input means through which are inputted a telephone number and information indicating an automatic answering telephone part or a data communication means in respect to the telephone number, a storage means for storing the information inputted through the information input means, and a control means which collates the telephone number sensed by a telephone number sensing means with the telephone number stored in the storage means and, when the numbers coincide with each other, operates either of the automatic answering telephone part or the data communication means is operated according to the information stored. In the composite telephone set, the storage means stores the telephone number and the information inputted from the information input means which indicates the data communication means or the automatic answering telephone part, and collates a telephone number inputted from the telephone circuit which is sensed by the telephone number sensing means with the telephone number stored in the storage means. When the former coincides with the latter, the control means selects the data communication means or the automatic answering telephone part according to the stored information corresponding to the telephone number and operates the selected one.
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This invention relates to a composite telephone capable of automatically changing over its functions using a telephone number data from a caller. BACKGROUNDRecently, function of the telephone has been improved, and the facsimile has been popularized. Moreover, a composite telephone appears, having the both functions integrated. Formerly, a composite telephone such as a facsimile with an answering telephone, in the automatic answering mode, makes connection with the telephone line automatically, then, determine whether the partner is a facsimile or not by observing an input signal from the partner's line, and selects either of that the facsimile is operated or that the answering telephone is operated. Hereinbelow will be described the above-mentioned prior art composite telephone with reference to drawings. Fig. 3 shows structure of a prior art composite telephone. In Fig. 3, numeral 1 is a telephone line, numeral 2 is ring signal detection means, numeral 3 is an interface circuit, numeral 4 is storing means for storing various operations, numeral 5 is control means, numeral 6 is facsimile communication means as data communication means, numeral 7 is answering message (hereinafter referred to as OGM) sending means, numeral 8 is incoming signal judging means, numeral 9 is massage (hereinafter referred to as ICM) recording means as signal recording means incoming from the telephone line, numeral 10 is a sending and receiving circuit, numeral 11 is a hand set, numeral 12 is external telephone connecting means, numeral 13 is ring sound generation means, numeral 14 is a speaker, and numeral 15 is an automatic answering selection switch. Hereinbelow will be described relations between structural elements and operation of the composite telephone comprising the above-mentioned structural elements. At first, the ring signal detection means 2 of the composite telephone detects a ring signal from a not-shown central exchange office and its output is sent to the control means 5. The control means 5 generates a ring sound signal by ring sound generation means 13 and it is outputted from a speaker 14. In the case that the automatic answering selection switch 15 is in ON-state, the control means 5 causes the interface circuit 3 to make connection with the telephone line 1. After completion of making connection of the telephone line 1, the control means 5 causes the OGM sending means 7 to send an OGM as well as causes the incoming signal judging means 8 to observe the signal incoming from the telephone line 1 through the interface circuit 3. When the caller sends a facsimile demand signal for demanding facsimile communication (for example, DTMF signal), the incoming signal judging means 8 detects this signal and sends its output signal to the control means 5. The control signal 5 causes the OGM sending means 7 to stop sending of the OGM and to operate the facsimile communication means 6 to start facsimile communication. In the case that the facsimile communication demand signal from a caller is not inputted during sending the OGM, when sending of the OGM ends, the control means 5 operates a timer means included therein as well as operates the ICM recording means 9. During this if the incoming judging means 8 detects a voice signal, the control means 5 resets operation of the internal timer and operates the massage recording means 9 as it is. When the incoming judging means 8 detects the silence for a given interval detected by counting of the timer or when the facsimile communication start signal is detected, the control means 5 does not cause recording operation by the ICM recording means but causes the facsimile communication means 6 to start facsimile communication. However, according to the above-mentioned structure, there is a problem that a considerable interval is necessary to start the facsimile communication because switching to the facsimile communication is made after judging whether the partner telephone is a facsimile or not in accordance with the signal inputted after the making of connection with the telephone line. Moreover, particularly, in the case of a facsimile communication, there is a specification that communication shall start within a predetermined interval after the caller sends its telephone number. As the result, there is also a problem that facsimile communication cannot be executed when an excessive interval has passed up to judgement. JP-A-63-191456 discloses a composite telephone including means to perform the functions of an answering machine and a facsimile as well as an ordinary telephone. In order to resolve the problem of the above-mentioned prior art, this invention provides a composite telephone, as defined in claim 1, capable of shortening the response interval by selectively operating either of the data communication apparatus or the answering telephone using caller's-telephone-number-indicating function whose service has been started, that is, in accordance with the telephone number of the caller input at the same instance as the ring signal. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 shows structure of an embodiment of the invention of a composite telephone, Fig. 2 shows a flow chart showing operation of automatic answering operation of the embodiment of the invention and Fig. 3 shows structure of a prior art telephone. PREFERRED EMBODIMENTS OF THE INVENTIONHereinbelow will be described an embodiment of the invention with reference to drawings. Fig. 1 shows a structure of the embodiment of the invention of a composite telephone. Fig. 2 shows a flow chart showing its operation. In Fig. 1, numeral 3a is an interface circuit, numeral 4a is a storing means, numeral 5a is control means, numeral 16 is indication means, numeral 17 is information input means, numeral 18 is a program switch, and numeral 19 is telephone number detection means. The elements having the same functions as those of the prior art are designated as the same references and their descriptions are omitted. Hereinbelow will be described relatidns between respective structural elements and operation of the composite telephone comprising the above-mentioned structural elements. At first, registration operation of telephone numbers will be described. This apparatus enters a program mode by depressing a program switch 18. A telephone number is input through the information input means 17 to indicate whether the automatic answering telephone portion comprising the OGM sending means 7 and the ICM recording means 9 or the facsimile communication means 6 is to be operated when a call from this telephone number is detected on the telephone line 1. The control means 5a stores the information in the storing means 4a. After the completion of registration operation, the program switch 18 is depressed again to end the program mode. Then, the automatic answering operation will be described. A ring signal from the telephone line 1 is observed (step 1). When the ring signal detection means 2 detects the ring signal in response to input of the ring signal, a ring sound is generated (step 2) as similar to the conventional manner. Moreover, the control means 5a counts up the detections of the ring signal (step 3). The telephone number detection means 19 detects a caller's telephone number following the first ring signal, input from the telephone line 1 and stores the detected telephone number in the storing means 4a and indicates it by the indication means 16 (step 4). Here, the control means 5a collates the telephone number of the caller inputted from the telephone line 1 with telephone numbers registered in the storing means 4a (step 5). If it is registered, the control means reads out the information recorded with correspondence to the telephone number, which indicates either of that the automatic answering telephone portion comprising the OGM sending means 7 and ICM recording means 9 is operated or that the facsimile communication means 6 is operated (step 6). At this instance, if the operation mode is in the automatic answering telephone mode and the information indicates that the answering telephone portion is operated (step 7), the control means 5a confirms that the ring signal detection means detects continuation of the ring signal after this (step 8). If it detects continuation of the ring signal, the control means counts up the detections of the ring signal (step 9). Then, the control means 5a judges whether the number of times the ring signal is detected reaches a predetermined number (step 10). If the number reaches the predetermined number, the control means causes the interface circuit 3a to make connection with the telephone line 1 (step 11). Then, the control means causes the OGM sending means 7 to send an OGM to the caller and then, it causes the ICM recording means 9 to operate to record a message sent from the caller after completion of sending the OGM (step 12). If the operation mode is not in the automatic answering telephone mode but in the ordinal operation mode, generation of the ring sound is continued until the user makes OFF-HOOK. Then, in step 7, when the information stored in the storing means 4a indicates that the facsimile communication means is operated, the control means 5a immediately causes the interface circuit 3a to make connection with the telephone line 1 (step 13) and causes the facsimile means to operate (step 14). In step 5, if the telephone number inputted from the telephone line 1 does not coincides any telephone number stored in the storing means 4a, in the case that the telephone number is not stored in the storing means 4a, or in the case that the telephone number data is not inputted from the telephone line 1, the control means causes the OGM sending means 7 to send the OGM after completion of connection with the telephone line 1 as similar to the prior art operation. Then, if the incoming signal judging means 8 detects the facsimile demand signal or the facsimile communication start signal or mute over a given interval, it causes the facsimile communication means 6 to operate. If the incoming signal judging means 8 detects a voice signal, it causes the ICM recording means 9 to operate. The facsimile communication as data communication has been described as an example. However, as a matter of course, this invention can deal with other data communication such as personal computer communication which is possible to be used in future by only changing the contents stored in the memory. The number of kinds of communication is not limited to two but can be three or four. POSSIBILITY OF INDUSTRIAL APPLICATIONAccording to the above-mentioned structure, the control means collates the telephone number data sent from an exchange through the telephone line with the telephone numbers stored in the storing means, if they agree with each other, the control means automatically determines whether or not the facsimile means is to be operated or not on the basis of the information stored in relation with the telephone number. Therefore, though the apparatus is set to the automatic answering telephone mode, if the caller is a special terminal such as a facsimile, it is possible to start operation corresponding to caller's terminal automatically without operation of sending a answering message. Moreover, it is possible to start operation before connection with the telephone line, so that the response interval can be shortened and to prevent bad connection.
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A composite telephone for connection to a telephone line (1), the telephone comprising: ring signal detection means (2) for detecting a ring signal input from the telephone line (1); interface means (3a) for automatically connecting to the telephone line when the ring signal is input; a telephone portion (10,11) for receiving a voice signal input from the telephone line and for sending a voice signal to the telephone line; and data communication means (6) for performing data communication; characterised by: telephone number detection means (19) for detecting telephone number data input from the telephone line; storing means (4a) for storing telephone numbers and for storing information in relation with said telephone numbers, the information indicating either of said telephone portion or data communication means; and control means (5a) for collating a telephone number detected by said telephone number detection means with the telephone numbers stored in said storing means and selecting for operation either said telephone portion or said data communication means in accordance with said information stored in relation with the telephone number when detected and stored telephone numbers coincide. A telephone according to claim 1 wherein said telephone portion comprises an automatic answering telephone portion having answering message sending means (7) for sending an answering message and incoming signal recording means (9) for recording a signal input from the telephone line. A telephone according to claim 2 wherein said control means is adapted to control said interface means, when information read out from said storing means indicates the telephone portion, to connect to the telephone line when said ring signal detection means detects the ring signal a predetermined number of times; and when information read out from said storing means indicates the data communication means, to connect to the telephone line immediately.
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MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
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TANAKA SEIJI - - YANASE -CHOME; TANAKA, SEIJI, 19-8-103, YANASE 1-CHOME
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EP-0489918-B1
| 489,918 |
EP
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B1
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EN
| 19,981,216 | 1,992 | 20,100,220 |
new
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C08L33
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C09D133, C08L43
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C09D133, C08L33, C09D143, C08L43
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C09D 143/04+B2, M08L33:06B4, M08L43:04, C09D 133/06B4+B2
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ONE-LIQUID TYPE COMPOSITION
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A one-liquid type coating composition excellent in shelf stability and workability in coating, which comprises: a hydroxylated acrylic resin; an acrylic copolymer containing an alkoxysilyl group of general formula (I), wherein R¹ represents C₁ to C₁₀ alkyl, R² represents hydrogen or a monovalent hydrocarbon group selected from among C₁ to C₁₀ alkyl, aryl and aralkyl, and α is 0.1 or 2; a curing catalyst; and at least one member selected from a dehydrating agent and an alkyl alcohol.
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TECHNICAL FIELDThe present invention relates to a one component composition which is used for various coatings such as coatings for outer walls of buildings, automobiles, industrial machines, steel furnitures, household electric appliances and plastics, especially, for coatings applied to uses requiring to have an excellent durability.BACKGROUND ARTConventional thermosetting coatings are ones wherein there is used as a crosslinking agent a melamine such as an alkyd melamine, an acrylic melamine or an epoxy melamine, so they are ones wherein the problem of bad-smelling caused by the melamine resin remains to be solved.In order to solve these problems, the present inventors found a crosslinking system of a polyol resin and a hydrolyzable silyl group-containing resin which is quite different from a conventional crosslinking system of a polyol resin and a melamine resin, and filed already a patent application (see Japanese Unexamined Patent Publication 1-141952).However, when such a mixture of the polyol resin and the hydrolyzable silyl group-containing polymer is used without a curing catalyst, the curing speed is slow at room temperature or under heating at a relatively low temperature. Accordingly, it is required to heat the mixture at a high temperature when desired to coat and cure at a high speed, so a large amount of energy is consumed.Such disadvantages can be, generally, improved by admixing a curing catalyst just before the use, whereby the curing speed of the coating film is heightened even at a relatively low temperature. However, if admixing the curing catalyst once, such compositions, which are used as a paint, coating agent, adhesive, sealant, coupling agent and the like, cannot be stored, since the compositions are cured in a short period of time. Accordingly, for instance, the rest of the composition used for coating quite comes to noting (such compositions are generally called as two component composition ).When there is aimed at a film formation utilizing a siloxy-crosslinking owing to a reaction of hydroxyl group of an acrylic resin having hydroxyl group with an alkoxysilyl group of an alkoxysilyl group-containing acrylic copolymer, a composition is required to contain an acrylic resin having hydroxyl groups enough to sufficiently crosslink. In such a case, hydroxyl group and the alkoxysilyl group are gradually reacted even in absence of a catalyst, thus resulting in gelation. Much less, it is technically difficult to stably store the composition containing a curing catalyst over several months.DISCLOSURE OF THE INVENTIONIn order to solve these problems, the present inventors have repeated an earnest study. As a result, they have found that even mixtures of an acrylic resin having hydroxyl groups which contains a curing catalyst and an alkoxysilyl group-containing acrylic copolymer can be made into a one component composition by further adding a combination of methanol and n-butanol and optionally a dehydrating agent and have accomplished the present invention.Accordingly the present invention is directed to a composition comprising: (A) an acrylic resin having hydroxyl groups,(B) an alkoxysilyl group-containing acrylic copolymer having a group represented by the general formula: wherein R1 is an alkyl group having 1 to 10 carbon atoms R2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 a carbon atoms selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and a is 0, 1 or 2,(C) a curing catalyst,(E) a combination of methanol and n-butanol and optionally (D) a dehydrating agent, wherein said composition is in the form of a one component composition containing all said components (A), (B), (C), (E) and optionally (D).The composition of the present invention is excellent in storage stability and is excellent in workability on coating.The acrylic resin having hydroxyl groups used in the present invention which is the component (A) [hereinafter also referred to as acrylic resin having hydroxyl groups (A) ] is a component used for exhibiting film properties such as hardness immediately after sintering and solvent resistance. Since its main chain is substantially composed of an acrylic copolymer chain, the weatherability, chemical resistance and water resistance of the cured product are improved.The acrylic resin having hydroxyl groups (A) can be obtained by, for instance, copolymerization of a hydroxyl group-containing vinyl monomer with acrylic acid, methacrylic acid or their derivatives.The reaction of moisture in the composition with the dehydrating agent progresses faster than the reaction of the alkoxysilyl group of the polymer (B) with the moisture, owing to the copolymerization of the acidic monomer such as acrylic acid or methacrylic acid, thereby improving the stability of one component composition.As the hydroxyl group-containing vinyl monomer to be included as the above-mentioned copolymerizable component, there are exemplified, for instance, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth)acrylamide, Aronix 5700 made by Toagosei Chemical Industry Co., Ltd., 4-hydroxyl styrene, HE-10, HE-20, HP-10 and HP-20 which are products made by Nippon Shokubai Kagaku Kogyo Kabushiki Kaisha (which are acrylate oligomers having hydroxyl groups at the oligomer end), Blenmer PP series (polypropylene glycol methacrylate), Blenmer PE serives (polyethylene glycol monomethacrylate), Blenmer PEP serives (polyethylene glycol polypropylene glycol methacrylate), Blenmer AP-400 (polypropylene glycol monoacrylate), Blenmer AE-350 (polyethylene glycol monoacrylate), Blenmer NKH-5050 (polypropylene glycol polytrimethylene monoacrylate) and Blenmer GLM (glycerol monomethacrylate), which are products made by Nippon Yushi Kabushiki Kaisha, and an ε-caprolactone-modified hydroxyalkyl vinyl monomer obtained by reaction of a hydroxyl group-containing vinyl compound with ε-caprolactone.As typical examples of the ε-caprolactone-modified hydroxyalkyl vinyl monomers, there are exemplified, for instance, monomers having a structure represented by the formula: wherein R is H or CH3 and n is an integer of not less than one, such as Placcel FA-1 (R=H, n=1), Placcel FA-4 (R=H, n=4), Placcel FM-1 (R=CH3, n=1) and Placcel FM-4 (R=CH3, n=4) which are products made by Daicel Chemical Industries, Ltd., TONE M-100 (R=H, n=2) and TONE M-201 (R= CH3, n=1) which are products made by UCC. By using the ε-caprolactone-modified hydroxyalkyl vinyl monomer as the hydroxyl group-containing vinyl monomer, the impact resistance and the flexibility of the coating film can be improved.These hydroxyl group-containing vinyl monomers may be used alone or as a mixture thereof.The derivatives of acrylic acid or methacrylic acid copolymerizable with the hydroxyl group-containing vinyl monomer are not particularly limited. As their concrete examples, there are exemplified, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trifluoroethyl (meth)acrylate, pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylamide, α-ethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N, N-dimethyl acrylamide, N-methyl acrylamide, acryloyl morpholine, N-methylol (meth)acrylamide, AS-6, AN-6, AA-6, AB-6 and AK-5, which are macromers made by Toagosei Chemical Industry Co., Ltd., a phosphate group-containing vinyl compound which is a condensation product of a hydroxyalkyl ester of α,β-ethylenically unsaturated carboxylic acid such as a hydroxyalkyl ester of (meth)acrylic acid with phosphoric acid or a phosphoric ester, and a (meth)acrylate containing an urethane bond or siloxane bond.The copolymer may contain segments formed by an urethane bond or siloxane bond or segments derived from monomers other than (meth)acrylic acid derivatives in its main chain within a range of less than 50 % (% by weight, hereinafter the same). The monomers are not limited. Examples of the monomers are, for instance, an aromatic hydrocarbon vinyl compound such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid or vinyl toluene; an unsaturated carboxylic acid such as maleic acid, fumaric acid or itaconic acid, its salt (alkali metal salt, ammonium salt, amine salt), its acid anhydride (maleic anhydride), or an ester of an unsaturated carboxylic acid such as a diester or half ester thereof with a linear or branched alcohol having 1 to 20 carbon atoms; a vinyl ester or an allyl compound such as vinyl acetate, vinyl propionate or diallyl phthalate; an amino group-containing vinyl compound such as vinylpyridine or aminoethyl vinyl ether; an amide group-containing vinyl compound such as itaconic acid diamide, crotonamide, maleic acid diamide, fumaric acid diamide or N-vinylpyrrolidone; other vinyl compounds such as methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole and vinylsulfonic acid.It is preferable that the acrylic resin having hydroxyl group (A) is prepared by solution polymerization using an azo radical polymerization initiator such as azobisisobutyronitrile, because of the easiness of synthesis.In the solution polymerization, if necessary, a chain transfer agent such as n-dodecyl mercaptane, t-dodecyl mercaptane or n-butyl mercaptane is used, thereby controlling the molecular weight.Any non-reactive solvents are used without particular limitations as the polymerization solvent. The acrylic resin having hydroxyl groups (A) may be used in the state of a solution, or as a non-aqueous dispersion type wherein the insoluble polymer particles are dispersed in a non-polar organic solvent such as heptane or pentane.The molecular weight of the acrylic resin having hydroxyl groups (A) is not particularly limited. It is preferable that the number average molecular weight is from 1,500 to 40,000, more preferably from 3,000 to 25,000, from the viewpoint of the film properties (the properties of the film prepared from the composition of the present invention) such as durability. Also, it is preferable that the resin (A) has hydroxyl groups enough to sufficiently crosslink. It is preferable that the hydroxyl value is from 10 to 300 mg KOH/g, more preferably from 30 to 150 mg KOH/g, from the viewpoint of the film properties such as strength and durability.Such acrylic resins having hydroxyl groups (A) may be used alone or as a mixture thereof.The alkoxysilyl group-containing acrylic copolymer used in the present invention which is the component (B) [ hereinafter also referred to as alkoxysilyl group-containing acrylic copolymer (B) ] is a polymer having, in one molecule, at least one, preferably not less than two alkoxysilyl groups represented by the formula: at its ends and(or) side chains.In the above-mentioned formula, R1 is an alkyl group having 1 to 10, preferably from 1 to 4, carbon atoms. When the number of carbon atoms is more than 10, the reactivity of the alkoxysilyl group is lowered. Also, when the group R1 is a group other than the alkyl group, such as phenyl group or benzyl group, the reactivity is lowered. Examples of the groups R1 are, for instance, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and isobutyl group.In the above-mentioned formula, R2 is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 10, preferably from 1 to 4, carbon atoms selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.Examples of the alkyl groups having 1 to 10 carbon atoms which are one kind of the group R2 are the same groups as the group R1, examples of the aryl groups are, for instance, phenyl group, and examples of the aralkyl groups are, for instance, benzyl group.In the above-mentioned formula, a is 0, 1 or 2.Examples of the alkoxysilyl group represented by the above-mentioned formula are, for instance, groups contained in alkoxysilyl group-containing monomers as mentioned below.The main chain of the alkoxysilyl group-containing acrylic copolymer (B) is substantially composed of the acrylic copolymer chain, so the cured product is improved in weatherability, chemical resistance and water resistance. Further, the alkoxysilyl group is bonded to carbon atom, so the cured product is, for example, improved in water resistance, alkali resistance and acid resistance.When the number of the alkoxysilyl groups in the alkoxysilyl group-containing acrylic copolymer (B) is less than one in one molecule, it becomes easy to lower the solvent resistance of the obtained film from the composition of the present invention.The number average molecular weight of the alkoxysilyl group-containing acrylic copolymer (B) is from 1,000 to 30,000, particularly preferably from 3,000 to 25,000, from the viewpoint of the properties such as durability of the film obtained from the composition of the present invention.The alkoxysilyl group-containing acrylic copolymer (B) can be obtained, for instance, by copolymerization of acrylic acid, methacrylic acid or a derivative therefrom with an alkoxysilyl group-containing monomer.The derivatives of acrylic acid or methacrylic acid are not limited. Examples thereof are, for instance, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trifluoroethyl (meth)acrylate, pentafluoropropyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylamide, α-ethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N, N-dimethyl acrylamide, N-methyl acrylamide, acryloyl morpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, N-methylol (meth)acrylamide, Aronix M-5700 made by Toagosei Chemical Industry Co., Ltd., AS-6, AN-6, AA-6, AB-6, and AK-5, which are macromers made by Toagosei Chemical Industry Co., Ltd., Placcel FA-1, Placcel FA-4, Placcel FM-1 and Placcel FM-4, which are products made by Daicel Chemical Industries, Ltd., a phosphate group-containing vinyl compound which is a condensation product of a hydroxyalkyl ester of α,β-ethylenically unsaturated carboxylic acid such as a hydroxyalkyl ester of (meth)acrylic acid with phosphoric acid or a phosphoric ester, and a (meth)acrylate containing an urethane bond or siloxane bond. When the hydroxyl group-containing monomer is used, it is preferable to use it in a small amount (for instance, not more than 2 % of the copolymer).The above-mentioned alkoxysilyl group-containing monomers are not particularly limited so long as the monomer has a polymerizable unsaturated double bond and has the alkoxysilyl group. Examples thereof are, for instance, CH2=C(CH3)COO(CH2)3Si(OC2H5)3, or a (meth)acrylate having the alkoxysilyl group at the molecular ends through an urethane bond or a siloxane bond such as or It is preferable that the alkoxysilyl group-containing acrylic copolymer (B) contains from 5 to 90 %, more preferably from 11 to 70 %, of units of the alkoxysilyl group-containing monomer, from the viewpoint of the curability of the composition and the durability of the film.The copolymer may contain segments formed by an urethane bond or siloxane bond or segments derived from monomers other than the (meth)acrylic acid derivative in its main chain within a range of less than 50 %. The monomers are not limited. Examples of the monomers are, for instance, an aromatic hydrocarbon vinyl compound such as styrene, a α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene or vinyl toluene; an unsaturated carboxylic acid such as maleic acid, fumaric acid or itaconic acid, its salt (alkali metal salt, ammonium salt, amine salt), its acid anhydride (maleic anhydride), an ester of an unsaturated carboxylic acid such as a diester or half ester thereof with a linear or branched alcohol having 1 to 20 carbon atoms; a vinyl ester or an allyl compound such as vinyl acetate, vinyl propionate or diallyl phthalate; an amino group-containing vinyl compound such as vinylpyridine or aminoethyl vinyl ether; an amide group-containing vinyl compound such as itaconic acid diamide, crotonamide, maleic acid diamide, fumaric acid diamide or N-vinylpyrrolidone; and other vinyl compounds such as 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin, maleimide, N-vinylimidazole or vinylsulfonic acid.The alkoxysilyl group-containing acrylic copolymer (B) can be prepared, for instance, in a manner as shown in Japanese examined Patent Publication No. 54-36395, No. 57-36109 and No. 58-157810. A solution polymerization using an azo radical polymerization intiator such as azobisisobutyronitrile is the most preferable, from the viewpoint of the easiness of synthesis.If necessary, in the above-mentioned solution polymerization, there is used a chain transfer agent such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, (CH3O)3Si-S-S-Si-(OCH3)3 and (CH3O)3Si-S8-Si(OCH3)3, whereby the molecular weight can be controlled. Particularly, when using the chain transfer agent having the alkoxysilyl group in its molecule, such as γ-mercaptopropyltrimethoxysilane, it is possible to introduce the alkoxysilyl group into the silyl group-containing acrylic copolymer at the polymer ends.As the polymerization solvents used in the above-mentioned solution polymerization, there are used any non-reactive solvents such as hydrocarbons (toluene, xylene, n-hexane and cyclohexane), acetic esters (ethyl acetate and butyl acetate), alcohols (methanol, ethanol, isopropanol and n-butanol), ethers (ethyl cellosolve, butyl cellosolve and cellosolve acetate), and ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone and acetone) without particular restrictions.The alkoxysilyl group-containing polymer (B) may be used alone or as a mixture thereof.The used ratio of the alkoxysilyl group-containing polymer (B) is not particularly limited. It is preferable that the component (A) / the component (B) is from 9/1 to 1/9, more preferably from 8/2 to 2/8 in weight ratio. When the ratio of the component (A) / the component (B) is more than 9/1, the film obtained from the composition of the present invention tends to lower in water resistance. When the ratio is less than 1/9, there is a tendency that the effects obtained by addition of the component (A) are unsatisfactorily obtained.Examples of the curing catalyst used in the present invention which is the component (C) [hereinafter also referred to as curing catalyst (C) ] are, for instance, an organotin compound such as dibutyl tin dilaurate, dibutyl tin dimaleate, dioctyl tin dilaurate, dioctyl tin dimaleate or tin octoate; phosphoric acid or a phosphoric ester such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate or didecyl phosphate; an addition reaction product of phosphoric acid and(or) monoacid phosphate with an epoxy compound such as propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acryl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Cardula E made by Yuka Shell Epoxy Kabushiki Kaisha, or Epicote 828 or Epicote 1001, which is a product made by Yuka Shell Epoxy Kabushiki Kaisha; an organic titanate compound; an organic aluminum compound; an acidic compound such as maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid, their acid anhydrides or p-toluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N,N-dimethyldodecylamine or dodecylamine; a mixture or a reaction product of the amine with the acid phosphate; and an alkali compound such as sodium hydroxide or potassium hydroxide.Among these curing catalysts (C), there are preferable the organotin compound, the acid phosphate, the mixture or the reaction product of the acid phosphate and the amine, the saturated or unsaturated polyvalent carboxylic acid or its acid anhydride, the reactive silicon compound, the organic titanate compound, the organic aluminum compound, and the mixture thereof, because of the high activity.The curing catalyst (C) may be used alone or as a mixture thereof.The amount of the component (C) is not particularly limited. The amount is usually from 0.1 to 20 parts (parts by weight, hereinafter the same), preferably from 0.1 to 10 parts, based on 100 parts of the solid matter of the component (A) and the component (B). When the used amount of the component (C) is less than 0.1 part, the curability tends to lower. When the amount is more than 20 parts, the appearance of the film tends to lower.In the composition of the present invention, the dehydrating agent (D) can optionally be included as the stabilizing agent.Examples of the dehydrating agents which is the component (D) are, for instance, hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate and ethyl silicate. These hydrolyzable ester compounds may be added before, after or during the polymerization of the alkoxysilyl group-containing acrylic copolymer (B).As the dehydrating agent (D), methyl orthoacetate is particularly preferable, since the effect for stabilizing the one component composition is great.The used amount of the dehydrating agent is not particularly limited. The amount is usually not more than 100 parts, preferably not more than 50 parts, based on 100 parts of the solid matter of the components (A) and (B).The effect can be further increased by using a dehydrating accelerator when the dehydrating agent is used.Preferable examples of the dehydrating accelerators are, for instance, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; an organic acid such as formic acid, acetic acid, oxalic acid, benzoic acid, phtharic acid, p-toluenesulfonic acid, acrylic acid or methacrylic acid; a metal salt of carboxylic acid such as an alkyl titanate or lead octylate; a carboxylic acid organotin compound such as tin octylate, dibutyl tin dilaurate, or dioctyl tin maleate; a sulfide or mercaptide organotin compound such as monobutyl tin sulfide or dioctyl tin mercaptide; an organotin oxide such as dioxtyl tin oxide; an organotin compound obtained by reaction of the organotin oxide with an ester compound such as ethyl silicate, Ethyl Silicate 40, dimethyl maleate or dioctyl phthalate; an amine such as tetraethylenepentamine, triethylenediamine or N-β-aminoethyl-γ-aminopropyltrimethyoxysilane; and an alkali catalyst such as potassium hydroxide or sodium hydroxide. The agents are not limited thereto. Among them, the organic acids, the inorganic acids and the organotin compounds are particularly effective.The dehydrating accelerator is used in an amount of from 0.0001 to 20 parts, preferably from 0.001 to 10 parts, based on 100 parts of the dehydrating agent. When the compound which is used also as the component (C) is used as the dehydrating accelerator, the amount is from 0.1 to 20 parts, preferably from 0.1 to 10 parts, in addition to the used amount of the component (C).The used amount of the combination of methanol and n-butanol (E) is not particularly limited. The amount is usually not more than 100 parts, preferably not more than 50 parts, based on 100 parts of the solid matter of the components (A) and (B). When the component (E) is used alone, without using the dehydrating agent (D), the amount is usually from 0.5 to 100 parts, preferably from 2 to 50 parts.When the component (E) is used together with the dehydrating agent (D), the storage stability can be remarkably improved compared to the case where the composition comprising the components (A), (B), (C) and (D) is stored.As the solvent used in the composition of the present invention, any non-reactive solvents can be used.Examples of such solvents are, for instance, solvents used in general paints or coating agents such as aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, alcoholic esters, ketone alcohols, ether alcohols, ketone ethers, ketone esters or ester ethers.The used amount of the total solvents varies depending on the molecular weight or composition of the component (A) and the component (B) in the composition of the present invention, so is not decided wholly. The amount is controlled so that the composition has a necessary solid concentration or viscosity for the practical use, and is usually from 250 to 25 parts based on 100 parts of the solid matter.In order to improve the film properties such as adhesion, hardness and solvent resistance, a hydrolyzable silicon compound can be added to the composition of the present invention. The hydrolyzable silicon compound is a compound having a hydrolyzable silyl group at the ends or side chains, and preferable examples are, for instance, hydrolyzable silane compounds, condensation products of their partial hydrolyzates, their reaction products and their mixture.Examples of the silane compounds are, for instance, methyl silicate, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethyoxysilane, γ-acryloyloxypropyltrimethoxylilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxy silane, dimethyldimethoxysilane, diethyldimethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane, vinylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triphenylmethoxysilane, ethyl silicate, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ aminopropyltriethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dibutyldiethoxysilane, diphenyldiethoxysilane, vinylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane and triphenylmethoxysilane. The condensation product of the partial hydrolyzate of the hydrolyzable silane compund can be easily produced by mixing one or more silane compounds as mentioned above with a necessary amount of H2O and, if necessary, a small amount of a condensation catalyst such as hydrochloric acid or sulfuric acid, and advancing the condensation reaction at room temperature to 100°C while removing the produced alcohol. Examples of the condensation products of partial hydrolyzate of methyl silicate, having methoxysilyl group are, for instance, Methyl Silicate 47, Methyl Silicate 51, Methyl Silicate 55, Methyl Silicate 58 and Methyl Silicate 60, which are products made by Nippon Colcoat Kagaku Kabushiki Kaisha. Examples of the condensation products of partial hydrolyzate of methyltrimethoxysilane or dimethyldimethoxysilane, having methoxysilyl groups are, for instance, AFP-1, AFR-2, AFP-6, KR213, KR217 and KR9218, which are products made by Shin-Etsu Chemical Co., Ltd.; TSR165 and TR3357, which are products made by Toshiba Silicone Co., Ltd.; Y-1587, FZ-3701 and FZ-3704, which are products made by Nippon Unicar Kabushiki Kaisha. Examples of the condensation products of partial hydrolyzate of ethyl silicate, having ethoxysilyl group are, for instance, Ethyl Silicate 40, HAS-1, HAS-6 and HAS-10, which are products made by Nippon Colcoat Kagaku Kabushiki Kaisha.Examples of the reaction products of the abovementioned hydrolyzable silane compound are, for instance, a reaction product of a silane coupling agent containing amino group with a silane coupling agent containing epoxy group; a reaction product of a silane coupling agent containing amino group with a compound containing epoxy group such as ethylene oxide, butylene oxide, epichlorohydrine, epoxidated soybean oil, in addition, Epicoat 828 and Epicoat 1001, which are products made by Yuka Shell Epoxy Kabushiki Kaisha; a reaction product of a silane coupling agent containing epoxy group with an amine such as an aliphatic amine e.g. ethyl amine, diethyl amine, triethyl amine, ethylene diamine, hexane diamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine, an aromatic amine e.g. aniline or diphenyl amine, or an alicyclic amine such as cyclopentyl amine or cyclohexyl amine.Such hydrolyzable silicon compounds may be used alone or as a mixture thereof.The used amount of the hydrolyzable silicon compound is not particularly limited. The amount is usually from 0.01 to 100 parts, preferably from 0.1 to 30 parts, based on 100 parts of the solid matter of the components (A) and (B). When the used amount of the hydrolyzable silicon compound is less than 0.01 part, the addition effects are insufficiently obtained. When the amount is more than 100 parts, the appearance of the film prepared from the composition of the present invention tends to lower.According to the uses, thereof, there can be added to the composition for instance of the present invention, various additives such as diluents, pigments (including extender pigments), ultraviolet absorbers, light stabilizers, agents for preventing precipitation and leveling agents; celluloses such as nitrocellulose and cellulose acetate butyrate; resins such as epoxy resins, melamine resins, vinyl chloride resins, chlorinated polypropylene, chlorinated rubbers and polyvinyl butyral; and fillers. Next, the preparation method of the composition of the present invention is explained The preparation method is not particularly limited. For instance, the component (A) and the component (B) are cold-blended, or they are mixed, then heated (hot-blended) to partially react them, and the component (C) and component (E) and optionally component (D) are mixed herewith to prepare the composition of the present invention. The thus prepared composition of the present invention is a composition utilizing the crosslinking reaction wherein the hydroxyl group of the acrylic resin having hydroxyl group (A) reacts with the silyl group of the alkoxysilyl group-containing polymer (B), and is clearly distinct from conventional techniques using a melamine as the crosslinking agent. The composition of the present invention is excellent in storage stability.Such compositions of the present invention are suitable for use as coating agents used for various coatings such as coating for outer walls of buildings, automobiles, industrial machines, steel furnitures, household electric appliances and plastics, particularly, coating for use requiring to have excellent durability. The composition is applied to a substrate in a usual manner such as dipping, spraying or brushing, then is cured at usually not less than 30°C, preferably from 55° to 350°C to give a coating film having excellent durability.BEST MODE FOR CARRYING OUT THE INVENTIONThe composition of the present invention is more specifically explained by means of Examples in which all part and % are part by weight and % by weight unless otherwise noted.Preparation Example 1[Synthesis of an alkoxysilyl group-containing polymer (B)]A reaction vessel equipped with a stirrer, a thermometer, a condenser, a nitrogen inlet tube and a dropping funnel was charged with 45.9 parts of xylene, and the temperature was elevated to 100°C, while introducing nitrogen gas thereto. A mixture (b) having a composition shown below was added dropwise at a uniform velocity through the dropping funnel over 5 hours. (Mixture (b))Styrene12.8 partsMethyl methacrylate50.1 partsStearyl methacrylate6.9 partsγ-Methacryloyloxypropyltrimethoxysilane30.2 partsXylene13.5 parts2,2'-Azobisisobutyronitrile4.5 partsAfter completing the dropping addition of the mixture (b), 0.5 part of 2,2'-azobisisobutyronitrile and 5 parts of toluene were added dropwise at a uniform velocity over 1 hour. After completing the dropping addition, it was aged at 110°C over 2 hours, then was cooled down and xylene was added to the resin solution so as to adjust the solid content to 60 %. The properties of the resin solution (1) are shown in Table 1.Preparation Example 2[Synthesis of an acrylic resin having hydroxyl groups (A-1)]The reaction vessel was charged with 31.3 parts of butyl acetate and 9.5 parts of xylene instead of 45.9 parts of xylene, and a mixture (a-1) having the following composition was added in the same manner as in Preparation Example 1.(Mixture (a-1))Xylene18 partsStyrene28.3 partsMethyl methacrylate7.1 partsn-Butyl acrylate32.5 partsMethacrylic acid0.3 partPlaccel FM-131.8 parts2,2'-Azobisisobutyronitrile4.5 partsAfter completing the dropping addition of the mixture (a-1), 0.2 part of 2,2'-azobisisobutyronitrile and 3.8 parts of toluene were added dropwise at a uniform velocity over 1 hour. After completing the dropping addition, it was aged at 110°C for 2 hours, then was cooled down, and xylene was added to the resin solution so as to adjust the resin content to 60 %. The properties of the resin solution (2) are shown in Table 1.Preparation Example 3[ Synthesis of an acrylic resin having hydroxyl groups (A-2)]The reaction vessel was charged with 31.3 parts of butyl acetate and 9.5 parts of xylene instead of 45.9 parts of xylene, and a mixture (a-2) having the following composition was added in the same manner as in Preparation Example 1. (Mixture (a-2))Xylene18 partsStyrene28.3 partsMethyl methacrylate4.4 partsn-Butyl acrylate32.5 partsAcrylic acid3 partsPlaccel FM-131.8 parts2,2'-Azobisisobutyronitrile4.5 partsAfter completing the dropping addition of the mixture (a-2), 0.2 part of 2,2'-azobisisobutyronitrile and 3.8 parts of toluene were added dropwise at a uniform velocity over 1 hour. After completing the dropping addition, it was aged at 110°C for 2 hours, then was cooled down, and xylene was added to the resin solution so as to adjust the resin content to 60 %. The properties of the resin solution (3) are shown in Table 1. Resin solution(1)(2)(3)PropertyNon-volatile matter (%)606060 Viscosity (28°C, mPas (cps))900850980 Acid value (mgKOH/g solid)02.023 Hydroxyl value (mgKOH/g solid)07373 Number average molecular weight6.0006.0006.000 Hue (Gardner)< 1<1<1Examples 1 - 7 and Comparative Examples 1 - 3Using each resin solution obtained in Preparation Examples 1 - 3, a composition as shown in Tables 2 and 3 was prepared.The obtained composition was subjected to a storing test wherein it was allowed to stand at 50°C for 7 days or for 14 days under sealing. The viscosities before storage and after storage were measured at 23°C by using a Brook-field type viscometer. The results are shown in Tables 2 and 3. From the estimation results of Table 2 and Table 3, it would be recognized that the composition of the present invention is a one component composition improved in storage stability.
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A composition comprising: (A) an acrylic resin having hydroxyl group,(B) an alkoxysilyl group-containing acrylic copolymer having a group represented by the formula: wherein R1 is an alkyl group having 1 to 10 carbon atoms, R2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms selected from the group consisting of an alkyl group, an aryl group and an aralkyl group, and a is 0, 1 or 2,(C) a curing catalyst,(E) a combination of methanol and n-butanol, and optionally (D) a dehydrating agent, wherein said composition is in the form of a one component composition containing all said components (A), (B), (C), (E) and optionally (D).The one component composition of Claim 1, wherein said acrylic resin having hydroxyl group (A) has a hydroxyl value of 10 to 300 mg KOH/g and a number average molecular weight of 1,500 to 40,000.The one component composition of Claim 1 or 2, wherein said alkoxysilyl group-containing acrylic copolymer (B) is a polymer containing 5 to 90 % by weight of units of an alkoxysilyl group-containing monomer having a polymerizable unsaturated double bond and an alkoxysilyl group in its molecule.The one component composition of Claim 1, 2 or 3, wherein said curing catalyst (C) is at least one member selected from the group consisting of an organotin compound, an acid phosphate, a mixture or a reaction product of an acid phosphate and an amine, a saturated or unsaturated polyvalent carboxylic acid, an acid anhydride of a saturated or unsaturated polyvalent carboxylic acid, a reactive silicon compound, an organic titanate compound, and an organic aluminum compound.The one component composition of any of Claims 1 to 4, wherein said dehydrating agent (D) is a hydrolyzable ester compound.The one component composition of any of Claims 1 to 5, wherein said dehydrating agent (D) is at least one hydrolyzable ester compound selected from the group consisting of methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, y-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate and ethyl silicate.The one component composition of any of Claims 1 to 6, wherein said dehydrating agent (D) is methyl orthoacetate.The one component composition of any of Claims 1 to 7, which further contains a dehydrating accelerator.The one component composition of any of Claims 1 to 8, wherein said composition contains a hydrolyzable silicon compound. The one component composition of Claim 9, wherein said hydrolyzable silicon compound is at least one member selected from the group consisting of a hydrolyzable silane compound, a condensation product of a partial hydrolyzate of a silane compound, a reaction product of a silane coupling agent containing amino group with a silane coupling agent containing epoxy group, a reaction product of a silane coupling agent containing amino group with a compound containing epoxy group, and a reaction product of a silane coupling agent containing epoxy group with an amine.
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KANEGAFUCHI CHEMICAL IND; KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
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KATO YASUSHI; KAWAGUCHI HIROTOSHI; NANBU TOSHIRO; KATO, YASUSHI; KAWAGUCHI, HIROTOSHI; NANBU, TOSHIRO
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EP-0489919-B1
| 489,919 |
EP
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B1
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EN
| 19,940,907 | 1,992 | 20,100,220 |
new
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B25J9
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G05B19, G05D3, B25J19
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B25J9, B25J13
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B25J 9/16V1, G06K 9/32P, G06K 9/20S
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CALIBRATION SYSTEM OF VISUAL SENSOR
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A system for calibrating a visual sensor in a robot system. An arm (2) of a robot (1) is provided with a pattern plate (3) for calibration, and calibration pattern data (CPDr) of a pattern plate on the base coordinates of the robot are sent from a robot controller (10) to a visual sensor controller (20). The visual sensor controller (20) takes the image of the pattern plate (3) by a camera (4) and obtains the calibration pattern data (CPDc). Calibration data (CD) are obtained from these calibration pattern data (CPDr) and (CPDs) to calibrate the visual sensor.
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The present invention relates to a visual sensor calibration method of calibrating a visual sensor in a robot system, and more particularly, to a visual sensor calibration method of calibrating a plurality of cameras or the like. In current practice a robot system is provided with a visual function to enable it to pick up an image of a workpiece by using a camera or the like to determine the position of the workpiece, and thus carry out an operation such as assembling or palletizing or the like. Further, a plurality of cameras are used to accurately determine the position of a workpiece, or to correspond to a plurality of robots. It is necessary to calibrate the relationship between a robot coordinate system and a camera coordinate system, to accurately determine the position of a workpiece, and when a plurality of cameras is used, an exclusively designed jig is prepared and used. Such a calibration jig is large, however. The jig must be moved by jogging or a similar operation, to thereby pick up images thereof by a camera, resulting in a poor operability. Further, because most calibration jigs are large, they incur high manufacturing costs and the like, and require a special installation space. Furthermore, when a plurality of cameras is used, it is difficult to calibrate each camera. The present invention is intended to solve the above-mentioned problem, and an object of the present invention is to provide a calibration method for a visual sensor which eliminates the need for moving a jig when implementing a calibration. Another object of the present invention is to provide a calibration method for a visual sensor by which a visual sensor can be calibrated with a simple calibration jig. Still another object of the present invention is to provide a calibration method for a visual sensor which permits an easy calibration of each camera. US-A-4796200 discloses a robot system in which a master for a workpiece is created in space, point-by-point, according to CAD design or other data of an object such as a car body. According to the present invention, there is provided a method of calibrating a visual sensor in a robot system, the method comprising the steps of: providing a pattern plate including a plurality of dots, for obtaining a calibration, on an arm of a robot; obtaining, using a robot controller, first calibration pattern data of the pattern plate at a position of the pattern plate on the robot arm, the first calibration pattern data being coordinate positions of each dot in the pattern plate; sending the first calibration pattern data of the pattern plate from the robot controller to a visual sensor controller; obtaining, using the visual sensor controller, a second calibration pattern data from an image of the pattern plate, the second calibration pattern data being coordinate positions of each dot in the image of the pattern plate; and, obtaining, using the visual sensor controller, calibration data from the first calibration pattern data and the second calibration pattern data, thereby to calibrate a visual sensor. A robot controller itself holds accurate position data of the pattern plate on the robot coordinate system. More specifically the robot controller holds the first calibration pattern data of the pattern plate based on a coordinate position of the end of the robot arm and an installation dimension of the pattern plate. The visual sensor controller reads the first calibration pattern data from the robot controller via a communication line and further the visual sensor controller receives an input of an image of the pattern plate from the visual sensor and detects each dot of the pattern to there by obtain the second calibration pattern data. The calibration data can be acquired by comparing the first calibration pattern data with the second calibration pattern data. In the drawings: FIG. 1 is a configuration block diagram of a whole robot system for implementing the visual sensor calibration method according to the present invention; FIG. 2 is a detailed view of dot patterns on the pattern plate; FIG. 3 shows an example of two cameras used to pick up an image of one pattern plate; and FIG. 4 shows an example whereby, in a robot system comprising four robots and four cameras, all four cameras are calibrated against a robot coordinate system common to all robots. Best Mode of Carrying Out of the InventionAn embodiment of the present invention is described with reference to the drawings. FIG. 1 is a configuration block diagram of an entire robot system for implementing the visual sensor calibration method according to the present invention. In FIG. 1, in order to give a brief description of the flow of the calibration pattern data, only one robot and one camera are used, but in an actual application, a plurality of robots or cameras is used. A pattern plate 3 provided with a plurality of dot patterns is connected to an arm 2 of a robot 1. The details of the pattern plate 3 will be given later. The robot 1 is controlled by a robot controller 10. The robot controller 10 determines a coordinate position of the end of the arm on the robot's base coordinates, i.e., a coordinate position of TCP (Tool Center Point) as the present position, and accordingly, holds in a memory 11 the calibration pattern data on the robot coordinates which indicates the position of each dot pattern of the pattern plate 3 based on the TCP of the arm 2 and the installation dimension of the pattern plate 3. The calibration pattern data is taken as a CPDr 11a. The robot controller 10 carries out a control such that the pattern plate 3 is not perpendicular to, but is at a certain angle with respect to, the optical axis of a camera 4. The camera 4 is connected to a visual sensor controller 20 which photographs the pattern plate 3 by using the camera 4, to thereby calibrate the camera 4. The configuration of the visual sensor controller 20 is centered around a processor (CPU) 21. Control software 22a for implementing the calibration is stored in a ROM 22 to control the calibrating operation, and a RAM 23 stores calibration data (CD) 23a, to be discussed later, and the calibration pattern data (CPDr) 11a received from the robot controller 10. The coordinate position data on each dot of the pattern plate and dot pattern data (DPD) 24a are stored in a RAM 24. The processor 21 picks up an image of the dot pattern on the pattern plate 3 through the camera 4, in accordance with the control software 22a, and the image data is temporarily stored in a RAM 25 via a camera interface 28. This image data is the video data of each dot pattern on the image surface of the camera 4. An image processing processor 28 obtains a calibration pattern data (CPDc) 25a of the camera 4 from the position data and the already stored dot pattern data (DPD) 24a, and stores same in the RAM 25. The calibration pattern data (CPDr) 11a in the robot controller 10 is read from the interface 27 through a communication line 13 and stored in the RAM 23. Then, the calibration pattern data (CPDr) 11a on the robot coordinates is compared with the calibration pattern data (CPDc) 25a on the camera coordinates, to thereby calculate the position and orientation of the camera coordinate system with respect to the robot coordinate system, and thus perform the calibration. The result is stored in the RAM 23 as the calibration data (CD) 23a. The calibration data (CD) 23a is used for assembling, palletizing and the like, and this data makes it possible to accurately determine the position and orientation of a workpiece in the robot coordinate system, through the camera 4 and the visual sensor controller. FIG. 2 is the detailed view of the dot patterns on the pattern plate, wherein dot patterns 3a, 3b, 3c and the like are arranged in the shape of a square on the pattern plate 3. Theoretically, six dot patterns should suffice, but 25 dot patterns are provided to obtain a more accurate calibration pattern data. The dot pattern 3a, in particular, is made larger than the other dot patterns, to serve as an origin. FIG. 3 illustrates an example where two cameras are used to pick up an image of one pattern plate. More specifically, by picking up an image of the dot patterns on the pattern plate 3 by two cameras 5 and 6, the calibration of the respective camera coordinate systems can be carried out independently. FIG. 4 illustrates an example where, in a robot system consisting of four robots and four cameras, all four cameras are calibrated with respect to the robot coordinate system common to all the robots. An image of a pattern plate 3a of a robot 31 is picked up by a camera 41, an image of a pattern plate 3b of a robot 32 is picked up by a camera 42, an image of a pattern plate 3c of a robot 33 is picked up by a camera 43, and an image of a pattern plate 3d of a robot 34 is picked up by a camera 44. The picked-up image data of each camera is input to a visual sensor controller, not shown in this drawing, and the calibration data for the respective cameras is calculated. The details of this process are the same as in the case of FIG. 1. As may be also seen from this example, calibration data can be obtained for each camera, and therefore, even when the position or the like of a camera is changed, only the calibration data of that camera need be obtained again. In the above explanation, an example wherein one robot an d two cameras are used and another example wherein four robots and four cameras are used are described, but it is of course understood that those numbers may be changed as necessary. Also, only one type of pattern plate is required, and as need not be large, it can be manufactured easily. Further, there is no need to perform a jogging or the like to obtain calibration data. Although cameras are used as visual sensors in the above description, other equipment such as laser length measuring instruments may be used to read dot patterns on a pattern plate, to thus obtain the calibration pattern data. As described above, according to the present invention, calibration pattern data in a robot system is sent to a visual sensor controller, which compares that calibration pattern data with the calibration pattern data on the visual sensor coordinates obtained by a visual sensor from the picked-up image data of a camera, to thereby obtain calibration data, and thus the calibration data is easily obtained. Further, if the visual sensor picks up an image of the pattern plate, this will suffice and no special operation is required. Furthermore, a plurality of visual sensors can be calibrated independently, and in addition, there is no need to use a special jig, thus eliminating the need for a jig installation space.
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A method of calibrating a visual sensor in a robot system, the method comprising the steps of: providing a pattern plate (3) including a plurality of dots (3a,3b,3c), for obtaining a calibration, on an arm (2) of a robot (1); obtaining, using a robot controller (10), first calibration pattern data (CPDr) of the pattern plate at a position of the pattern plate on the robot arm, the first calibration pattern data (CPDr) being coordinate positions of each dot in the pattern plate; sending the first calibration pattern data (CPDr) of the pattern plate from the robot controller to a visual sensor controller (20); obtaining, using the visual sensor controller (20), a second calibration pattern data (CPDc) from an image of the pattern plate, the second calibration pattern data (CPDc) being coordinate positions of each dot in the image of the pattern plate; and, obtaining, using the visual sensor controller (20), calibration data (CD) from the first calibration pattern data and the second calibration pattern data, thereby to calibrate a visual sensor. A method according to claim 1, further including the step of obtaining the second calibration pattern data from the image generated by a camera. A method according to claim 1, further including the step of obtaining the second calibration pattern data by a laser length measuring instrument. A method according to claim 1, further including the step of obtaining the second calibration pattern data by a plurality of cameras from one pattern plate of the robot, thereby to calibrate each of the plurality of cameras. A method according to claim 1, further including the step of obtaining the second calibration pattern data for a plurality of cameras from pattern plates of a plurality of robots, thereby to carry out a calibration. A method according to claim 1, further including the step of providing the pattern plate (3) including one dot pattern (3a) as an origin and a plurality of dot patterns arranged in a square shape. A method according to claim 1, further including the step of providing the calibration data as matrix data.
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FANUC LTD; FANUC LTD.
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WATANABE ATSUSHI FANUC MANSHIO; WATANABE, ATSUSHI FANUC MANSHION HARIMONI 7-207
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EP-0489920-B1
| 489,920 |
EP
|
B1
|
EN
| 19,970,903 | 1,992 | 20,100,220 |
new
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H01J9
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H01J29
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H01J29
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T01J229:07F3A2, H01J 29/07
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COLOR CATHODE-RAY TUBE
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A color cathode-ray tube (20) in which, opposing to a color fluorescent screen (5) so configured that stripes (9) of luminescent materials each capable of emitting light of a color are arranged in parallel to each other in a predetermined order, an aperture grille (10) in which a number of slits (4) extending in the longitudinal direction of the stripes (9) are made in parallel to each other is provided, the aperture grille (10) is so configured as to stretch a thin plate (1) having the slits (4) on a frame (3) with a required tension in the longitudinal direction of the slits (4). The thin plate (1) is a thin high purity iron plate having a thickness of 0.05 mm or less. Since the controllability of the widths of the slits in manufacturing is improved by virtue of the specified thickness of the thin plate, the precision and productivity of the aperture grille can be improved and the weight thereof can be reduced. Further, a fine structure screen for color cathode-ray tubes can be manufactured.
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This invention generally relates to color cathode ray tubes for use in a wide variety of display devices such as TV and so on and, more particularly, to a color cathode ray tube of Trinitron (registered trademark) type. BACKGROUND ARTIn a color cathode ray tube, a color selecting mechanism is provided in an opposing relation to a color fluorescent screen to thereby cause an electron beam to land on predetermined fluorescent patterns. In an ordinary color cathode ray tube, a shadow mask in which a single circular beam aperture, for example, is bored through a metal plate for dot-shaped red, green and blue fluorescent triplet, for example, is provided in an opposing relation to the color fluorescent screen as a color selecting mechanism. Such shadow mask is supported to a frame by welding a circumferential portion of the metal plate molded as a dome shape by a press-treatment or the like. In this case, the shadow mask is supported to the frame without the application of tension so that, when a temperature of the shadow mask rises due to the electron beam scanned thereon, a so-called doming phenomenon which gives rise to a color misregistration is caused by the thermal expansion. To solve this problem, an Invar material having a low coefficient of thermal expansion is utilized as a mask material and the plate thickness thereof tends to increase in order to increase strength. On the other hand, in the color cathode ray tube of Trinitron type, three election beams corresponding to red, green and blue colors are arranged on the horizontal plane and a color fluorescent screen is formed by arranging red, green and blue fluorescent stripes, each extending in the vertical direction, in a predetermined order in parallel. Also, an aperture grill in which a large number of slits extended along the extending direction of the fluorescent stripes are formed is disposed in an opposing relation to the fluorescent stripes as a color selecting mechanism. In the ordinary aperture grill, as shown in FIG. 6 which is a schematic perspective view of an example of the ordinary aperture grill, a large number of slits 4 are bored through a metal plate 42 formed of a high purity iron thin plate having a thickness of 0.08 to 0.15 mm and this metal plate 42 is stretched over a frame 3. The frame 3 is composed of a pair of opposing frame side members 3A, 3B and arm members 3C, 3D disposed across these frame side members 3A, 3B. The front end faces of the frame side members 3A, 3B are formed as curved surfaces forming the same cylindrical surface and the metal plate 42 is stretched over these frame side members 3A and 3B. When this metal plate 42 is stretched over and attached to the frame 3, the frame side members 3A and 3B of the frame 3 are drawn closer to each other by a turnbuckle. Then, under this condition, the metal plate 42 is secured at its edge portions corresponding to the respective ends of each slit 4 to the front end faces of the frame side members 3A and 3B by the welding-process. Thereafter, the external force applied to the frame 3 is released, whereby the band-shaped portions between the slits 4 on the metal plate 42 are extended in the extending direction of the slit 4 with a predetermined tension by a force of restitution. On the other hand, as the color cathode ray tube becomes larger in size recently, the length of the band-shaped portion between the slits 4 of the metal plate 42 of the aperture grill 10is increased so that, when an electron beam strikes the fluorescent screen, the band-shaped portion tends to vibrate due to vibration caused by sound, impulse or the like, which gives rise to problems such as occurrence of color misregistration or the like. Therefore, in order to suppress the vibration of the band-shaped portion, the thickness of the metal plate 42 is increased to increase rigidity or the thickness of the material forming the frame 3 is increased to increase a resilient force which removes the above-mentioned distortion, thereby suppressing the vibration of the band-shaped portion. The slits 4 are formed on the relatively thick metal plate 42 by etching both surfaces 42A and 42B of the metal plate 42 according to the photolithography technique. That is, as shown in FIG. 7A, a photoresist is coated on one surface 42A of the metal plate 42, subjected to the pattern exposure, developed and removed by the photolithography technique to form a predetermined stripe pattern through which openings 42AC are opened,thereby an etching mask 11A being formed. Then, in a like manner, an etching mask 11B having openings 42BC whose opening width is made large as compared with the width of the openings 42AC is formed on the rear surface 42B in a just opposing relation to the pattern of the former etching mask 11A. Then, as shown in FIG. 7B, the first etching process is carried out, in which stripe-shaped grooves are formed on the two surfaces 42A and 42B by the etching process which uses an etchant such as FeCℓ3 (ferric chloride) or the like. Then, as shown in FIG. 7C, a protecting film 12 such as a varnish or the like is coated on the stripe-shaped groove on the surface 42A side and used as an etching mask to carry out for the other surface 42B a relatively gentle etching with an etchant such as FeCℓ3 having a relatively low concentration until the protecting film 12 is exposed as shown in FIG. 7D. Thereafter, by removing the protecting film 12, the slit 4 whose cross section is substantially 8 -letter shape is formed as shown in FIG. 8. When the etching is carried out twice and the slit 4 is formed by the second etching whose etching rate is slow as compared with the case such that the groove is formed by one etching-process, the etching time can be controlled with ease reliably so that the excess proceeding of the etching can be prevented. As a consequence, each etching depth can be formed with accuracy and therefore an effective width of the slit 4, i.e., a distance SW between the edges 7 produced by the etching process of the two surfaces can be formed with excellent controllability and with high accuracy even when the metal plate 42 is thick. However, this technique cannot avoid the problem such that a workability is deteriorated as compared with the case that the groove is formed by one etching process. When the edge 7 is formed as described above, a tapered portion 8 of a gentle curved shape is formed from the respective surfaces 42A, 42B to the edge 7. Accordingly, as shown in FIG. 9 which is a cross-sectional view illustrating that electron beams impinge upon a color fluorescent screen 5 when this aperture grill 10 is used, an incident electron beam Ei becomes incident on the color fluorescent screen 5 through the slit 4 to make the fluorescent dots of stripe shapes luminous. On the other hand, a reflected electron beam Er1 from the color fluorescent screen 5 due to the secondary emission is reflected on the surface of the aperture grill 10 and on the tapered portion 8 to cause scattered electron beams Es or a reflected electron beam Er2 to occur. As a result, the light emission of the color fluorescent screen 5 becomes inaccurate, which gives rise to the deterioration of color contrast and color purity. Further, when the slits 4 of the aperture grill 10 are formed through the thick metal plate 42 by one etching process, the surface area of the tapered portion 8 is increased more, which makes the problem of the deterioration of the color contrast and color purity more remarkable. As described above, in the conventional color cathode ray tube of Trinitron type, it is preferable that the aperture grill thereof uses the relatively thick metal plate 42. In this case, however, since the weight of the aperture grill 10 is increased because the resilient force must be increased in order to suppress the vibration as earlier noted, there is the problem that the total weight of the color cathode ray tube is unavoidably increased. Further, the width SW of the slit 4 which can be formed in the above-mentioned etching process is about 50 % of a thickness t of the metal plate 42 due to the restrictions from an etching characteristic standpoint. For this reason, if the thickness of the metal plate 42 is increased, the width SW of the slit 4 is increased in proportion to the thickness t of the metal plate. There is then the problem such that the slits cannot be densified, that is, the color cathode ray tube cannot be formed as a high definition color cathode ray tube. US-A-4,926,089 discloses a front assembly for a color cathode ray tube with a metal foil shadow mask which is mounted in tension on a frame. The mask comprises a series of parallel strips seperated by slits, the strips being coupled by widely spaced ties. Further, the mask has between the strips one or more ties extending partially between but not interconnecting adjacent strips. The spaced ties have the disadvantage ofblocking electron beam emission through the mask. DISCLOSURE OF INVENTIONThe present invention is directed to a color cathode ray tube comprising: a color fluorescent screen having a plurality of respective color fluorescent stripes arranged in a predetermined order in parallel on the fluorescent screen; adjacent to and spaced from the screen an aperture grill being formed of a frame having first and second frame side members, and an aperture grill plate stretched on the frame and connected to and extending between the first and second frame side members at a predetermined tension; said aperture grill plate having band-shaped portions defining a plurality of slits each of which extends parallel with the fluorescent stripes; and said aperture grill plate having a thickness of equal to or less than 0.05 mm; characterized in that said aperture grill plate is formed of high purity iron; that said slits are extending continuously without interruption from the first frame side member to the second frame side member; and that a natural resonance frequency of the plate band-shaped portions is in a region which does not respond to sound and impulse vibrations. That is, in the present invention, contrary to an accomplished idea concerning the thickness of the metal plate forming the existing aperture grill, the thickness of the metal plate of the aperture grill is selected to be 0.05 mm. Even when the thickness of the metal plate is reduced as described above, the vibration of the band-shaped portions of the aperture grill caused by the sound and impulse can be suppressed similarly to the prior art. The reason for this will be understood as follows. Assuming that the band-shaped portion of the aperture grill is a string, then the resonance frequency f thereof is given by the following equation (11): f = (gT/ρ)1/2 /2ℓ where g is the gravitational acceleration, ρ the linear density of string, T the stress and ℓ the length of the string. Accordingly, in the prior art, while the length ℓ of the string is increased as the color cathode ray tube becomes larger, the value of the resonance frequency f is increased by increasing the stress T to avoid the frequency band of the principal vibration such as sound or the like, thereby the vibration being controlled. According to the present invention, when the thickness of the aperture grill is reduced, then the linear density of the string, that is, ρ is decreased and accordingly, the resonance frequency f is increased and therefore can be deviated from the principal resonance frequency band relating to the frequency such as sound, vibration or the like. Thus, even when the thickness of the metal plate is reduced as described above, then the vibration of the band-shaped portion in the aperture grill can be suppressed similarly to the prior art. Therefore, the occurrence of color misregistration or the like caused by the vibration such as sound, impulse or the like when electron beams strike the fluorescent screen can be avoided, which can improve the image quality of the color cathode ray tube. As shown in FIG. 4 which is a cross-sectional view of an aperture grill thin plate 1, the thickness of the aperture grill thin plate is thin so that slits 4 can be formed with high accuracy even by one etching process. Also, productivity can be improved by the reduction of the etching time and yield can be improved by the reduction of the material. Further, since the width of the slit, which can be formed in the etching process, is about 0.5t relative to the thickness t of the metal plate through which the slit is formed, the thickness t is reduced and therefore the width of the slit can be reduced as compared with the prior art. Thus, the accuracy of the aperture grill can be increased, which can densify the slits, that is, which can provide a high definition color cathode ray tube. Furthermore, the surface area of a tapered portion is reduced in accordance with the reduction of the thickness so that, as shown in FIG. 5 which is a schematic cross-sectional view of impingement of electron beams, reflection and scattering of electron beams at the tapered portion 8 can be suppressed. Thus, the deterioration of the color contrast and color purity can be suppressed, which can provide the color cathode ray tube of high definition. Also, since the thickness of the aperture grill thin plate is reduced, rigidity of the frame member can be reduced and the aperture grill can be reduced in weight. In addition, in accordance with the reduction of the weight, a power required by a degauss coil which degausses an external magnetism in the color cathode ray tube can be reduced, which can improve characteristics such as low power consumption or the like. BRIEF DESCRIPTION OF DRAWINGSFIG. 1 is a schematic perspective view illustrating a preferred embodiment of a color cathode ray tube according to the present invention, FIGS. 2A, 2B and FIGS. 3A, 3B are manufacturing process diagrams showing a method of producing an aperture grill of the color cathode ray tube according to the present invention, FIG. 4 is a schematic enlarged cross-sectional view illustrating an aperture grill of the color cathode ray tube according to the present invention, FIG. 5 is a cross-sectional view illustrating the incident condition of electron beams of the color cathode ray tube according to the present invention, FIG. 6 is a perspective view illustrating a conventional aperture grill, FIGS. 7A through 7D are manufacturing process diagrams showing a method of producing the conventional aperture grill, FIG. 8 is a schematic enlarged cross-sectional view of the conventional aperture grill, and FIG. 9 is a cross-sectional view illustrating the incident condition of electron beams of the color cathode ray tube according to the prior art. BEST MODE FOR CARRYING OUT THE INVENTIONIn a color cathode ray tube according to the present invention, as shown in FIG. 1 which shows an example thereof, an aperture grill 10 having a number of slits 4 extended in the extending direction of fluorescent stripes 9 bored therethrough in parallel is disposed in an opposing relation to a color fluorescent screen 5 on which the fluorescent stripes of respective colors are arranged in a predetermined order in parallel. This aperture grill 10 is constructed in such a manner that a large number of slits 4 are bored through an aperture grill thin plate 1 having a thickness of less than 0.05 mm, for example, a 0.05 mm-thick thin plate made of iron of high purity and this aperture grill thin plate 1 is stretched over a frame 3. The frame 3 is comprised of a pair of opposing frame side members 3A, 3B and arm members 3C, 3D extended between these frame side members 3A and 3B. The front end faces of the frame side members 3A, 3B are formed as curved surfaces forming the same cylindrical surface and the aperture grill thin plate 1 is stretched over these frame side members 3A and 3B. When this aperture grill thin plate 1 is stretched on the frame 3, the frame side members 3A and 3B of the frame 3 are drawn closer to each other by a turnbuckle. Then, under this condition, the aperture grill thin plate 1 is secured at its edge portions corresponding to the respective ends of each slit 4 to the front end faces of the frame side members 3A and 3B by the welding-process. Thereafter, the external force applied to the frame 3 is released, whereby the band-shaped portions between the slits 4 of the aperture grill thin plate 1 are extended in the extending direction of the slits 4 with a predetermined tension by a force of restitution of the frame 3. Respective examples of methods of forming the slits 4 of the aperture grill thin plate 1 are represented in process diagrams of FIGS. 2A and 2B and FIGS. 3A and 3B. Initially, as shown in FIG. 2A, on one surface 1A of the thin plate 1 formed of a high purity iron thin plate having a thickness of, for example, 0.05 mm, an etching mask 11A is formed so as to have a predetermined stripe-shaped pattern, that is, so as to be extended in the direction perpendicular to the sheet of drawing of FIG. 2 by the photolithography technique such as the coating of photoresist, the pattern exposure, the development or the like. Further, a photoresist or the like is coated on the whole surface of the other surface 1B to form an etching mask 11B. Then, as shown in FIG. 2B, the etching process is carried out from the surface 1A side by using an etchant such as FeCℓ3 or the like, thereby the stripe-shaped slits 4 being formed. In this case, the thickness of the aperture grill thin plate 1 is as thin as about 0.05 mm so that, even when the etching speed is made relatively low, the slits 4 of a predetermined width can be formed accurately without increasing the etching time considerably, that is, with excellent productivity only by the etching process from one surface 1A side as described above. Alternatively, as shown in FIG. 3A, on the two surfaces 1A and 1B of the aperture grill thin plate 1 formed of a high purity iron thin plate having a thickness of about 0.05 mm, by the application of the photolithography technique, there are formed etching masks 11A and 11B of stripe-shaped patterns extending in the direction perpendicular to the sheet of drawing of, for example, FIG. 3 and in which respective openings 11AC and 11BC are provided in a correct opposing relation, the opening widths thereof being substantially made equal. Then, these etching masks are used as the masks and from the two surfaces 1A and 1B, the etching is carried out by using the etchant such as FeCℓ3 or the like to thereby form the stripe-shaped slit 4 as shown in FIG. 3B. Also in this case, the thickness of the aperture grill thin plate 1 is selected to be as thin as about 0.05 mm so that, even when the etching rate is decreased relatively, the slit 4 of the predetermined width can be formed with high accuracy and with excellent productivity similarly to the method shown in FIG. 2. After the slit 4 is formed as described above, the etching masks 11A and 11B are removed and an aperture grill having a predetermined slit width SW can be obtained as shown in FIG. 4. In this case, since the thickness t of the aperture grill thin plate 1 is 0.05 mm and is sufficiently thin, the width SW of the slit 4, which can be formed by the etching-process, becomes 0.5t, i.e., 0.025 mm, which can provide the slits 4 more densified as compared with those of the prior art. Therefore, the color cathode ray tube 20 can be formed as the high definition color cathode ray tube. As shown in FIG. 5 which shows the condition such that electron beams become incident on the aperture grill 10, since the thickness of the aperture grill thin plate 1 is reduced, the surface area of the tapered portion 8 and the surface area of the aperture grill 10 on its surface opposing the color fluorescent screen 9 side also are reduced. Consequently, it is possible to suppress the occurrence of the scattered electron beam Es and the reflected electron beam Er2 which cause the color contrast and the color purity to be deteriorated in the prior art.
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A color cathode ray tube (20), comprising: a color fluorescent screen (5) having a plurality of respective color fluorescent stripes (9) arranged in a predetermined order in parallel on the fluorescent screen; adjacent to and spaced from the screen an aperture grill (10) being formed of a frame (3) having first and second frame side members (3A, 3B), and an aperture grill plate (1) stretched on the frame and connected to and extending between the first and second frame side members at a predetermined tension; said aperture grill plate having band-shaped portions defining a plurality of slits (4) each ofwhich extends parallel with the fluorescent stripes: and said aperture grill plate having a thickness of equal to or less than 0.05 mm; characterized in thatsaid aperture grill plate (1) is formed of high purity iron; said slits (4) are extending continuously without interruption from the first frame side member (3A) to the second frame side member (3B); and that a natural resonance frequency ofthe plate band-shaped portions is in a region which does not respond to sound and impulse vibrations.
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SONY CORP; SONY CORPORATION
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KAWASE MITSUHIRO; KUME HISAO; KAWASE, MITSUHIRO; KUME, HISAO; KAWASE, MITSUHIRO, SONY CORPORATION; KUME, HISAO, SONY CORPORATION
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EP-0489921-B1
| 489,921 |
EP
|
B1
|
EN
| 19,950,913 | 1,992 | 20,100,220 |
new
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C08L9
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C08K5, C08L11
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C08C19, C08K5
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C08C 19/44, C08K 5/46+L21/00, C08K 5/34+L15/00, C08K 5/17+L15/00, C08K 5/41+L21/00, C08K 5/47+L15/00, C08K 5/3445+L21/00, C08K 5/3432+L21/00, C08K 5/19+L21/00, C08K 5/17+L21/00
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REDUCED HEAT-BUILDUP RUBBER COMPOSITION
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A reduced heat-buildup rubber composition prepared by compounding 100 parts by weight of either a polymer prepared by the reaction of a conjugated diene polymer terminated with an alkali metal atom and a specified tin compound or a rubber blend comprising at least 30 parts by weight of said polymer and other diene polymer with 20 to 100 parts by weight of a reinforcing filler, 0.1 to 5 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole, and 0.2 to 10 parts by weight of a specified nitrogen or sulfur compound. The composition is useful over a wide application range and particularly suitable for a tire of low fuel consumption.
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This invention relates to a low heat-generation rubber composition, and more particularly to a rubber composition having a heat-generation lower than that of the conventional low heat-generation rubber composition. In order to satisfy social demands of resource-saving and energy-saving, the developmen of low fuel-consumption tires has been conducted for several years in the rubber industry, particularly the tire industry. In the development of such low fuel-consumption tires, it is inevitable to use low heat-generation rubber compositions. As a technique of improving low heat-generation by polymer, particularly conjugated diene based polymer, there are some techniques disclosed, for example in Japanese Patent Application Publication No. 44-4966, U.S. Patent No. 3956232, Japanese Patent laid open No. 57-205414, and Japanese Patent laid open No. 61-141741. They are concerned with an improving technique through the reaction between the polymer and tin compound or isocyanate compound, whereby it is attempted to improve fuel consumption and reinforcing properties. On the other hand, techniques of improving low heat-generation rubber compositions by compounding chemicals are disclosed in Japanese Patent laid open No. 1-207337. Recently, it is more demanded to lower the fuel consumption of a vehicle for preventing global warming. However, it has been confirmed that the improving techniques with the above polymer or compounded chemical composition itself are not sufficient for this purpose. Therefore, it is naturally considered to use a combination of the low heat-generation polymer and compounded chemical compositions for further improving the low heat-generation. The present inventors have confirmed that, even when low heat-generation improver is compounded with the low heat-generation polymer, remarkable effects are not obtained as compared with the effect obtained by adding the low heat-generation improver to a conventional polymer. The present invention aims to provide a combination of low heat-generation polymer and low heat-generation improver capable of developing low heat-generation effect by synergistic action of such a combination. The inventors have made various studies in order to solve the above problem and found that an unexpected low heat-generation improving effect is developed by combining particular tin-modified diene series rubber with a low heat-generation improver inclusive of 2,5-dimercapto-1,3,4-thiadiazole, and as a result the invention has been accomplished. The present invention provides a low heat-generation rubber composition comprising 20-100 parts by weight of a reinforcing filler, 0.1-5 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole and 0.2-10 parts by weight of at least one compound selected from compounds of the following formulae (I) - (VIII): (wherein R₃, R₆, R₉, R₁₁ in (I)-(VIII) are alkyl group having a carbon number of 8-18 or aryl group, R₄, R₅, R₇, R₈, R₁₀ are alkyl group having a carbon number of 1-2, R₁₂ is aryl group or cyclohexyl group, R₁₃ is alkyl group having a carbon number of 1-6, cyclohexyl group or hydrogen atom, R₁₄, R₁₅ are alkyl groups having a carbon number of 1-18, benzyl group or hydrogen atom, and each of m and n is an integer of 1-3) based on 100 parts by weight of a polymer obtained by reacting a conjugated diene series polymer containing an alkali metal in its polymer terminal, which is obtained by polymerizing or copolymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent in the presence of an organic alkali metal as a polymerization initiator, with a tin compound represented by the following general formula:Sn(R₁)pX4-p or (wherein R₁ and R₂ are substituents selected from the group consisting of alkyl group, alkenyl group, cycloalkyl group and aryl group and are the same or different, X is a halogen atom and p is an integer of 0-3) (hereinafter referred to as a tin compound-modified polymer) alone or a rubber blend of not less than 30 parts by weight of this polymer and another diene series polymer. The tin compound-modified polymer used in the rubber composition according to the invention is produced, for example, by methods as mentioned later. In general, the production is carried out in an inert organic solvent. In this case, pentane, hexane, cyclohexane, heptane, benzene, xylene, toluene, tetrahydrofuran, and diethyl ether are used as the inert organic solvent. At first, the homopolymerization of the conjugated diene compound such as butadiene, or the copolymerization of the conjugated diene compound and the aromatic vinyl compound such as butadiene and styrene is conducted. As the polymerization initiator is used an organic alkali metal. As the organic alkali metal catalyst, mention may be made of alkyl lithiums such as n-butyllithium, sec-butyllithium, t-butyllithium, 1,4-dilithium butane, and a reaction product of butyllithium and divinylbenzene; alkylene dilithiums, stilbene dilithium, diisopropenylbenzene dilithium, sodium naphthalene, and lithium naphthalene. In the copolymerization, a Lewis base may be used as a randomizing agent and an adjusting agent for the microstructure of the butadiene unit in the polymer, if necessary. As this base, mention may be made of ethers and tertiary amines such as dimethoxybenzene, tetrahydrofuran, dimethoxy ethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, triethylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylene diamine; and 1,2-dipyperidino ethane. In the polymerization for the production of living polymers, the above inert organic solvent, monomer such as 1,3-butadiene or 1,3-butadiene and styrene and an organic alkali metal catalyst and, if necessary, a Lewis base are charged into a reaction vessel purged with nitrogen as a polymerization system simultaneously or discontinuously or continuously to conduct polymerization. The polymerization temperature is usually -120 to +150°C, preferably -80 to +120°C, and the polymerization time is usually 5 minutes to 24 hours, preferably 10 minutes to 10 hours. The reaction may be carried out at a constant temperature within the above polymerization temperature range, or the polymerization may be made by raising the temperature or under adiabatic conditions. Furthermore, the polymerization reaction may be a batch system or a continuous system. Moreover, the concentration of the monomer in the solvent is usually 5-50% by weight, preferably 10-35% by weight. In the production of the living polymer, in order to deactivate the organic alkali metal catalyst and the living polymer, it is required to take care to prevent the incorporation of deactivating compound such as halogen compound, oxygen, water, or carbon dioxide gas into the polymerization system as far as possible. The tin compound-modified polymer used in the invention is a tin compound-modified polymer obtained by reacting an active terminal of the living polymer contained in the above polymer system with the following particular tin compound. As a particular example of the tin compound, use may preferably be made of tetrachlorotin, tetrabromotin, methyl trichlorotin, butyl trichlorotin, octyl trichlorotin, phenyl trichlorotin, phenyl tribromotin, dimethyl dichlorotin, dimethyl dibromotin, diethyl dichlorotin, dibutyl dichlorotin, diphenyl dichlorotin, diallyl dichlorotin, tributenyl monochlorotin, methyl tin trisstearate, ethyl tin trisstearate, butyl tin trisoctanoate, butyl tin trisstearate, octyl tin trisstearate, octyl tin trisstearate, butyl tin trislaurate, dibutyl tin bisoctanoate, dibutyl tin bisstearate, dibutyl tin bislaurate, dimethyl tin bisstearate, diethyl tin bislaurate, dioctyl tin bisstearate, trimethyl tin laurate, trimethyl tin stearate, tributyl tin octanoate, tributyl tin stearate, tributyl tin laurate, trioctyl tin stearate, phenyl tin trisstearate, phenyl tin trisoctanoate, phenyl tin trislaurate, diphenyl tin bisstearate, diphenyl tin bisoctanoate, diphenyl tin bislaurate, triphenyl tin stearate, triphenyl tin laurate, cyclohexyl tin trisstearate, dicyclohexyl tin bisstearate, tricyclohexyl tin stearate, tributyl tin acetate, dibutyl tin bisacerate, and butyl tin trisacerate. The tin compound-modified polymer according to the invention is obtained by reacting the active terminal of the living polymer with the above particular tin compound. The reaction between the active terminal of the living polymer and the tin compound having a functional group is carried out by adding the compound to the solution of polymer system of the living polymer, or by adding the solution of the living polymer to an organic solution containing the tin compound. The reaction temperature is -120 to +150°C, preferably -80 to +120°C, and the reaction time is 1 minute to 5 hours, preferably 5 minutes to 2 hours. After the completion of the reaction, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the tin compound-modified polymer and then drying is carried out on a hot roll or under reduced pressure, whereby the tin compound-modified polymer can be obtained. Alternatively, the tin compound-modified polymer can be obtained by directly removing the solvent from the polymer solution under reduced pressure. The compound of the general formula (I) used in the rubber composition according to the invention includes dimethyldodecylamine, hexadecyldimethylamine and octadecyldimethylamine. The compound of the general formula (II) includes dimethyldodecylbetaine, dimethylhexadecylbetaine and dimethyloctadecylbetaine. The compound of the general formula (III) includes sodium acylmethyl taurate. The compound of the general formula (IV) includes sodium dodecylbenzene sulfonate, sodium hexadecylbenzene sulfonate and sodium octadecylbenzene sulfonate. The compound of the general formula (V) includes N-methylaniline, aniline, p-methoxyaniline, N-ethylaniline, N,N'-diphenyl, p-phenylene diamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylene diamine, N-phenyl-N'-isopropyl-p-phenylene diamine and dicyclohexylamine. The compound of the general formula (VI) includes imidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-undecyl-2-stearylimidazole and 1-cyanoethyl-2-methylimidazole. Furthermore, the compound represented by the formula (VII) is 1,4-diazabicyclo [2,2,2] octane, and the compound represented by the formula (VIII) is piperazine. When the amount of 2,5-dimercapto-1,3,4-thiadiazole compounded is less than 0.1 part by weight or the amount of the compounds represented by the formulae (I)-(VIII) compounded is less than 0.2 part by weight, the synergistic effect of improving heat generation of the rubber composition cannot be expected, while when the amount of 2,5-dimercapto-1,3,4-thiadiazole exceeds 5 parts by weight or the amount of the compound of the formulae (I)-(VIII) exceeds 10 parts by weight, the effect of improving heat generation of the rubber composition is not recognized and also the mechanical properties of the rubber composition are undesirably lower. Preferably, 2,5-dimercapto-1,3,4-thiadiazole is compounded in an amount of 0.2-1.5 parts by weight, and at least one compound among the compounds represented by the formulae (I)-(VIII) is compounded in an amount of 0.4-4 parts by weight. In the mixing of these compounds with the above polymer, they may be mixed separately, or a salt of 2,5-dimercapto-1,3,4-thiadiazole and at least one compound selected from the formulae (I)-(VIII) is previously synthesized and may be mixed with the polymer. As the reinforcing filler used in the rubber composition according to the invention, carbon black is preferably used. The compounding amount is 20-100 parts by weight. When the amount is less than 20 parts by weight, the reinforcing property of the rubber composition is poor, while when it exceeds 100 parts by weight, not only the heat generation but also the wear resistance are considerably degraded. In the rubber composition according to the invention, additives usually used in the rubber industry such as softening agent, antioxidant, vulcanization accelerator, accelerator promoter, and vulcanizing agent may properly be added, if necessary, in addition to the above reinforcing filler and the heat generation improver. The invention will be described in detail with reference to the following Synthesis Examples, Examples of the invention, and Comparative examples. Synthesis Example 1 (Synthesis of polymers A-C)Into a reaction vessel of 5 ℓ capacity were charged 2500 g of cyclohexane, 375 g of 1,3-butadiene, 125 g of styrene, 17.5 g of tetrahydrofuran and 5.0 mmol of n-butyllithium, and then polymerization was started at 15°C and conducted for 35 minutes. The temperature at the completion of polymerization was 95°C. After the completion of the polymerization, a given amount of a tin compound shown in the following Table 1 was added to conduct reaction for 15 minutes. Then, the thus obtained polymer solution was added with 2.5 g of 2,6-di-t-butyl-p-cresol and subjected to steam stripping to solidify the resulting polymer, which was dried on a hot roll at 100°C for 15 minutes. The microstructure of the thus obtained three polymers A-C had a cis/trans/vinyl ratio of 19/31/50. Tin compound Addition amount (mmoℓ) Polymer ATetrachlorotin1.2 Polymer BTributylmonochlorotin5.0 Polymer CButyl tin trisstearate5.0 Synthesis Example 2Into a flask of 100 mℓ capacity were charged 1.50 g of 2,5-dimercapto-1.3.4-thiadiazole, 3.10 g of dimethyldodecylamine and 50 mℓ of tetrahydrofuran as a solvent, which were reacted at room temperature for 2 hours. After the completion of the reaction, the solvent was distilled off to obtain a salt of 2,5-dimercapto-1,3,4-thiadiazole·dimethyldodecylamine as a target compound. Synthesis Example 3Into a flask of 100 mℓ capacity were charged 1.50 g of 2,5-dimercapto-1,3,4-thiadiazole, 6.10g of dimethyldodecylamine and 50 mℓ of tetrahydrofuran as a solvent, which were reacted at room temperature for 2 hours. After the completion of the reaction, the solvent was distilled off to obtain a salt of 2,5-dimercapto-1,3,4-thiadiazole·2-dimethyldodecylamine as a target compound. Examples 1-14, Comparative Examples 1-14Each of various rubber compositions having a compounding ratio shown in Table 2 was kneaded by means of a Banbury mixer and then vulcanized to prepare a vulcanized rubber sample. The value of tan δ was measured by using a viscoelastic measuring testing machine made by Rheometrics Corporation under conditions of a dynamic strain of 1% and 50°C. The measured results are shown in Table 2. As shown in Table 2, when 2,5-dimercapto-1,3,4-thiadiazole is added to each of SBR 1500, Tafuden 2000 and BR01, an improving effect of low heat generation of not less than 20% is developed, while the effect in respect of the polymer of Synthesis Example 1 is only 12%. This is considered to be due to the fact that the rubber composition containing the polymer of Synthesis Example 1 is fairly low in tan δ even in the case of compounding no 2,5-dimercapto-1,3,4-thiadiazole so that it is difficult to further lower the heat generation. However, when 2,5-dimercapto-1,3,4-thiadiazole is used together with dimethyldodecylamine, Anon BL, NewRex powder T, Noclac 6C, imidazole, 1,4-diazabicycl[2,2,2] octane, piperadine, p-methoxyaniline, dicyclohexylamine or Diapo T powder, it is found to obtain a considerably improved effect. Furthermore, it has been confirmed that a similar effect of low heat generation is developed by separately adding these compounds, or by previously synthesizing a salt (Synthesis Examples 2, 3) and adding it in the compounding with the rubber composition. On the other hand, the effect of improving heat generation is hardly obtained when adding the compounds of the general formulae (I)-(VIII) alone. Furthermore, it has been found that the synergistic effect obtained by 2,5-dimercapto-1,3,4-thiadiazole and dimethyldodecylamine or the like is developed only in the use of the tin-modified polymer (polymers A-C of Synthesis Example 1). As seen from the Examples and Comparative Examples, the rubber compositions obtained by compounding a particular low heat-generation improving agent being a combination of 2,5-dimercapto-1,3,4-thiadiazole and a particular compound selected from the compounds of formulae (I)-(VIII) with a particular tin-modified polymer develop the effect of improving low heat-generation, which has not been attained in the conventional low heat-generation rubber composition, so that they may be widely utilized as a low heat-generation rubber, for example in the field of all rubber articles such as tires, conveyor belts, and hoses.
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A low heat-generation rubber composition comprising 20-100 parts by weight of a reinforcing filler, 0.1-5 parts by weight of 2,5-dimercapto-1,3,4-thiadiazole and 0.2-10 parts by weight of at least one compound selected from compounds of the following formulae (I) - (VIII): (wherein R₃, R₆, R₉, R₁₁ in (I)-(VIII) are alkyl group having a carbon number of 8-18 or aryl group, R₄, R₅, R₇, R₈, R₁₀ are alkyl group having a carbon number of 1-2, R₁₂ is aryl group or cyclohexyl group, R₁₃ is alkyl group having a carbon number of 1-6, cyclohexyl group or hydrogen atom, R₁₄, R₁₅ are alkyl groups having a carbon number of 1-18, benzyl group or hydrogen atom, and each of m and n is an integer of 1-3) based on 100 parts by weight of a polymer obtained by reacting a conjugated diene series polymer containing an alkali metal in its polymer terminal, which is obtained by polymerizing or copolymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent in the presence of an organic alkali metal as a polymerization initiator, with a tin compound represented by the following general formula:Sn(R₁)pX4-p or (wherein R₁ and R₂ are substituents selected from the group consisting of alkyl group, alkenyl group, cycloalkyl group and aryl group and are the same or different, X is a halogen atom and p is an integer of 0-3) alone or a rubber blend of not less than 30 parts by weight of this polymer and another diene series polymer. A rubber composition as claimed in claim 1, characterized in that 2,5-dimercapto-1,3,4-thiadiazole is compounded in an amount of 0.2-1.5 parts by weight. A rubber composition as claimed in claim 1 or 2, characterized in that at least one compound among the compounds represented by the formulae (I)-(VIII) is compounded in an amount of 0.4-4 parts by weight.
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BRIDGESTONE CORP; BRIDGESTONE CORPORATION
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HAMADA TATSUROU; HATAKEYAMA KAZUYA; HIRATA YASUSHI; HOUJYOU MASAHIRO; TAKIMURA MAMORU; HAMADA, TATSUROU; HATAKEYAMA, KAZUYA; HIRATA, YASUSHI; HOUJYOU, MASAHIRO; TAKIMURA, MAMORU
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EP-0489923-B1
| 489,923 |
EP
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B1
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EN
| 19,950,823 | 1,992 | 20,100,220 |
new
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B60R22
| null |
B60R22
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B60R 22/42
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RETRACTOR FOR SEAT BELT
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A retractor for a seat belt device mounted on a vehicle and, in particular, to a seat belt retractor for locking the seat belt to prevent it from being pulled out in case of emergency at collision of vehicles. When the vehicle encounters an emergency, a second clamping member (136) tightly clamps a seat belt (18) between it and a first clamping member (120) and, at this time, is subjected to a great deal of external force. In this state, a sleeve (170) is resiliently deformed, a supporting hole (138) comes into direct contact with a shaft (134), and the second clamping member (136) is supported directly by the shaft (134). A sleeve or bush (170) made of resin is fitted over said shaft (134) and an extremely slight gap is formed between the inner peripheral surface of the supporting hole (138) and the outer peripheral surface of the shaft (134) during non-emergency time of the vehicle, whereby abnormal noise which may be generated by contact of the shaft (134) with the clamping member (136) is completely prevented.
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TECHNICAL FIELDThe present invention relates to a retractor for use in a seat belt system mounted in an automotive vehicle and particularly, to a seat belt retractor lockable to prevent extraction of a seat belt in emergency situations such as a vehicle collision. BACKGROUND ARTConventionally, a seat belt system is mounted in a vehicle seat to protect an occupant in emergency situations such as a vehicle collision. The seat belt system includes a retractor attached to a vehicle rigid member and locked to take up a seat belt. This retractor is adapted to permit extraction of the seat belt when the seat belt is fastened around the occupant. The seat belt can also be extracted in a nonemergency situation so as not to restrain the occupant. In a vehicle collision or other emergency situations, the resultant impact or acceleration is sensed to cause a reel lock mechanism to lock a reel around which the seat belt is wound. Locking of the reel enables the seat belt to restrain the occupant or prevent sudden movement of the occupant to protect the occupant. The reel lock mechanism is able to stop rotation of the reel per se. However, if the seat belt is loosely wound around the reel, then further extraction of the seat belt may result, even if the reel is firmly locked. To prevent this, there has previously been proposed a seat belt retractor as shown in Figs. 5 and 6. Fig. 6 is a sectional view taken on the line VI-VI in Fig. 5. In Fig. 5, a seat belt retractor 201 comprises a frame 205 including a pair of side walls 202, 203 and a rear wall 204 extending between the side walls 202, 203, a pendulum 206 oscillatable when excessive impacts are applied, a ratchet 208 connected to a reel (not shown) around which a seat belt 207 is wound, a link 210 including a pawl 209 engageable with teeth of the ratchet 208 and moved up as the ratchet 208 is rotated, a first gripping member 211 mounted to the rear wall 204 of the frame 205, and a shaft 212 extending between the side walls 202, 203, and a second gripping member 214 including a support hole 213 (Fig. 6) at its one end to receive the shaft 212. As the link 210 is moved up, the free end of the second gripping member 214 is moved toward the first gripping member 211. The seat belt 207 is then firmly sandwiched between the first gripping member 211 and the second gripping member 214 to prevent extraction of the seat belt 207 from the reel. The shaft 212, the second gripping member 214 and the frame 205 of the seat belt retractor 201 are all made of metal of high strength. When a vehicle is moved or vibrated, the shaft 212 is brought into metal-to-metal contact with the support hole 213 of the second gripping member 214 to cause undesirable sound. This sound makes a vehicle occupant not only feel uncomfortable, but also suspect that there may be some fault. In the prior art, the second gripping member 214 may also be brought into metal-to-metal contact with the side walls 202, 203 of the frame 205 to cause similar undesirable sound. DISCLOSURE OF THE INVENTIONAccording to the present invention, there is provided a seat belt retractor comprising a frame including a pair of opposite side walls and a rear wall extending between the side walls; a seat belt take-up reel situated between the side walls of the frame; a first gripping member mounted on the rear wall of the frame; a shaft extending between the side walls of the frame; a second gripping member having a support hole at one side and a pusher at a side opposite to the support hole, said second gripping member being situated between the side walls and rotatably held by the shaft extending through the support hole; lock actuating means for moving the second gripping member to a locking position upon detection of a predetermined deceleration of the vehicle; and a sleeve having a cylindrical portion and a flange said second gripping member being supported by the shaft through the sleeve when the predetermined deceleration of the vehicle is not detected, said seat belt retractor being characterized in that said sleeve is made of synthetic resin, said sleeve being resiliently deformable to allow the second gripping member to directly contact the shaft when the predetermined deceleration is detected so that the seat belt is securely retained between the first gripping member and the pusher. In the seat belt retractor according to the present invention, the sleeve made of synthetic resin is disposed between the second gripping member and the second gripping member support shaft. This prevents metal-to-metal contact between these members and thus, undesirable sound. In the present invention, the next seat belt is sandwiched between the first gripping member and the second gripping member to prevent extraction of the seat belt in emergency situations such as a vehicle collision. With the seat belt retractor of the present invention, the sleeve includes a flange. This flange is preferably disposed between the second gripping member and the side walls of the frame. This arrangement prevents metal-to-metal contact between the second gripping member and the side walls of the frame and thus, undesirable sound. Preferably, the seat belt retractor of the present invention includes a reel lock mechanism adapted to lock the reel in emergency situations. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a perspective view of a seat belt retractor according to one embodiment of the present invention; Fig. 2 is an exploded view, in perspective, of a reel lock mechanism; Fig. 3 is a vertical sectional view of the seat belt retractor taken on the line III-III in Fig. 1; Fig. 4 is a sectional view taken on the line IV-IV in Fig. 1; Fig. 5 is a perspective view of a conventional seat belt retractor; and Fig. 6 is a sectional view taken on the line IV-IV in Fig. 5. BEST MODE FOR CARRYING OUT THE INVENTIONOne embodiment of the present invention will now be described with reference to the drawings. Fig. 1 is a perspective view of a seat belt retractor according to one embodiment of the present invention (with a soundproof cover removed). Fig. 2 is an exploded perspective view of a reel lock mechanism. Fig. 3 is a vertical sectional view of the seat belt retractor taken on the line III-III in Fig. 1. Fig. 4 is a sectional view taken on the line IV-IV in Fig. 1. A frame 10 includes a pair of parallel side walls 12, 14, and a rear wall 16 extending between the side walls 12, 14. A reel 20 is mounted to the lower part of the frame 10 to take up a seat belt 18. A lock mechanism is also mounted to the lower part of the frame 10 to lock the reel 20 in emergency situations. A belt lock mechanism 24 is mounted to the upper part of the frame 10 to prevent extraction of the seat belt from the reel 20 in emergency situations. The reel lock mechanism 22 will now be described with reference mainly to Fig. 2. Two support openings 26, 28 are coaxially formed in the side walls 12, 14 to receive a reel shaft 30 through bushings 32 made of synthetic resin. The reel shaft 30 is rotatable about its own axis. The reel 20 is fit around the reel shaft 30. A return spring 34 has a central end connected to one end of the shaft 30. The outer end of the return spring 34 is secured to the side wall 12 through a cover 36. When the seat belt 18 is extracted, the reel 20 is rotated to allow the return spring 34 to store energy. When the seat belt is released, the reel 20 is rotated under the action of the return spring 34 to allow for automatic winding of the seat belt 18 on the reel 20. The reel 20 and the reel shaft 30 are rotated in the direction of the arrow A₁ when the seat belt 18 is extracted. The reel lock mechanism 22 is mounted to the outer surface of the side wall 14. The reel lock mechanism 22 includes a ratchet wheel 38 integral with the other end of the reel shaft 30. A pin 40 extends outwardly from the ratchet wheel 38 in a coaxial relation to the shaft 30. A tie plate 42 has an opening 45 to receive the pin 40. A lock ring 44 has a central opening 48 in which the pin 40 is loosely fit. 50 is an arcuate spring element 50 having one end engaged with an engagement hole (spring hanger) which is formed substantially centrally in the tie plate 42, and the other end engaged with an engagement hole (spring hanger) 54 of the lock ring 44. The lock ring 44 has internal teeth 56. The spring element 50 extending between the spring hanger 54 of the lock ring 44 and the spring hanger 52 of the tie plate 42 provides a biasing force to rotate the lock ring 44 in the direction of the arrow A₂. A control lever 58 has a base end pivotally connected to the side wall 14 of the frame 10 by a pivot pin 60. The other, free end of the control lever 58 is engageable with the ratchet wheel 38. A pin 62 extends from one side of the control lever 58. The pivot pin 60 extends through an opening 64 which is formed in the front end of the tie plate 42. The lock ring 44 has a pair of diametrically opposite integral tabs 66 and 68. The tab 66 is adapted to rotate the control lever 58. The tab 68 is adapted to operate the belt lock mechanism 24. The tab 66 of the lock ring 44 has an elongated hole 70 to receive the pin 62 of the control lever 58. A hook retainer 72 is secured to the pin 40 of the shaft 30 which extends through the central opening 48 of the lock ring 44. Diametrically opposite projections 76 and 78 extend from the peripheral edge of the hook retainer 72 to support a hook 74. The hook 74 has two openings 80 and 82 to receive the projections 76 and 78. This allows the hook 74 to move to and from the hook retainer 72 along the line extending between the projections 76 and 78 (shown by the arrows B₁ and B₂). A compression coil spring 84 is disposed between the hook retainer 72 and the hook 74 to urge the hook 74 in the direction of the arrow B₁. A pawl 86 extends from the outer peripheral edge of the hook 74 to engage with the internal teeth of the lock ring 44. A connecting pin 88 extends from the outer side of the hook 74. The hook 74 is normally urged in the direction of the arrow B₁ under the influence of the compression coil spring 84 or shifted to the left in Fig. 2. As a result, the pawl 86 is separated from the internal teeth 56. A frictional lock member 90 is substantially in the form of a ring and has an opening 92 adjacent its outer peripheral edge to receive the connecting pin 88. A flywheel 96 is fit over the frictional lock member 90 and includes a ratchet 94. The flywheel 96 has a central opening in which the pin 40 of the shaft 30 is loosely fit. The flywheel 96 is in the form of a short cylinder to receive the frictional lock member 90. An arcuate spring 98 is fit on the outer periphery of the friction lock member 90 and slidably urged against the inner periphery of the flywheel 96. The flywheel 96 is slid around the frictional lock member 90 while friction is applied to the flywheel 96. 99 is a rivet fit into a bore 40A of the pin 40 to hold the flywheel 96 in position. As shown in Fig. 1, an actuator 100 is mounted to the side wall 14 of the frame 10 and generally includes a case 104 fixed to the side wall 14, a barrel shaped operating element 106 loosely fit within the case 104, an operating lever 110 including a protrusion 108 in contact with the upper surface of the operating element 106, and a support 112 adapted to pivotally support the proximal end of the operating lever 110. As shown in Fig. 1, a cover 114 surrounds the reel lock mechanism assembled as shown in Fig. 4. With the retractor of the seat belt thus constructed, the operating lever 110 is disengaged from the flywheel 96 when the seat belt 18 is extracted by the occupant. The reel 20 and the shaft 30 are free to rotate to allow extraction of the seat belt 18. If the seat belt 18 is released, then the shaft 30 is rotated under the influence of the return spring 34 within the cover 36 so as to wind the seat belt 18 around the reel 20. If there is a substantial change in the speed of a vehicle, for example, in the case of a collision, the actuator 100 is rendered operative to inhibit extraction of the seat belt 18. That is, when substantial acceleration is applied to the actuator 100, then the operating barrel 106 is inclined to cause the protrusion 108 to raise the operating lever 110. The distal end of the operating lever 110 is then brought into engagement with the ratchet 94 to stop the flywheel 96. Stoppage of the flywheel 96 results in corresponding stoppage of the frictional lock member 90. On the other hand, the seat belt 18 tends to be extracted during crash to cause the reel shaft 30 to rotate in the direction of the arrow A₁. As the reel shaft 30 rotates, the hook retainer 72 and the hook 74 are caused to rotate in the direction of the arrow A₁. However, the hook 74 can not be rotated since the frictional lock member 90 is prevented from rotating as a result of engagement with the pin 88. Under the circumstances, the hook 74 is slid in the direction of the arrow B₂ a distance corresponding to the rotation of the hook retainer 74 in the direction of the arrow A₁. The pawl 86 is then brought into engagement with the internal teeth 56 of the lock ring 44. Upon rotation of the reel shaft 30, the lock ring 44 is rotated in the direction of the arrow A₁ to allow the the tab 66 to rotate the control lever 58 in the direction of the arrow C₁ as the pin 62 is engaged with the elongate hole 70. The free end of the control lever 58 is then brought into engagement with the ratchet wheel 38 of the reel shaft 30 to firmly lock the reel shaft 30 and the reel 20. The construction of the belt lock mechanism 24 will next be described with reference to Figs. 1, 3, and 4. A first gripping member 120 is attached to the rear wall 16 of the frame 10 and includes a holder 122 secured to the rear wall 16, a receiver 124 held by the holder 122 and vertically moved along the rear wall 16, and a spring 126 disposed to urge the receiver in a downward direction. The receiver 124 has a rugged front surface. The holder 122 has a guide or slit 127 at its upper end to guide the seat belt 18. A pair of openings 130 and 132 are coaxially formed in the side walls 12 and 14 of the frame 10. A shaft 134 extends between the openings 130 and 132. A second gripping member 136 has a support hole 138 through which the shaft 134 extends to rotatably mount the second gripping member 136 to the frame 10. As shown in Fig. 3, a semicylindrical pusher 138 is attached to the free end of the second gripping member 136 and has a rugged surface in a face-to-face relation to the receiver 124. The seat belt 18 extends between the pusher 138 and the receiver 124. A pin 140 (Fig. 3) extends from one side of the second gripping member 136 into an elongate hole 142 which is formed in the side wall 14 of the frame 10. A pivot pin 144 extends from the outer surface of the side wall 14 of the frame 10. A locker arm 146 is pivoted about the pivot pin 144. The locker arm 146 is bent to a L-shape. A recess 148 is formed at one end of the locker arm 146 to engage with the pin 140. A joint 152 is provided at the other end of the locker arm 146. A lever 150 has an upper end pivotally connected to the joint 152. The lever 150 is pivotally connected to the joint 152 of the locker arm 146 so as to rotate by a very small angle. The lower end of the lever 150 overlaps with the tab 68 of the lock ring 44. A pin 154 extends from the lower end of the lever 150 into an elongated hole 156 of the tab 68. A spring 158 extends around the pivot pin 144 and has one end fit into an opening 160 of the side wall 14 of the frame 10 and the other end fit into an opening 162 of the locker arm 146. The spring 158 urges the locker arm 146 in the direction of the arrow G₁. Reference will now be made to the operation of the belt lock mechanism 24 thus far constructed. When the vehicle is in a nonemergency situation, the locker arm 146 is urged in the direction of the arrow G₁ under the action of the spring 158 to press the pin 140 in the same direction. This causes the pusher 138, which is connected to the free end of the second gripping member 136, to separate from the receiver 124 of the first gripping member 120. Under the circumstances, the seat belt 18 is free to pass between the pusher 138 and the receiver 124. In an emergency situation or during crash, the operating element 106 of the actuator 100 is inclined to allow the operating lever 110 to engage with the ratchet 94 of the flywheel 96. The lock ring 44 is then rotated in the direction of the arrow A₁. Thereafter, the seat belt 18 is locked in the following steps. 1. The tab 68 of the lock ring is rotated in the direction of the arrow A₁ to cause the pin 154 to move toward the lower end of the elongated hole 156. That is, the lever 150 is rotated in the direction of the arrow E. 2. Rotation of the lever 150 causes a leading end 150a to engage with the ratchet wheel 38. 3. As the ratchet wheel 38 rotates, the lever 150 is raised. That is, the locker arm 146 is rotated about the pin 144 in the direction of the arrow G₂ to press the pin 140 in the same direction (An elongated hole 70 is shaped so that at this time, the control lever 58 is not yet in engagement with the ratchet wheel 38). 4. As a result, the pusher 138 of the second gripping member 136 is moved toward the receiver 124 of the first gripping member 120 to grip the seat belt 18 therebetween. 5. Once the seat belt 18 is sandwiched between the pusher 138 and the receiver 124, extraction of the seat belt 18 causes the pusher 138 and the receiver 124 to move toward one another so as to strongly grip the seat belt 18 between the pusher 138 and the receiver 124. The seat belt 18 is thus locked and can no longer be extracted. As shown in Fig. 4, a sleeve or bushing 170 is made of synthetic resin and fit around the shaft 134 to leave a slight clearance between the inner peripheral surface of a support hole 138 and the outer peripheral surface of the shaft 134. This prevents metal-to-metal contact between the metallic shaft 134 and the metallic gripping member 136 and thus, undesirable sound which may otherwise occur due to contact of the shaft 134 with the gripping member 136. When the vehicle is in an emergency situation, the second gripping member 136 cooperates with the first gripping member 120 to firmly sandwich the seat belt 18. At this time, substantial force is applied to the second gripping member 136. Under the circumstances, the sleeve 170 is resiliently deformed to cause direct contact between the support hole 138 and the shaft 134. This allows the shaft 134 to directly support the second gripping member 136. The second gripping member 136 can firmly be held in the frame 10 if substantial force is applied thereto. When the external force is released, the sleeve 170 is resiliently returned to its original state to allow the shaft 134 to support the second gripping member 136 again through the sleeve 170. In the illustrated embodiment, the sleeve 170 has a flange 172 located between the second gripping member 136 and the side walls 12, 14 of the frame 10. This also prevents metal-to-metal contact between the second gripping member 136 and the side walls 12, 14 and thus, undesirable sound due thereto. INDUSTRIAL APPLICABILITYThe seat belt retractor of the present invention thus far described prevents metal-to-metal contact between the second gripping member and the shaft which supports the second gripping member and thus, undesirable sound. The present invention also prevents metal-to-metal contact between the second gripping member and the side walls of the frame and thus, undesirable sound due thereto. In the present invention, the seat belt is firmly locked by the belt lock mechanism and the reel lock mechanism to provide a fail-safe mechanism.
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A seat belt retractor comprising: a frame (10) including a pair of opposite side walls (12, 14) and a rear wall (16) extending between the side walls; a seat belt take-up reel (20) situated between the side walls (12, 14) of the frame (10); a first gripping member (120) mounted on the rear wall (16) of the frame; a shaft (134) extending between the side walls of the frame; a second gripping member (136) having a support hole (138) at one side and a pusher (138) at a side opposite to the support hole, said second gripping member being situated between the side walls and rotatably held by the shaft (134) extending through the support hole; lock actuating means for moving the second gripping member to a locking position upon detection of a predetermined deceleration of the vehicle; and a sleeve (170) having a cylindrical portion and a flange (172), said second gripping member being supported by the shaft (134) through the sleeve when the predetermined deceleration of the vehicle is not detected, said seat belt retractor being characterized in that said sleeve (170) is made of synthetic resin, said sleeve being resiliently deformable to allow the second gripping member to directly contact the shaft when the predetermined deceleration is detected so that the seat belt (18) is securely retained between the first gripping member and the pusher. A seat belt retractor according to claim 1, wherein said cylindrical portion of the sleeve (170) has an equal diameter throughout the entire length thereof to stably support the second gripping member. A seat belt retractor according to either claim 1 or claim 2, wherein said second gripping member has a recess having a size corresponding to the flange of the sleeve so that when the sleeve is inserted into the support hole, the flange is situated in the recess while an outer surface of the flange projects outwardly from the outer surface of the second gripping member. A seat belt retractor according to any one preceding claim, further comprising a reel lock mechanism to lock the reel upon detection of the predetermined deceleration.
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TAKATA CORP; TAKATA CORPORATION
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FUJIMURA YOSHIICHI - HIGASHIDE; TANABE MASAHIRO MIYASHI-CHO; FUJIMURA, YOSHIICHI, 452-2, HIGASHIDE HATASHO-CHO; TANABE, MASAHIRO, 930, MIYASHI-CHO
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EP-0489925-B1
| 489,925 |
EP
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B1
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EN
| 19,960,612 | 1,992 | 20,100,220 |
new
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A61K31
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C07D405, C07D403, C07D401, C07D239
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C07D239, C07D401, C07D403
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M07D239:48B1, M07D401:04, M07D403:04, M07D401:14, C07D 239/48, C07D 401/04, C07D 403/04, M07D401:14+239B+217+207, M07D401:14+239B+215+207, M07D401:14+239B+211+207, M07D403:04+239B+207, C07D 401/14, M07D403:04+239B+209C, M07D401:04+239B+211
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PYRIMIDINE COMPOUND AND PHARMACEUTICALLY ACCEPTABLE SALT THEREOF
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A pyrimidine compound represented by general formula (I), pharmaceutically acceptable salts thereof, and a drug containing the same for treating neural diseases, wherein X represents substituted or cyclic amino and Y represents substituted amino or substituted carbonyl. These compounds have activities of promoting the growth of nerve cells and the formation and extension of neurites, so that they are useful in treating various neural diseases.
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Field of the Invention:This invention relates to novel pyrimidines or their pharmaceutically acceptable salts thereof, and novel therapeutic agents for neurological diseases of the peripheral and central nervous systems of animals containing the above compounds as active ingredients. Prior Art:Japanese Patent Publication No. 23,394/1971 discloses that aminopyrimidines represented by the following formula wherein A represents an alkylene group having up to 16 carbon atoms, or a lower alkylene group substituted by an amino group or C₂₋₅ acylamino group, M represents H, Na, K, NH₄, Mg, Ca or an organic basic ammoniun salt, and n is a value equal to the atomic valency of M, have interesting therapeutic activity, particularly as an anti-melanchoric agent and psychoanaleptic agent in the filed of psychosis. Japanese Laid-Open Patent Publication No. 22044/1976 discloses that dichloro-lower aliphatic carboxylic acid salts of 2-isopropylaminopyrimidine, such as 2-isopropyl-aminopyrimidine dicloroacetate, are useful as a therapeutic agent for a neurological disease. Japanese Laid-Open Patent Publication No. 100477/1977 (Patent Publication No. 28548/1984) discloses that 2-isopropylaminopyrimidine phosphate is useful as a therapeutic agent for a neurological disease. Japanese Laid-Open Patent Publication No. 157575/1979 discloses a process for producing 2-chloropyrimidine in a high yield. A working example in this patent publication describes the preparation of 2-chloropyrimidine in a yield of 69%. Japanese Laid-Open Patent Publication No. 393/1980 discloses a process for producing 2-isopropylamino-pyrimidine in a high yield. A working example of this patent publication describes the preparation of 2-isopropylaminopyrimidine in a yield of 60%. Japanese Laid-Open Patent Publication No. 122768/1980 discloses that a hydroxy derivative of 2-isopropylaminopyrimidine represented by the following formula wherein A⁴, A⁵ and A⁶ each represent H or OH, and at least one of them represents OH, is useful in the field of nerve regeneration and for treatment of myodystrophy. Japanese Laid-Open Patent Publication No. 145670/1980 discloses that 2-isopropylaminohalogenopyrimidines represented by the following formula wherein A4', A5' and A6' each represent H or a halogen atom, and at least one of them is a halogen atom, are useful for treatment of various neurological diseases and myodystrophy. Japanese Laid-Open Patent Publication No. 145,671/1980 discloses a process for producing a hydroxy derivative of 2-isopropylaminopyrimidine. Japanese Laid-Open Patent Publication No. 151,571/1980 discloses that 2-isopropylamino-5-halogenopyrimidines are interesting in the treatment of neurological diseases. Japanese Laid-Open Patent Publication No. 10177/1981 discloses a process for producing 2-isopropylaminopyrimidine substantially in a quantitative yield by aminolyzing 2-methylsulfornylpyrimidine with isopropylamine. Japanese Laid-Open Patent Publication No. 26880/1981 discloses a process for producing 2-isopropylaminopyrimidine which comprises reacting bis (isopropylguanidine) sulfate with 1,1,3,3-tetraethoxypropane. Japanese Laid-Open Patent Publication No. 90,013/1981 describes a therapeutic agent for myodystropy, myopathy, muscle rigidity and/or dysfunction of neuro-musclar transmission comprising substituted derivative of pyrimidine or its therapeutically acceptable salt of its metabolite as an active ingredient. However, it merely discloses various salts such as an or 2-isopropylaminopyrimidine orthophosphate as an active compound. Japanese Laid-Open Patent Publication No. 65873/1986 discloses that 2-piperazinopyrimidine derivatives of the following formula wherein R¹ is H or aralkyl, and Y is a divalent organic group defined in the claim of this patent publication are useful as a herbicide for paddies and upland farms. The present inventors previously provided a novel therapeutic agent for neurological diseases comprising a specified 2-piperazinopyrimidine derivative or its pharmaceutically acceptable salt (International Laid-Open No. WO87/04928, Japanese Patent Application No. 41729/1989, Japanese Patent Application No. 334759/1989). Problems to be solved by the invention:It is an object of this invention to provide novel pyrimidines and their pharmaceutically acceptable salts. Another object of this invention is to provide therapeutic agents for neurological diseases comprising the above novel compounds. Another object of this invention is to provide a novel therapeutic agent for neurological diseases having the effect of regeneration and repairing nerve cells. Another object of this invention is to provide a novel therapeutic agent for neurological diseases which can be applied to disorders of peripheral nerves and spinal injuries. Another object of this invention is to provide a novel therapeutic agent for neurological diseases which can be applied to diseases of central nerves which are different from psycosis and in which abnormality, in the operating system or the metabolic system of chemical transmitters is regarded to be primarily involved. Another object of this invention is to provide a novel therapeutic agent for cerebral diseases which has the effect of improving and restoring learning and memory. Another object of this invention is to provide a novel therapeutic agent for neurological diseases or cerebral diseases, which comprises a comprehensively excellent and useful compound having pharmacological actions suitable for treatment of neurological diseases or cerebral diseases with little side effects such as liver disorder. Still other objects of this invention along with its advantages will become apparent from the following description. Means for solving the Problem:The present invention provides a pyrimidine compound represented by the following formula (I) {wherein X is selected from the group consisting of; (wherein R¹, R1' may be the same or different and represents a hydrogen atom, a lower alkyl group, a benzyl group, a phenyl group or a lower alkoxycarbonyl group), (wherein R2' and R3' represents a lower alkyl group) or (wherein R4' is a hydrogen atom, a lower alkyl group, a phenyl group or a benzyl group) and Y represents [wherein R² is a hydrogen atom or a lower alkyl group and R³ is a lower acyl group, (wherein R⁴ is a hydrogen atom, or a trifluoromethyl group, a hydroxyl group, a cyano group, a formyl group, a lower acyl group, a lower alkoxycarbonyl group, or a fluorosulfonyl group), (wherein R⁵ is a hydrogen atom, a lower alkyl group or a phenyl group), ;provided that when Y is and R³ is a lower acyl group or X is selected from the group consisting of; or their pharmaceutically acceptable salts. In addition, the present invention provides therapeutic agents for neurological diseases containing the compounds of the formula (I) or their pharmaceutically acceptable salts as active ingredients. The compounds of the above formula (I) of the present invention may be produced by methods known in the art, specifically the methods described in Japanese Patent Publication No. 140568/1986 and No. 87627/1986, or by treating the intermediates obtained by the methods described above by methods known in the art (e.g., reductive elimination of a protecting group). The examples 1 -3 described below will illustrate a process for producing each compound in detail. For example, when compounds of the formula (I) wherein Y is - NR²R³ and R² is a lower alkyl group are attempted to be produced, the compounds can be produced by the following Reaction Sheme 1. The source of the compound (II) of the Reaction Sheme 1 is produced using a starting material, according to the method described in J. Chem. Soc., 1965, p755 - 761. The reaction of the Reaction Sheme 1 is preferably carried out in solvents such as toluene, dioxane, pyridine or water at 20°C-150°C and, if necessary, in the presence of basic compounds. Suitable basic compounds include organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine and inorganic bases such as sodium carbonate and potassium carbonate. Compounds of the formula (I) wherein X is and Y is may be produced by reacting, for example, carbonyl chlorides having a structural formula with compounds having the following structural formula which are generated from a starting material, 2, 4-dichloropyrimidine. Compounds of the formula (I) wherein Y is may be produced by the following Reaction Scheme2. The reaction to synthesize the compounds (IV) in the Reaction Scheme 2 may be preferably carried out in solvents such as isopropanol, n-butanol, n-pentanol, isopentanol at 60 - 200 °C and, if necessary, in the presence of basic compounds. Suitable basic compounds include organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine and inorganic bases such as sodium carbonate and potassium carbonate. The reaction to synthesize the compound(V) may be preferably carried out in the absence or presence of solvents, e.g., methylene chloride, chloroform, ethylenedichloride and toluene at 0 °C- 100 °C. A process of producing the compounds (I) and salts thereof of the present invention may be described in the Examples in detail. The typical compounds (I) and salts thereof of the present invention are listed in Table 1. In the Table 1, the abbreviation listed under a salts column, the right side of the Table, represents the following : -: free compounds PTSOH: p-toluenesulfonate MALEATE: Maleate Investigations of the present inventors show that the compounds of formula (I) provided by this invention have been found to be useful as therapeutic agents for neurological diseases. The compounds of formula (I) are used normally in the form of a pharmaceutical composition, and administered through various routes, for example oral, subcutaneous, intramuscular, intravenous, intrarhinal, skin permeation and intrarectal routes. The present invention also includes a pharmaceutical composition comprising a pharmaceutically acceptable carrier and a compound of general formula (I) or its pharmaceutically acceptable salt as an active ingredient. The pharmaceutically acceptable salt includes, for example, acid addition salts and quaternary ammonium (or amine) salts. Examples of the pharmaceutically acceptable salts of the compounds (I) include salts formed from acids capable of forming pharmaceutically acceptable non-toxic acid-addition salts containing anions, such as hydrochlorides, hydrobromides, sulfates, bisulfites, phosphates, acid phosphates, acetates, maleates, fumarates, succinates, lactates, tartrates, benzoates, citrates, gluconates, glycarates, methanesulfonates, p-toluenesulfonates and naphthalanesulfonates or their hydrates, and quaternary ammonium (or amine) salts or their hydrates. The composition of this invention may be formulated into tablets, capsules, powders, granules, troches, cachet wafer capsules, elixirs, emulsions, solutions, syrups, suspensions, aerosols, ointments, aseptic injectable, molded cataplasmas, soft and hard gelatin capsules, suppositories, and aseptic packed powders. Examples of the pharmaceutically acceptable carrier include lactose, glucose, sucrose, sorbitol, mannitol, corn starch, crystalline cellulose, gum arabic calcium phosphate, alginates, calcium silicate, microcrystalline cellulos, polyvinyl pyrrolidone, tragacanth gum, gelatin, syrup, methyl cellulose, carboxymethyl cellulose, methylhydroxybenzoic acid esters, propylhydroxybenzoic acid esters, talc, magnesium stearates, inert polymers, water and mineral oils. Both solid and liquid compositions may contain the aforesaid fillers, binders, lubricants, wetting agents, disintegrants, emulsifying agents, suspending agents, preservatives, sweetening agents and flavoring agents. The composition of this invention may be formulated such that after administration to a patient, the active compound is released rapidly, continuously or slowly. In the case of oral administration, the compound of formula (I) is mixed with a carrier or diluent and formed into tablets, capsules, etc. In the case of parenteral administration, the active ingredient is dissolved in a 10% aqueous solution of glucose, isotonic salt water, sterlized water or a like liquid, and enclosed in vials or ampoules for intravenous instillation or injection or intramuscular injection. Advantageously, a dissolution aid, a local anesthetic agent, a preservative and a buffer may also be included into the medium . To increase stability, it is possible to lyophilize the present composition after introduction into a vial or ampoule. Another example of parenteral administration is the administration of the pharmaceutical composition through the skin as an ointment or a cataplasm. In this case, a molded cataplasm or a tape is advantageous. The composition of this invention contains 0.1 to 2000 mg, more generally 0.5 to 1000 mg, of the active component for each unit dosage form. The compound of formula (I) is effective over a wide dosage range. For example, the amount of the compound administered for one day usually falls within the range of 0.03 mg/kg to 100 mg/kg. The amount of the compound to be actually administered is determined by a physician depending, for example, upon the type of the compound administered, and the age, body weight, reaction, condition, etc. of the patient and the administration route. The above dosage range, therefore, does not limit the scope of the invention. The suitable number of administrations is 1 to 6, usually 1 to 4, daily. The compound of formula (I) by itself is an effective therapeutic agent for disorders of the periphral nervous system and the central nervous system. If required, it may be administered in combination with at least one other equally effective drug. Examples of such an additional drug are gangliosides, mecobalamin and isaxonine. The formulations of the compounds (I) in accordance with this invention and their biological activities will be illustrated in detail by a series of Examples given below. It should be understood however that they do not limit the scope of the invention. Each of the following examples showing the composition of the invention uses one of the compounds described hereinabove or one of other pharmaceutically active compounds encompassed within general formula (I) ExampleExample 14-(N-methyl-4-trifluoromethyl benzoylamino)-2-(4-phenylpiperidino) pyrimidine (compound No. 108)10 ml of tetrahydrofuran solution containing 1.0g of 4-trifluoromethylbenzoylchloride (4.8 mM) was added to 30 ml of tetrahydrofuran solution containing 1.1g of 4-methylamino-2-(4-phenylperidino) pyrimidine (4mM) and 2 ml of triethylamine over a period of 30 minutes at room temperature. The mixture was stirred for 12 hours. Water and dichloromethane were added to the reaction mixture. The organic layer was separated, dried with sodium sulfate anhydride and concentrated under reduced pressure. The concentrate was purified by a solica gel chromatography to give a desired product, an oil-like substance (1.6g, yield 83%). ¹H-NMR spectrum (deuterochloroform, δppm) 1.2-1.9 (4H, m), 2.5-2.9 (3H, m), 3.52 (3H, s), 4.48 (2H, br. d, J=12Hz), 6.14 (1H, d, J=7Hz), 7.1-7.4 (5H, m), 7.56 (4H, s), 8.12 (1H, d, J=7Hz) Compounds produced by the same method as described above and their physical properties are listed in Table 2. Comp. No. Yield (%) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 100863.12 (2H, t, J=8Hz), 3.63 (3H, s), 4.06 (2H, t, J=8Hz), 6.34 (1H, d, J=7Hz), 6.8-7.6 (9H, m), 8.10(1H, d, J=7Hz) 116801.1-1.9 (4H, m), 2.5-2.9 (3H, m), 3.52 (3H, s), 3.83 (3H, s), 4.48 (2H, br. d, J=12Hz), 6.14 (1H, d, J=7Hz), 7.0-7.4 (5H, m), 7.46 (2H, d, J=8Hz), 7.98 (2H, d, J=8Hz), 8.08 (1H, d, J=7Hz) 124761.2-2.0 (4H, m), 2.5-2.9 (3H, m), 3.50 (3H, s), 4.46 (2H, br. d, J=12Hz), 6.14 (1H, d, J=7Hz), 7.0-7.4 (5H, m), 7.4-7.7 (4H, m), 8.12 (1H, d, J=7Hz) 132681.2-1.9 (4H, m), 2.4-2.9 (3H, m), 3.52 (3H, s), 4.38 (2H, br. d, J=12Hz), 6.10 (1H, d, J=7Hz), 7.0-7.4 (5H, m), 7.62 (2H, d, J=8Hz), 7.94 (2H, d, J=8Hz), 8.16 (1H, d, J=7Hz) Comp. No. Yield (%) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 140711.1-1.7 (4H, m), 2.4-2.8 (3H, m), 3.55 (3H, s), 4.44 (2H, br. d, J=12Hz), 6.06 (1H, d, J=7Hz), 6.9-7.9 (12H, m), 7.98 (1H, d, J=7Hz) 148631.1-1.9 (4H, m), 2.5-3.0 (3H, m), 3.54 (3H, s), 4.52 (2H, br. d, J=12Hz), 6.18 (1H, d, J=7Hz), 7.0-7.4 (5H, m), 7.58 (2H, d, J=8Hz), 7.84 (2H, d, J=8Hz), 8.13 (1H, d, J=7Hz), 9.98 (1H, s) 156471.5-3.2 (20H, m), 3.24 (3H, s), 4.92 (2H, m), 6.35 (1H, d, J=7Hz), 7.23 (5H, m), 8.23 (1H, d, J=7Hz) 164451.1-2.9 (7H, m), 3.57 (3H, s), 4.40 (2H, m), 6.1-8.7 (10H, m) 172801.3-2.0 (m, 4H), 2.02 (s, 3H), 2.5-3.0 (m, 3H), 3.02 (s, 3H), 4.6-5.0 (m, 2H), 5.92 (d, 1H, J=7Hz), 7.0-7.4 (m, 9H), 8.04 (d, 1H, J=7Hz) Comp. No. Yield (%) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 180403.68 (3H, s), 4.10 (2H, s), 4.58 (2H, s), 6.06 (1H, d, J=7Hz), 7.2-7.6 (9H, m), 8.10 (1H, d, J=7Hz) 188921.1-1.8 (6H, m), 3.06 (s, 3H), 3.0-3.6 (4H, m), 3.80 (s, 3H), 6.10 (d, 1H, J=7Hz), 7.90 (d. 1H, J=7Hz), 7.43 (d, 2H, J=7Hz), 7.76 (d, 2H, J=7Hz) 196721.1-1.8 (m, 6H), 3.47 (s, 3H), 3.0-3.5 (m, 4H), 6.15 (1H, d, J=7Hz), 8.09 (d, 1H, J=7Hz), 7.55 (d, 2H, J=7Hz), 7.80 (d, 2H, J=7Hz), 9.93 (s, 1H) 204831.2-1.7 (m, 6H), 2.04 (s, 3H), 3.08 (s, 3H), 3.0-3.5 (m, 4H), 5.93 (d, 1H, J=7Hz), 8.03 (d, 1H, J=7Hz), 7.0-7.4 (m, 4H) 212372.32 (3H, s), 2.64 (4H, m), 3.36 (3H, s), 4.12 (4H, m), 6.63 (1H, d, J=7Hz), 8.23 (1H, d, J=7Hz) Comp. No. Yield (%) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 220821.62 (6H, br. s), 3.3-4.0 (12H, m), 5.92 (1H, d, J=7Hz), 7.88 (1H, d, J=7Hz), 8.10 (1H, s) 228751.62 (6H, br. s), 3.5-3.9 (12H, m), 5.82 (1H, d, J=7Hz), 7.44 (5H, s), 7.98 (1H, d, J=7Hz) 236651.64 (6H, br. s), 2.16 (3H, s), 3.4-3.9 (12H, m), 5.80 (1H, d, J=7Hz), 7.94 (1H, d, J=7Hz) 244811.2-2.1 (4H, m), 2.5-3.1 (3H, m), 3.64 (8H, br. s), 4.86 (2H, br. s, J=8Hz), 5.84 (1H, d, J=7Hz), 7.1-7.4 (5H, m), 7.38 (5H, s), 7.98 (1H, d, J=7Hz) 260861.4-2.1 (4H, m), 2.6-3.2 (3H, m), 3.54 (3H, s), 4.70 (2H, br. d, J=12Hz), 7.2-7.4 (5H, m), 7.38 (2H, d, J=8Hz), 8.00 (1H, d, J=7Hz) 252841.4-2.0 (4H, m), 2.12 (3H, s), 2.5-3.1 (3H, m), 3.4-3.8 (8H, m), 4.90 (2H, br. s, d, J=12Hz), 5.84 (1H, d, J=7Hz), 7.1-7.4 (5H, m), 7.98 (1H, d, J=7Hz) Example 24-(N-methyl-4-trifluoromethylbenzoylamino)-2-(4-phenylpiperidino) pyrimidine p-toluenesulfonate (compound No.112)30 ml of ethyl acetate containing 0.63g of p-toluenesulfonic acid hydrate(3.3 mM) was added to 10 ml of ethyl acetate containing 1.45g of 4-(N-methyl-4-trifluoro-methylbenzoylamino)-2-(4-phenylpiperidino) pyrimidine (3.3 mM). 100 ml of hexane was added to the mixture to form suspension. After the addition of hexane, the suspension was stirred for an hour. The solid substance thus formed was separated by filtration and 2.0g of a white solid substance, a desired product, was obtained (yield 96%). Melting point 177-177.5°C ¹H-NMR spectrum (deuterochloroform, δppm) 1.4-2.0 (4H, m), 2.32 (3H, s), 2.6-3.2 (3H, m), 3.53 (3H, s), 4.2-4.6 (2H, m), 6.74 (1H, d, J=7Hz), 7.0-7.4 (7H, m), 7.72 (4H, s), 7.78 (2H, d, J=8Hz), 8.46 (1H, d, J=7Hz), The physical properties of compounds produced by the same method as described above are shown in Table 3 Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 10450147-1492.35 (3H, s), 3.13 (2H, t, J=8Hz), 3.65 (3H, s), 4.00 (2H, t, J=8Hz), 6.02 (1H, d, J=7Hz), 7.16 (2H, d, J=8Hz), 6.8-7.6 (9H, m), 7.86 (2H, d, J=8Hz), 8.55 (1H, d, J=7Hz) 12095210-2111.3-2.1 (4H, m), 2.34 (3H, s), 3.54(3H, s), 3.90(3H, s), 4.2-4.6(2H, m), 6.68 (1H, d, J=7Hz), 7.14 (2H, d, J=8Hz), 7.1-7.4 (5H, m), 7.64(2H, d, J=8Hz), 7.80 (2H, d, J=8Hz), 8.12 (2H, d, J=8Hz), 8.47 (1H, d, J=7Hz) 12893168-1691.4-2.1 (4H, m), 2.38 (3H, s), 2.6-3.3 (3H, m), 3.57 (3H, s), 4.2-4.6 (2H, m), 6.86 (1H, d, J=7Hz), 7.18 (2H, d, J=8Hz), 7.1-7.4 (5H, m), 7.78 (4H, s), 7.80 (2H, d, J=8Hz) 8.54 (1H, d, J=7Hz) 13685208-208.51.3-2.1 (4H, m), 2.36 (3H, s), 2.6-3.2 (3H, m), 3.58 (3H, s), 4.1-4.6 (2H, m), 6.88 (1H, d, J=7Hz), 7.14 (2H, d, J=8Hz), 7.1-7.4 (5H, m), 7.74 (2H, d, J=8Hz), 7.84 (2H, d, J=8Hz), 8.09 (2H, d, J=8Hz), 8.54 (1H, d, J=7Hz) 14488175-1771.2-2.0 (4H, m), 2.35 (3H, s), 2.5-3.2 (3H, m), 3.64 (3H, s), 4.3-4.5 (2H, m), 6.62 (1H, d, J=7Hz), 7.16 (2H, d, J=8Hz), 7.1-8.2 (12H, m), 7.80 (2H, d, J=8Hz), 8.38 (1H, J=7Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 15279162-1641.2-2.1 (4H, m), 2.36 (3H, s), 2.5-3.4 (3H, m), 3.54 (3H, s), 4.3-4.6 (2H, m), 6.74 (1H, d, J=7Hz), 7.14 (2H, d, J=8Hz), 7.1-7.4 (5H, m), 7.74 (2H, d, J=8Hz), 7.78 (2H, d, J=8Hz), 8.00 (2H, d, J=8Hz), 8.30 (1H, d, J=7Hz), 10.1 (1H, s) 16074143-1451.6-3.2 (23H, m), 3.29 (3H, s), 4.72 (2H, m), 6.22 (1H, d, J=7Hz), 7.20 (5H, m), 8.24 (1H, d, J=7Hz), 16872135-140[CDCl₃-CD₃OD] 1.2-2.0 (3H, m), 2.35 (3H, s), 2.5-3.4 (4H, m), 3.54 (3H, s), 3.85 (2H, m), 6.88 (1H, d, J=7Hz), 7.0-8.3 (9H, m) 17684180-1821.5-2.0 (m, 4H), 2.28 (s, 3H), 2.52 (s, 3H), 3.47 (s, 3H), 2.6-3.2 (m, 3H), 4.2-4.6 (m, 2H), 6.64 (d, 1H, J=7Hz), 6.9-8.0 (m, 13H), 8.36 (d, 1H, J=7Hz) 18410066-692.35 (3H, s), 3.69 (3H, s), 4.16 (2H, s), 4.80 (2H, s), 6.64 (1H, d, J=7Hz), 7.14 (2H, d, J=8Hz), 7.2-7.7 (9H, m), 7.84 (2H, d, J=8Hz), 8.58 (1H, d, J=7Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 27293196-1971.74 (6H, br. s), 1.9-2.4 (2H, m), 2.40 (3H, s), 2.6-2.9 (2H, m), 3.86 (4H, br. s), 4.06 (2H, t, J=8Hz), 7.18 (2H, d, J=8Hz), 7.82 (2H, d, J=8Hz), 7.86 (1H, d, J=7Hz), 8.38 (1H, d, J=7Hz), 28073177-1781.5-2.5 (5H, m), 2.37 (3H, s), 2.6-3.4 (6H, m), 4.07 (2H, t, J=8Hz), 4.80 (2H, br. d, J=12Hz), 7.16 (2H, d, J=8Hz), 7.28 (5H, s), 7.82 (2H, d, J=7Hz), 7.90 (2H, d, J=8Hz), 8.44 (2H, d, J=7Hz) 30490186-1880.97 (3H, d, J=7Hz), 1.0-2.3 (7H, m), 2.36 (3H, s), 2.6-3.3 (4H, m), 4.03 (2H, t, J=7Hz), 4.56 (2H, m), 7.16 (2H, d, J=7Hz), 7.80 (3H, m), 8.35 (1H, d, J=7Hz) 31292152-1540.91 (3H, t, J=7Hz), 1.0-2.3 (11H, m), 2.36 (3H, s), 2.72 (2H, t, J=7Hz), 3.06 (2H, m), 4.03 (2H, t, J=7Hz), 4.57 (2H, m), 7.16 (2H, d, J=7Hz), 7.80 (3H, m), 8.34 (1H, d, J=7Hz) Example 34-(N-formylpiperazino)-2-piperidino pyrimidine maleate (compound No. 224)30 ml of ethyl acetate containing 0.42g of maleic acid (3.6 mM) was added to 10ml of ethyl acetate containing 1.0g of 4-(N-formylpiperazino)-2-piperidinopyrimidine (3.6 mM) at room temperature. The mixture was then stirred for an hour and concentrated under reduced pressure. Ether was added to the concentrate to crystalize and the crystal was resuspended. The solid substance thus formed was separated by filtration and 1.38g of a white solid substance, a desired product, was obtained (yield 97%). Melting point 124-126°C ¹H-NMR spectrum (deuterochloroform, δppm) 1.76 (6H, br.s), 3.5-4.1 (12H, m), 6.18 (1H, d, J=7Hz), 6.31 (2H, s), 8.00 (1H, d, J=7Hz), 8.12 (1H, s) The physical properties of compounds produced by the same method as described above are shown in Table 4. Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 19293121-1231.2-1.8 (6H, m), 3.52 (s, 3H), 3.2-3.7 (4H, m), 3.95(s, 3H), 6.35 (s, 2H), 6.60 (d, 1H, J=7Hz), 7.60 (d, 2H, J=7Hz), 8.08 (d, 2H, J=7Hz), 8.22 (d, 1H, J=7Hz), 11.6 (br, 2H) 20081101-1031.2-1.8 (m, 6H), 3.51 (s, 3H), 3.2-3.7 (m, 4H), 6.36 (s, 2H), 6.72 (1H, d, J=7Hz), 7.65 (d, 2H, J=7Hz), 8.04 (d, 2H, J=7Hz), 8.26 (d, 1H, J=7Hz), 9.99 (s, 1H) 20893169-1711.4-2.0 (m, 6H), 2.41 (s, 3H), 3.45 (s, 3H), 3.2-3.7 (m, 4H), 6.61 (d, 1H, J=7Hz), 8.78 (d, 1H, J=7Hz), 7.0-7.6 (m, 4H), 6.40 (s, 2H) 2167883-842.43 (3H, s), 2.72 (4H, m), 3.46 (3H, s), 4.15 (4H, m), 6.40 (2H, s), 7.22 (1H, d, J=7Hz), 8.30 (1H, d, J=7Hz) 23292162-1631.72 (6H, br. s), 3.82 (12H, br. s), 6.14 (1H, d, J=7Hz), 6.34 (2H, s), 7.50 (5H, s), 8.10 (1H, s) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 24093123-1241.74 (6H, br. s), 2.20 (3H, s), 3.80 (12H, br. s), 6.16 (1H, d, J=7Hz), 6.32 (2H, s), 8.16 (1H, d, J=7Hz) 2489097-1001.5-2.3 (4H, m), 2.6-3.5 (3H, m), 3.82 (8H, br. s), 4.70 (2H, br. d, J=8Hz), 6.18 (1H, d, J=7Hz), 7.1-7.4 (5H, m), 7.46 (5H, s), 8.14 (1H, d, J=7Hz), 6.30 (2H, s) 25693149-1511.6-2.2 (4H, m), 2.20 (3H, s), 2.8-3.5 (3H, m), 3.80 (8H, br. s), 4.72 (2H, br. d, J=12Hz), 6.10 (1H, d, J=7Hz), 6.33 (2H, s), 7.1-7.5 (5H, m), 8.16 (1H, d, J=7Hz) 2645878-811.5-2.2 (4H, m), 2.6-3.3 (3H, m) 3.52 (3H, s), 4.68 (2H, br. d, J=12Hz) 6.24 (1H, d, J=7Hz), 6.34 (2H, s), 6.90 (2H, d, J=8Hz), 7.2-7.4 (5H, m), 7.50 (2H, d, J=8Hz), 7.96 (1H, d, J=7Hz) 27388163-1641.73 (6H, m), 1.9-2.4 (2H, m) 2.74 (2H, t, J=7Hz), 3.92 (4H, m), 4.07 (2H, t, J=7Hz), 6.16 (2H, s), 7.84 (2H, d, J=7Hz), 8.34 (1H, d, J=7Hz) Example 44-(2-oxopyrrolidino)-2-(4-phenylpiperidino) pyrimidine (compound No. 276)0.5g of 4-chloro-2-(4-phenylpiperidino) pyrimidine (1.8mM), 0.38g of 4-amino butyric acid (3.7mM) and 0.25g of potassium carbonate (1.8mM) were added to 30 ml of n-butanol. The mixture was heated at 120°C for 6 hours and concentrated under reduced pressure. To the residue, chloroform and water were added for extraction. The organic layer was concentrated under reduced pressure. The concentrate was purified by a silca gel chromatography [developing solvent; methanol: methylene chloride (1:1)] to give 0.4g of 4-(3-carboxylpropylamino)-2-(4-phenylpiperidino) pyrimidine (yield 66%). 0.4g of 4-(3-carboxyl propylamino)-2-(4-phenylpiperidino) pyrimidine was dissolved in 10 ml of chloroform. 1 ml of thionyl chloride was added to the solution. The mixture was stirred at room temperature for 5 hours. Sodium carbonate solution was added to the mixture. The organic layer was separated and concentrated under reduced pressure. 0.19g of white solid sobstance, a desired product, was obtained (yield 50%). Melting point 177-178°C ¹H-NMR spectrum (deuterochloroform, δppm) 1.6-2.3 (5H,m), 2.4-4.2 (6H,m), 4.07 (2H, t, J=8Hz), 4.90 (2H, br.d, J=12Hz), 7.1-7.4 (5H, m), 7.56 (1H, d, J=7Hz), 8.24 (1H, d, J=7Hz) The physical properties of compounds produced by the same method as described above are shown in Table 5. Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 30052109-1110.96 (3H, d, J=7Hz), 1.0-3.0 (11H, m), 4.03 (2H, t, J=7Hz), 4.66 (2H, m), 7.50 (1H, d, J=6Hz), 8.18 (1H, d, J=6Hz) 3085093-980.8-3.0 (16H, m), 4.04 (2H, t, J=7Hz), 4.68 (2H, m), 7.50 (1H, d, J=5Hz), 8.18 (1H, d, J=5Hz) 31693153-1551.85-1.30 (6H, m), 2.64 (2H, t, J=7Hz), 3.56 (4H, m), 4.07 (2H, t, J=7Hz), 7.54 (1H, d, J=6Hz), 8.22 (1H, d, J=6Hz) 32491oil1.18 (3H, d, J=7Hz), 1.65 (6H, m), 2.18 (2H, m), 2.64 (2H, t, J=7Hz), 2.92 (1H, m), 4.04 (2H, t, J=7Hz), 4.40-5.10 (2H, m), 7.50 (1H, d, J=6Hz), 8.20 (1H, d, J=6Hz) 3329593-940.94 (3H, d, J=7Hz), 1.20-3.00 (11H, m), 4.04 (2H, t, J=7Hz), 4.54 (2H, m), 7.50 (1H, d, J=6Hz), 8.20 (1H, d, J=6Hz) 3409693-960.94 (6H, d, J=7Hz), 1.40-3.60 (10H, m), 4.03 (2H, t, J=7Hz), 4.66 (2H, m), 7.48 (1H, d, J=6Hz), 8.19 (1H, d, J=6Hz) 34861135-1372.12 (2H, m), 2.65 (2H, t, J=7Hz), 2.92 (2H, t, J=7Hz), 4.03 (2H, t, J=7Hz), 4.09 (2H, t, J=7Hz), 4.88 (2H, s), 7.18 (4H, m), 7.58 (1H, d, J=6Hz), 8.25 (1H, d, J=6Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 35643127-1292.08 (4H m), 2.64 (2H, t, J=7Hz), 2.80 (2H, t, J=7Hz), 4.00 (4H, m), 7.07 (3H, m), 7.72 (1H, d, J=6Hz), 7.76 (1H, m), 8.30 (1H, d, J=6Hz) 36482110-1121.04-2.96 (13H, m), 4.02 (2H, t, J=7Hz), 4.70 (2H, m), 7.24 (5H, m), 7.50 (1H, d, J=6Hz), 8.19 (1H, d, J=6Hz) 3729581-832.27 (3H, t, J=7Hz), 1.50-3.20 (11H, m), 4.03 (2H, t, J=7Hz), 4.14 (2H, q, J=7Hz), 4.60 (2H, m), 7.54 (1H, d, J=6Hz), 8.20 (1H, d, J=6Hz) 38067141-1432.10 (2H, m), 2.64 (2H, t, J=7Hz), 2.92 (4H, m), 3.76 (4H, m), 4.03 (2H, t, J=7Hz), 7.55 (1H, d, J=6Hz), 8.20 (1H, d, J=6Hz) 38883140-1432.10 (2H, t, J=7Hz), 2.65 (2H, t, J=7Hz), 3.76 (8H, s), 4.03 (2H, t, J=7Hz), 7.61 (1H, d, J=6Hz), 8.22 (1H, d, J=6Hz) 39685118-1202.10 (2H, m), 2.64 (6H, m), 4.10 (6H, m), 7.57 (1H, d, J=6Hz), 8.21 (1H, d, J=6Hz) 40480128-1292.10 (2H, m), 2.35 (3H, s), 2.46 (4H, m), 2.65 (2H, t, J=7Hz), 3.82 (4H, m), 4.04 (2H, t, J=7Hz), 7.57 (1H, d, J=6Hz), 8.22 (1H, d, J=6Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 41259182-1852.09 (2H, m), 2.63 (2H, t, J=7Hz), 3.20 (4H, m), 3.96 (6H, m), 6.92 (3H, m), 7.22 (2H, m), 7.54 (1H, d, J=6Hz), 8.18 (1H, d, J=6Hz) 42095104-1072.08 (2H, m), 2.55 (6H, m), 3.55 (2H, s), 3.79 (4H, m), 4.02 (2H, t, J=7Hz), 7.33 (5H, m), 7.55 (1H, d, J=6Hz), 8.21 (1H, d, J=6Hz) 42896115-1182.10 (2H, m), 2.64 (2H, t, J=7Hz), 3.16 (6H, s), 4.06 (2H, t, J=7Hz), 7.52 (1H, d, J=6Hz), 8.21 (1H, d, J=6Hz) 43648oil0.94 (6H, t, J=7Hz), 1.2-1.8 (8H, m), 2.08 (2H, m), 2.62 (2H, t, J=7Hz), 3.50 (4H, t, J=7Hz), 4.00 (2H, t, J=7Hz), 7.42 (1H, d, J=6Hz), 8.14 (1H, d, J=6Hz) 26870-1.68 (6H, br. s), 1.9-2.4 (2H, m), 2.4-2.6 (2H, m), 3.74 (4H, br. s), 4.07 (2H, t, J=8Hz), 7.52 (1H, d, J=7Hz), 8.22 (1H, d, J=7Hz) Example 54-(2-oxopyrrolidino)-2-(4-piperidino) pyrimidine hydrochloride (compound No.274)1.25g of concentrated hydrochloric acid was added to 50 ml of methanol solution containing 3.05g of 4-(2-oxopyrrolidino)-2-(4-piperidino) pyrimidine (12.4 mM) at room temperature. The mixture was stirred for an hour and concentrated under reduced pressure. Ethyl acetate was added to the concentrate for crystalization and the mixture was filtered to give 3.26g of a white solid substance, a desired product (yield 90%). Melting point: 260-262°C (dec.) ¹H-NMR spectrum (deuterochloroform, δppm) 1.75 (6H, m), 2.20 (2H, m), 2.75 (2H, t, J=7Hz), 3.98 (4H, m), 4.06 (2H, t, J=7Hz), 7.86 (1H, d, J=7Hz), 8.16 (1H, d, J=7Hz) The physical properties of compounds produced by the same method as described above are shown in Table 6. Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 32095263-266 (decom position)2.12 (6H, m), 2.76 (2H, t, J=7Hz), 3.56-4.20 (6H, m), 7.90 (1H, d, J=7Hz), 8.18 (1H, d, J=7Hz) 32893161-1641.34 (3H, d, J=7Hz), 1.74 (6H, m), 2.20 (2H, m), 2.75 (2H, t, J=7Hz), 3.24 (1H, m), 4.08 (2H, t, J=7Hz), 4.50-5.20 (2H, m), 7.88 (1H, d, J=7Hz), 8.22 (1H, d, J=7Hz) 33684213-217 (decom position)1.04 (3H, d, J=7Hz), 1.20-3.40 (11H, m), 4.07 (2H, t, J=7Hz), 4.66 (2H, m), 7.86 (1H, d, J=7Hz), 8.17 (1H, d, J=7Hz) 34498178-1801.04 (6H, d, J=7Hz), 1.40-3.80 (10H, m), 4.06 (2H, t, J=7Hz), 4.80 (2H, m), 7.85 (1H, d, J=7Hz), 8.18 (1H, d, J=7Hz) 35284158-1632.21 (2H, m), 2.74 (2H, t, J=7Hz), 3.06 (2H, m), 4.10 (4H, m), 4.8-5.3 (2H, m), 7.18 (4H, m), 7.88 (1H, d, J=7Hz), 8.18 (1H, d, J=7Hz) 36097140-1452.18 (4H, m), 2.72 (4H, m), 3.87 (2H, t, J=7Hz), 4.26 (2H, t, J=7Hz), 7.20 (3H, m), 7.48 (1H, m), 8.06 (1H, d, J=7Hz), 8.40 (1H, d, J=7Hz) 36881150-1551.1-3.3 (13H, m), 4.01 (2H, t, J=7Hz), 4.80 (2H, m), 7.19 (5H, m), 7.81 (1H, d, J=7Hz), 8.12 (1H, d, J=7Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 37687143-1461.27 (3H, t, J=7Hz), 1.6-2.7 (7H, m), 2.74 (2H, t, J=7Hz), 3.47 (2H, m), 4.04 (2H, t, J=7Hz), 4.15 (2H, q, J=7Hz), 7.87 (1H, d, J=7Hz), 8.15 (1H, d, J=7Hz) 38498285-289 (decom position)[CDCl₃-CD₃OD] 1.18 (2H, m), 2.71 (2H, t, J=7Hz), 3.32 (4H, m), 4.12 (6H, m), 7.79 (1H, d, J=7Hz), 8.20 (1H, d, J=7Hz) 39287169-1732.23 (2H, m), 2.78 (2H, t, J=7Hz), 3.70-4.40 (10H, m), 7.96 (1H, d, J=7Hz), 8.20 (1H, d, J=7Hz) 40085172-176[CDCl₃-CD₃OD] 2.22 (2H, m), 2.80 (6H, m), 4.08 (2H, t, J=7Hz), 4.28 (4H, m), 7.96 (1H, d, J=7Hz), 8.18 (1H, d, J=7Hz) 40896266-270[CDCl₃-CD₃OD] 2.08 (2H, m), 2.68 (2H, t, J=7Hz), 2.90 (3H, s), 3.1-4.9 (10H, m), 7.68 (1H, d, J=7Hz), 8.23 (1H, d, J=7Hz) 41660187-189[CDCl₃-CD₃OD] 2.21 (2H, m), 2.76 (2H, t, J=7Hz), 3.7-4.6 (10H, m), 7.43 (3H, m), 7.69 (2H, m), 7.98 (1H, d, J=7Hz), 8.10 (1H, d, J=7Hz) 42496262-2662.12 (2H, m), 2.66 (2H, t, J=7Hz), 2.80-4.90 (12H, m), 7.46 (3H, m), 7.64 (2H, m), 7.70 (1H, d, J=7Hz), 8.21 (1H, d, J=7Hz) Comp. No. Yield (%) Melting Point (°C) ¹H-NMR spectrum (CDCl₃ solution, δ ppm) 43297205-2102.20 (2H, m), 2.74 (2H, t, J=7Hz), 3.30 (3H, br. s), 3.50 (3H, br. s), 4.07 (2H, t, J=7Hz), 7.86 (1H, d, J=7Hz), 8.16 (1H, d, J=7Hz) 44064124-1270.96 (6H, t, J=7Hz), 1.2-1.9 (8H, m), 2.18 (2H, m), 2.72 (2H, t, J=7Hz), 3.58 (2H, t, J=7Hz), 3.82 (2H, t, J=7Hz), 4.02 (2H, t, J=7Hz), 7.82 (1H, d, J=7Hz), 8.16 (1H, d, J=7Hz) Example 1BTablets each containing 10 mg of an active ingredient were prepared by the following procedure. Per tablet Active ingredient10 mg Corn starch55 mg Crystalline cellulose35 mg Polyvinyl pyrrolidone (as 10% aqueous solution)5 mg Carboxymethyl cellulose calcium10 mg Magnesium stearate4 mg Talc1mg Total120 mg The active ingredient, corn starch and crystalline cellulose were passed through an 80-mesh sieve and thoroughly mixed. The mixed powder was granulated together with the polyvinyl pyrrolidone solution, and passed through an 18-mesh sieve. The resulting granules were dried at 50 to 60°C and again passed through an 18-mesh sieve to adjust their sizes. The carboxymethyl cellulose calcium, magnesium stearate and talc which had been passed through an 80-mesh sieve, were added to the granules. They were mixed and tableted by a tableting machine to produce tablets each having a weight of 120 mg. Example 2BTablets each containing 200 mg of an active ingredient were produced by the following procedure. Per tablet Active ingredient200 mg Corn starch50 mg Crystalline cellulose42 mg Silicic anhydride7 mg Magnesium stearate1 mg Total300 mg The above components were passed through an 80-mesh sieve and thoroughly mixed. The resulting mixed powder was compression-molded to produce tablets each having a weight of 300 mg. Example 3BCapsules each containing 100 mg of an active ingredient were produced by the following procedure. Per capsule Active ingredient100 mg Corn Starch40 mg Lactose5 mg Magnesium stearate5 mg Total150 mg The above components were mixed, passed through an 80-mesh sieve, and thoroughly mixed. The resulting mixed powder was filled into capsules in an amount of 150 mg for each. Example 4BInjectable preparations in vials each containing 5 mg of an active ingredient were produced by the following procedure. Per vial Active ingredient5 mg Mannitol50 mg Just prior to use, these compounds were dissolved in 1 ml of distilled water for injection, and administered. Example 5BInjectable preparations in ampoules each containing 50 mg of an active ingredients were produced in accordance with the following recipe. Per ampoule Active ingredient50 mg Sodium chloride18 mg Distilled water for injectionproper amount Total2 ml Example 6BAn adhesive patch containing 17.5 mg of an active ingredient was produced by the following procedure. Ten parts of poly(ammonium acrylate) was dissolved in 60 parts of water. Two parts of glycerin diglycidyl ether was dissolved under heat in 10 parts of water. Furthermore, 10 parts of polyethylene glycol (grade 400) 10 parts of water and 1 part of an active ingredient were stirred to form, a solution. While the aqueous solution of poly(ammonium acrylate) was stirred, the aqueous solution of glycerin diglycidyl ether and the solution containing the active ingredient, polyethylene glycol and water were added and mixed. The resulting solution for hydrogel was coated on a pliable plastic film so that the rate of the active ingredient was 0.5 mg per cm². The surface was covered with releasing paper and cut to a size of 35 cm² to form an adhesive patch. Example 7BAn adhesive patch containing 10 mg of an active ingredient was produced by the following procedure. An aqueous sol prepared from 100 parts of poly (sodium acrylate), 100 parts of glycerin, 150 parts of water, 0.2 part of triepoxypropyl isocyanurate, 100 parts of ethanol, 25 parts of isopropyl myristate, 25 parts of propylene glycol and 15 parts of the active ingredient. The sol was then coated to a thickness of 100 micrometers on the non-moven fabric surface of a composite film composed of rayon non-woven fabric and a polyethylene film to form an adhesive layer containing the drug. The amount of the release aids (isopropyl myristate and propylene glycol) contained in this layer was about 20 % by weight. The adhesive layer was then crosslinked at 25°C for 24 hours, and a releasing film was bonded to the adhesive layer surface. The entire film was then cut into pieces each having an area of 35 cm². The biological activities invitro of the compounds of formula (I) on cells of the nervous system were tested. The cells tested were mouse neuroblastoma cell line neuro-2a (Dainippon Pharmaceutical Co., Ltd.) which have been established as the cells of the nervous system. The above nerve cells were grown in an incubator at 37°C in the presence of 5% carbon dioxide gas exponentially, and the cultured for a certain period of time together with the compounds of formula (I). The results demonstrate that the compounds of formula (I) have nerve cell growth promoting activity and neurite formation and sprouting promoting activity which are markedly higher with a significance than a control, and are equal to, or higher than, isaxonine as a control drug (the compound described in Japanese Patent Publication No. 28548/1984). The biological activities of the compounds of this invention on rat PC-12 pheochromocytoma cell line were also tested. When NGF is added to PC-12 cells, the neurites sprout, it was shown that when the compound of this invention is added at this time, the binding of NGF to the PC-12 cells and the up-take of NGF into the cells increased. When the effect of the compounds of this invention on the binding of NGF to rabbit superior cervical ganglion was examined, they were found to promote the NGF binding. Rats whose sciatic nerves were crushed were prepared as a model for peripheral nervous disorders and the effects of the compounds of this invention on it were tested. It was made clear that the compounds of the present invention have an effect of promoting recovery of the interdigit distance and the weight of the soleus muscle to normal values. Rat and mouse models of central nervous disorders were prepared, and the pharmacological effects of the compounds of this invention were tested. Specifically, nigral dopamine cells of the rat brain were chemically destroyed by injecting a very small amount of 6-hydroxydopamine to induce motor imbalance. Two weeks later, dopamine cells of fatal brain were transplanted in the caudate nucleus into the lesioned side of the rat brain and an attempt was made to improve the motor trouble. Specifically, beginning on the day of transplantation, the compound of the invention was intraperitoneally administered every day over 2 weeks, and the activity of the compounds of the invention on the improvement of the motor imbalance and the growth of the transplanted cells was examined. It was found that the compounds of the invention have a promoting effect on the improvement of the motor trouble. The forebrain fundus of animals was destroyed by ibotenic acid and the like and then the compound of the present invention was administered to the animals. An amount of acetyl choline release and choline acetyl transferase activity of various sites in the cortex of cerebrum were tested. It was found that the compounds of the invention have a improved effect on them. Rats and mice having a nerve trouble by mercury poisoning were prepared and the activity of the compounds of the invention was tested. The compounds were found to have a promoting effect on the improvement of the condition and recovery to a normal condition, a curative effect on chemicals-induced disorders and an effect of improving and recovering learning and memory. Thus, it has been made clear that the compounds of this invention are useful as agents for improving or curing various neurological diseases of mammals, such as troubles in peripheral and central nerves, and also as agents for improving learning and memory. Various types of neuropathy including, for example, various peripheral nerve disorders accompanied by motorgenic, sensory or objective flex retardation, and alcohol-induced or drug-induced, diabetic and metabolic, or idiopathic peripheral nerve disorders, including traumatic, inflammatory or immunological nerve root lesions may be cited as such neurological diseases. More specific examples include facial palsy, sciatic nerve paralysis, spinal muscular atrophy, muscular dystrophy, myasthenia gravis, multiple sclerosis, amyotrophic lateral sclerosis, acute disseminated cerebromyelitis, Guillan-Barre syndrome, postvaccinal encephalomyelitis, SMON disease, dementia, Alzheimer syndrome, a condition after cranial injury cerebral ischemia, sequela of cerebral infarction or cerebral hemorrhage, and rheumatism. These examples are not limitative. By a toxicity test, the compounds of this invention were found to have only weak toxicity and side effect, and be used as safe and highly useful medicines. Experimental example 1 The effects of the compounds of this invention on neuroblastoma cells were examined by the following method. Mouse neuro 2a cells in the logarithmic growth period in the Dulbecco's modified Eagle's medium [DMEM, containing 100 units/ml of penicillin G sodium and 100 micrograms/ml of streptomycin sulfate] containing 10% of FCS were seeded in a 48-well plate so that the number of cells was 1,000 cells/well, and cultured for one day in 0.25 ml of the culture fluid in each well in an incubator containing 5 % of carbon dioxide gas in air at 37°C. The medium was replaced by a medium containing each antibiotics and FCS and the cells were further cultured for 24 hours. Then, a 4 % aqueous glutaraldehyde solution in the same amount as a medium (0.25 ml) was added, and the culture was left to stand at room temperature for 2 hours to fix the cells. After washing with water, a 0.05 % aqueous solution of methylene blue was added to stain the cells. Under a microscope, the number of cells containing outgrown neurites (cells having at least one neurite with a length of at least two times as large as the long diameter of the cell) was counted visually, and the proportion of these cells in the entire cells was calculated. The well was observed over 5 or more visual fields (at least 2 % of the entire surface area of the well) continuous to the left and right from a mark put at the center of the well, and more than 200 cells was counted. One drug compound was used in 6 different concentrations at most, and three runs were conducted for each concentration. The results are expressed as a mean ± S.D., and the results are shown in Table 7. Mouse neuroblastoma cells NS-20Y were similarly cultured in a dish coated with polyornithine, and the effects after 24 hours and 48 hours from the start of culturing are shown in Table 8. Experiment 1 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 1043.4±1.0 (0.03), 5.2±2.9 (0.1) 1125.9±0.9 (0.03), 43.3±1.8 (0.1), 21.6±3.3 (0.3), 10.0±3.8 (1) 12012.6±1.6 (0.03), 8.6±5.5 (0.1) 1284.3±1.6 (0.1), 4.8±1.2 (0.3) 1365.2±1.8 (0.03), 5.4±1.7 (0.1) 10.3±0.2 (0.3), 11.8±1.4 (1) Isaxonine23.0±5.0 (10) Control2.6±1.5 Experiment 2 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 1445.1±0.9 (0.01), 4.2±0.6 (0.1) 1525.2±0.4 (0.01), 16.5±1.8 (0.03) 1605.1±1.2 (0.03), 11.4±1.3 (0.1), 23.5±2.9 (0.3), 20.7±2.7 (1) 1688.7±2.0 (0.3), 14.6±3.7 (1) Isaxonine23.8±4.7 (10) Control2.4±1.1 Experiment 3 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 17611.5±2.1 (0.03), 18.4±2.0 (0.01), 13.6±0.9 (0.3), 14.8±2.9 (1) Isaxonine23.8±4.7 (10) Control3.0±0.7 Experiment 4 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 1840.5±0.8 (0.01), 0.9±0.8 (0.1) Isaxonine20.2±0.8 (10) Control2.6±1.0 Experiment 5 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 1928.0±1.3 (0.1), 13.8±2.8 (0.3) 2005.8±1.3 (0.1), 19.7±3.1 (0.3) 2087.9±0.6 (0.3), 12.7±3.0 (1) 2164.4±1.3 (0.3), 15.8±3.2 (1) 2248.9±1.5 (0.1), 21.4±3.3 (0.3) Isaxonine25.1±2.8 (10) Control5.5±1.2 Experiment 6 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 2725.4±0.4 (0.01), 10.5±2.5 (0.1), 25.1±2.7 (0.3), 20.4±4.9 (1) 2807.1±1.7 (0.01), 6.9±1.4 (0.1), 7.5±1.1 (0.3), 8.1±6.3 (1) Isaxonine16.0±4.7 (10) Control3.6±0.5 Experiment 7 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 2735.3±0.8 (0.01), 7.7±2.0 (0.1), 24.0±3.2 (0.3), 10.3±4.0 (1) 3043.7±1.2 (0.03), 6.8±1.0 (0.1), 17.7±2.9 (0.3) 16.3±4.5 (1) 3123.8±0.6 (0.01), 4.1±1.2 (0.03) 12.7±2.8 (0.1) 27425.8±3.5 (0.3) Isaxonine18.3±2.4 (10) Control2.4±1.0 Experiment 8 Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 3204.2±1.9 (0.01), 4.2±0.3 (0.1), 11.0±0.8 (0.3), 10.7±4.7 (1) 3283.9±0.9 (0.01), 5.6±1.7 (0.3), 3364.0±1.0 (0.03), 5.7±1.6 (0.1), 21.3±3.0 (0.3), 21.2±1.6 (1) 3445.6±1.6 (0.01), 7.5±3.3 (0.1) 10.4±3.4 (0.3), 12.5±1.3 (1) 3523.4±0.1 (0.01), 4.2±0.6 (0.3) 3604.8±1.2 (0.03), 6.7±0.8 (0.3) 3683.4±0.3 (0.01), 14.4±1.7 (0.1) 3763.4±0.6 (0.01), 4.4±0.8 (0.1), 6.0±0.5 (0.3) 3844.1±1.5 (0.01), 5.1±2.1 (0.1), 8.3±2.7 (0.3), 11.5±1.3 (1) 3926.6±2.2 (0.03), 5.6±3.7 (0.1), 6.1±4.0 (0.3) 4005.0±0.1 (0.03), 6.3±0.7 (0.1), 11.2±1.5 (0.3), 12.1±1.4 (1) 4084.9±0.2 (0.03), 4.4±0.2 (0.3) 4165.0±1.9 (0.01), 4.4±0.4 (0.1), 5.1±1.2 (0.3) 4244.5±2.4 (0.03), 5.9±1.7 (0.1), 5.2±2.5 (0.3) Comp. No. Ratio of the number of cells having neurites with a length of at least two times as large as the diameter of cells to the total number of cells (%) (concentration of compound solution, mM) 4324.0±2.2 (0.03), 4.2±1.7 (0.1), 5.1±1.2 (1) 4404.3±0.8 (0.1) Isaxonine18.8±1.6 (10) Control2.6±0.7 Comp. The number of cells in which neurites appeared/Total number of cells (concentration of compound solution) 24 hour 48 hour 2483/50 (0.2mM)3/50 (0.1mM) Control1/502/50 2563/50 (0.2mM)4/50 (0.1mM) 3/50 (0.1mM)3/50 (0.2mM) Control0/500/50 2643/50 (0.5mM)3/50 (0.2mM) Control1/502/50 1925/50 (0.5mM)11/50 (0.5mM) 5/50 (0.2mM)7/50 (0.2mM) Control0/503/50 20016/50 (0.5mM)18/50 (0.5mM) 8/50 (0.2mM)11/50 (0.2mM) Control1/502/50 2323/50 (0.2mM)4/50 (0.1mM) Control0/502/50 2405/50 (0.5mM)6/50 (0.5mM) 3/50 (0.1mM)5/50 (0.2mM) Control1/502/50 2163/50 (0.5mM)4/50 (0.5mM) 3/50 (0.2mM)4/50 (0.5mM) Control0/501/50 1044/50 (0.5mM)3/50 (0.5mM) 3/50 (0.2mM)4/50 (0.2mM) Control2/501/50 Comp. The number of cells in which neurites appeared/Total number of cells (concentration of compound solution) 24 hour 48 hour 1123/50 (0.1mM)2/50 (0.1mM) Control1/501/50 1203/50 (0.2mM)3/50 (0.2mM) Control0/502/50 1283/50 (0.5mM)4/50 (0.1mM) Control1/502/50 1364/50 (0.5mM)3/50 (0.2mM) Control2/502/50 2083/50 (0.5mM)6/50 (0.2mM) 2/50 (0.2mM)5/50 (0.5mM) Control1/502/50 1602/50 (0.2mM)3/50 (0.1mM) Control1/502/50 1683/50 (0.2mM)3/50 (0.5mM) Control1/502/50 1764/50 (0.2mM)4/50 (0.2mM) Control1/502/50 1842/50 (0.1mM)3/50 (0.1mM) Control1/502/50 Comp. The number of cells in which neurites appeared/Total number of cells (concentration of compound solution) 24 hour 48 hour 1443/50 (0.5mM)4/50 (0.1mM) Control2/503/50 1522/50 (0.1mM)3/50 (0.1mM) Control1/500/50 2242/50 (0.1mM)3/50 (0.1mM) Control1/502/50 27318/50 (0.5mM)22/50 (0.5mM) 15/50 (0.2mM)16/50 (0.2mM) 10/50 (0.1mM)8/50 (0.1mM) Control1/502/50 30416/50 (0.5mM)17/50 (0.5mM) 12/50 (0.2mM)14/50 (0.2mM) 8/50 (0.1mM)7/50 (0.1mM) Control1/502/50 31217/50 (0.5mM)18/50 (0.5mM) 13/50 (0.2mM)13/50 (0.2mM) 6/50 (0.1mM)8/50 (0.1mM) Control0/501/50 Comp. The number of cells in which neurites appeared/Total number of cells (concentration of compound solution) 24 hour 48 hour 2746/50 (0.2mM)6/50 (0.5mM) 4/50 (0.1mM)4/50 (0.2mM) Control1/501/50 3206/50 (0.5mM)3/50 (0.5mM) 5/50 (0.1mM) Control1/500/50 3283/50 (0.1mM)3/50 (0.1mM) Control1/501/50 3363/50 (0.1mM)5/50 (0.1mM) Control1/502/50 3443/50 (0.1mM)3/50 (0.1mM) Control1/501/50 3525/50 (0.2mM)3/50 (0.2mM) Control0/501/50 3606/50 (0.5mM)3/50 (0.1mM) 5/50 (0.1mM) Control1/501/50 3686/50 (0.2mM)2/50 (0.2mM) Control2/501/50 3765/50 (0.2mM)5/50 (0.2mM) Control1/501/50 Comp. The number of cells in which neurites appeared/Total number of cells (concentration of compound solution) 24 hour 48 hour 38414/50 (0.5mM)17/50 (0.5mM) 10/50 (0.2mM)10/50 (0.2mM) Control1/503/50 39215/50 (0.5mM)21/50 (0.5mM) 10/50 (0.2mM)12/50 (0.2mM) Control1/503/50 4009/50 (0.5mM)13/50 (0.5mM) 8/50 (0.2mM)11/50 (0.2mM) Control0/502/50 40810/50 (0.5mM)11/50 (0.5mM) 7/50 (0.2mM)8/50 (0.2mM) Control2/501/50 4169/50 (0.5mM)9/50 (0.5mM) 6/50 (0.2mM)7/50 (0.2mM) Control2/502/50 4245/50 (0.2mM)2/50 (0.1mM) 3/50 (0.1mM) Control1/501/50 4326/50 (0.5mM)8/50 (0.5mM) 6/50 (0.5mM)7/50 (0.2mM) Control2/503/50 4404/50 (0.5mM)4/50 (0.1mM) 3/50 (0.1mM) Control2/501/50 Experimental example 2Curative effect on rats with crushed sciatic nerves: The curing effect of the compound of the invention was tested on rats having crushed sciatic nerves as a model of peripheral nervous disorder using (1) a change in the action of the hind paw with the crushed sciatic nerves and (2) a change in the weight of the muscle as an index of the course of degeneration and regeneration of peripheral nerves. In the experiment, male Wistar rats (6 weeks old), 10-15 per group, were used. The sciatic nerves were crushed by a method similar to the method of Yamatsu et al. (see Kiyomi Yamatsu, Takenori Kaneko, Akifumi Kitahara and Isao Ohkawa, Journal of Japanese Pharmacological Society, 72, 259-268 (1976) and the method of Hasegawa et al. (see Kazuo Hasegawa, Naoji Mikuni and Yutaka Sakai, Journal of Japanese Pharmacological Society, 74 721-734 (1978). Specifically, under anesthesia with pentobarbital (40 mg/kg, i.p.), the left side sciatic nerve was exposed at the femur and a given site was crushed with hemostat (2mm in width) for 30 seconds. After crushing, the operated site was immediately sitched. Vincristine, known to delay the regeneration of peripheral nerves, was administered intraperitoneally at 100 µg/kg per week. Test compounds selected from the compounds of the invention were administered intraperitoneally or orally once a day from the day of operation to the 30th day. A group to which 0.9% saline was administered was used as control. (1) Functional change in the hind paw with crushed nerves.Twitch tension, a temporary tension accompanied by contraction of muscles controlled by electrical stimuli of motor nerves, reflects functional changes of nerves and muscles similar to those of interdigital distances described below. Thirty days later, the twitch tension of rats was measured under anesthesia with chloral hydrate (400 mg/kg, i.p.) according to the method described by Kern et al., in J. Neurosci. Methods 19: 259, 1987. After the hair of the hind paws of rats were shaved, the hind paws were coated with cardiocream. Electrodes with crocodile clips were attached to the skins of the hind paws. A cathode was attached to the rear portion of the greater trochanter and the anode was attached to the rear portion 1 cm distal from the cathode, and 1 cm toward its back. Rats were fixed with laying on their backs and their hind paws to be measured are fixed upright. One end of a 20-cm silk thread was tied to the distal joint of the third toe of the hind paw to be measured and at the other end to a tension transducer and an isotonic contraction of the bending muscle of the third toe was recorded on polygraph as electrically stimulated. An electric stimuli was carried out at 100 V for 1 millisecond at a square wave of 2 Hz. Static tension was 15 - 30 g and 10 stimuli were repeated 3 times at a 15-second interval. Contraction was represented by tension g. The recovery rate of contraction [left side/right side (%)] was calculated from the measurement of both hind paws. The test compounds were found to enhance the recovery of twich tension, which is an electrophysiological index, and to improve symptons. The distance between digits was measured because this is a good index which functionally shows the degeneration and regeneration of the nerve and its change can be measured with the lapse of time. According to the method of Hasegawa [Hasegawa, K., Experientia 34, 750-751 (1978)], the distance between the first and fifth digits of the hind paw was measured and the ratio of a crushed-side distance to a normal-side distance was calculated. The distance between the digits of the hind paw with crushed nerves was no more than 40% of that of the normal hind paw. The recovery of the interdigital distance started 7 - 16 days later. Drug-administered groups had tendency of quicker recovery from 24th day to 30th day, that is a last day for measurment, compared to the controls. The results are shown in Table 9. (2) Change in the weight of muscleIt is known that the removal of a nerve or its disorder causes atrophy of the muscle which is under its control, and the atrophy is gradually cured by recontrol by the nerve. For this reason, a change in the weight of the muscle, which is quantitative, was selected as an index. 30 days after the operation, the soleus muscles of both sides of paws were measured under anesthesia. The ratio of the weight of the soleus muscle on the crushed side to that of normal side was calculated and expressed in percentage (%). The results show that the test compounds are useful as improvers and therapeutic agents for the disorder of peripheral nerves. Rate of recovery of the interdigital distanceDose mg/kg Days after crush 7 14 16 18 20 Control37.2±3.739.1±3.336.9±2.041.1±6.343.4±10.7 7.542.6±6.837.6±3.538.4±3.840.9±6.245.6±14.0 1539.8±5.238.2±2.839.4±2.540.5±4.246.7±7.3 3038.8±4.439.2±3.438.3±3.540.8±4.543.8±6.7 Rate of recovery of the interdigital distanceDose mg/kg Days after crush 22 24 26 28 30 Control49.6±15.152.9±19.256.3±20.857.7±21.963.0±23.0 7.546.8±13.248.2±15.254.8±18.366.9±19.664.0±21.2 1550.0±10.056.8±17.862.2±18.765.5±19.870.1±21.4 3047.8±11.557.0±16.160.9±18.868.6±17.173.6±20.0 The ratio of the weight of the soleus muscle on the crushed side to that of normal side (%) in (1) and (2), Mean ± S.D. (n= 15) Experimental example 3Promoting effect on the improvement of motor imbalance due to injury of the rat's brain cells by transplantaion of fetal cerebral cells:-Nigral dopaminergic nerve cells at the left side of the brain of 4-week old female Wistar rats (body weight 100 g) were lesioned by injecting a very small quantity of 6-hydroxydopamine. The rats showed a tendency to rotate spontaneously in a direction opposite to the lesioned side for several days, but no apparent abnormal action was observed after that. Upon administration of methamphethamine (5 mg/kg, i.p.) to the rats having the lesioned nigral dopaminergic nerve cells, they began rotational movement toward the lesioned side. After two weeks from the destruction by the administration of the drug, portions of the truncus corporis callosi-containing dopamine cells. (i.e., substantia nigra and the tagmentum at the abdomen side) were cut from the brain of a fetal rat of 14 to 17 days of age, cut finely, and treated with trypsin. Then, the extracted tissues were incubated at 37°C for 30 minutes, and the tissues were subjected to pipetting to form a suspension. Five microliters of the suspension was transplanted each into two sites of the caudate nucleus of the lesioned side (10 microliters in total, about 10⁵ cells). Test compounds of the present invention was administered (i.p., or p.o.) over 14 days from the day of transplantation. The rotational movements induced by administration of methamphetamine were examined 2 weeks and 1 week before, and 2 weeks, 4 weeks, 6 weeks and 8 weeks after, the transplantation and the administration of the drug. The number of rotational movements within one minute was counted at intervals of 10 minutes after the administration of methamphetamine, and the total number of rotational movements counted six times was averaged to find a mean number of the rotational movements. The test compounds apparently reduced the number of rotational movements on each test day as compared to controls so that the test compounds are found to be useful as improvers and therapeutic agents for the disorders of the peripheral nerves. Exprimental examples 4Improvement of learning and memory of mice with nerve disorder induced by mercury poisoning, and recovery effect:-Male Balb C strain mice, 7 weeks old, were first caused to learn at T-shaped maze three times in a week so that they run straight from a starting point to a safety area. Then, methylmercury chloride (MMC for short) was administered orally to 8 weeks old mice for 6 days in a dose of 6 mg/kg/day. A group of mice to which saline was administered in a dose of 0.1 ml/10g/day was used as a control group. Beginning with the day next to the day of administering MMC, compounds of the present invention were intraperitoneally administered over 10 days. On the sixth day after administration of the drug (namely, on the 12th day after start of the experiment), learning of the T-shaped maze was resumed, and the running behaviour of the mice were observed. The number of mice which could be experimented in the T-shaped maze on the 10th and 11th days after the resumption (21st and 22nd days after the start of the experiment) was counted and expressed as a denominator. The number of mice which ran to the safety area within 5 seconds at least 8 times out of ten trial runnings was counted and expressed as a numerator. The decrease in the number of the test animals was due to death by MMC poisoning. The time (seconds) required for the animals to run to the safety area was measured, and the mean ± standard error (SE) was calculated. The results demonstrate the effect of the compounds of the invention to improve learning and memory of the mouse and their recovery effect. Experimental example 5The acute toxicity of the compounds of the invention was examined by the following method. Male ddy-strain 5-week old mice, 4-6 per group, were used as experimental animals. Each of the compounds was dissolved or suspended in saline and administered perorally (p.o.) or intraperitoneally (i.p.), and the toxicity of the compound was assessed 24 hours after the administration. The results are shown in Table 10. Acute toxicity in mouse Comp. No. Estimated LD₅₀ (mg/kg i.p.) 104>1000 112>1000 120>1000 128>1000 136>1000 152>1000 160500∼1000 168>1000 176>1000 192500∼1000 200>1000 208>1000 216500∼1000 223>1000 232>1000 240>1000 248>1000 Acute toxicity in mouse Comp. No. Estimated LD₅₀ (mg/kg i.p.) 256>1000 264>1000 272250∼500 273>500 274250∼500 280>1000 288>1000 296>1000 304>250∼500 312>500 320>500 328250∼500 336250∼500 344250∼500 352>500 360>500 368>500 376>500 384>500 392>500 400>500 408>500 416>500 424>500 432>500 440>500 Effect of the Invention:The compounds of general formula (I) provided by this invention have a promoting effect on the proliferation of nerve cells and the formation and sprouting of neurites and a nerve regenerating effect and a motor function recovering effect in rats and mice having nerve disorders, and can be used suitably for improving and curing neurological diseases such as disorders of peripheral nerves or central nerves and dementia. They are expected to be used also suitably for the recovery, improving and curing of neurological diseases caused by disorder of nervous tissues and cells which have to do with perceptive and sensory functions and an autonomic function. It has been found that the compounds of the invention have biological activities equal to, or higher than, those of isaxonine as a control as shown in Experimental Examples 1 to 4 and Tables 7 to 9. The toxicity of the compounds of this invention are generally weak as shown in Experimental Examples 5 and Table 10. Thus, the compounds of this invention are generally considered to be highly active and highly safe drugs and very useful with weak toxicity.
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Claims for the following Contracting States : AT, BE, CH, DE, DK, FR, GB, IT, LI, NL, SEA compound which is a pyrimidine derivative of formula (I) wherein X is a group selected from: wherein R¹ and R1' may be the same or different and are hydrogen, lower alkyl, benzyl, phenyl or lower alkoxycarbonyl; wherein R2' and R3' are lower alkyl; or wherein R4' is hydrogen, lower alkyl, phenyl or benzyl; and Y is a group of the formula:- wherein R² is hydrogen or lower alkyl and R³ is lower acyl, wherein R⁴ is hydrogen, trifluoromethyl, hydroxyl, cyano, formyl, lower acyl, lower akoxycarbonyl or fluorosulfonyl; wherein R⁵ is hydrogen, lower alkyl, or phenyl; provided that when Y is and R³ is lower acyl or X is a group of the formula:- or a pharmaceutically acceptable salt thereof. A compound according to claim 1 in which the pharmaceutically acceptable salt is a hydrochloride, hydrobromide, sulfate, bisulfate, phosphate, acidic phosphate, acetate, maleate, fumarate, succinate, lactate, tartrate, benzoate, citrate, gluconate, glycarate, methane sulfonate, p-toluenesulfonate, naphthalene sulfonate or quaternary ammonium. A compound as claimed in claim 1 or 2 for use as an active therapeutic substance. A compound as claimed in claim 1 or 2 in a combined preparation with another therapeutically active ingredient for simultaneous, separate or sequential use in the treatment of neurological disease. A therapeutic agent for the treatment of a neurological disease comprising a compound as claimed in claim 1 or 2 as an active ingredient. Claims for the following Contracting State : ESA process for producing a compound which is a pyrimidine derivative of formula (Ia) wherein X is a group selected from: wherein R¹ and R1' may be the same or different and are hydrogen, lower alkyl, benzyl, phenyl or lower alkoxycarbonyl; wherein R2' and R3' are lower alkyl; or wherein R4' is hydrogen, lower alkyl, phenyl or benzyl; and R² is lower alkyl, and R³ is lower acyl, wherein R⁴ is hydrogen, trifluoromethyl, hydroxyl, cyano, formyl, lower acyl, lower alkoxycarbonyl or fluorosulfonyl; provided that when R³ is lower acyl or X is or a pharmaceutically acceptable salt thereof, said process comprising reacting R³-Cl with a compound of formula (II) wherein X, R² and R³ are as defined herein, to obtain a derivative of formula (Ia), and optionally converting said derivative into a pharmaceutically acceptable salt. A process for producing a compound which is a pyrimidine derivative of formula (Ib) wherein X is wherein R¹ and R1' may be the same or different and are hydrogen, lower alkyl, benzyl, phenyl or lower alkoxycarbonyl; and Y is wherein R⁵ is hydrogen, lower alkyl or phenyl, or a pharmaceutically acceptable salt thereof, said process comprising reacting a carbonyl chloride of formula R⁵COCl with a compound of formula wherein X is as defined herein, to obtain a derivative of formula (Ib) and optionally converting said derivative into a pharmaceutically acceptable salt. A process for producing a compound which is a pyrimidene derivative of formula (Ic) wherein X is as defined in claim 1 and Y is or a pharmaceutically acceptable salt thereof, said process comprising reacting a compound of formula SOCl₂ with a compound of formula (IV) wherein X is as defined herein and n is 3 or 4, to obtain a derivative of formula (Ic), and optionally converting said derivative into a pharmaceutically acceptable salt. A process according to claim 3 in which the compound of formula (IV) is obtained by reacting a compound of formula H₂N-(CH₂)n-COOH wherein n is as defined in claim 3 with a compound of formula (III) wherein X is as defined in claim 3. A process according to claim 1, 2 or 3 in which the pharmaceutically acceptable salt is a hydrochloride, hydrobromide, sulfate, bisulfate, phosphate, acidic phosphate, acetate, maleate, fumarate, succinate, lactate, tartrate, benzoate, citrate, gluconate, glycarate, methane sulfonate, p-toluenesulfonate, naphthalene sulfonate or quaternary ammonium.
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MITSUI PETROCHEMICAL IND; MITSUI PHARMACEUTICALS; MITSUI PETROCHEMICAL INDUSTRIES, LTD.; MITSUI PHARMACEUTICALS, INC.
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AWAYA AKIRA; HORIKOMI KAZUTOSHI; IKEDA KEN; ISHIGURO MASAHARU; KIHARA NORIAKI; KITAHARA TAKUMI; KOKUBUN YUICHIRO; MIZUCHI AKIRA; SASAKI TADAYUKI; TOMINO IKUO; AWAYA, AKIRA; HORIKOMI, KAZUTOSHI; IKEDA, KEN; ISHIGURO, MASAHARU; KIHARA, NORIAKI; KITAHARA, TAKUMI; KOKUBUN, YUICHIRO; MIZUCHI, AKIRA; SASAKI, TADAYUKI; TOMINO, IKUO
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EP-0489926-B1
| 489,926 |
EP
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B1
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EN
| 19,950,510 | 1,992 | 20,100,220 |
new
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B41J29
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B41J3, B41J29
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B41J29, B41J3
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B41J 3/36
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PORTABLE PRINTER
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A portable printer suitable for and easy of carrying and conveying as well as less susceptible to damage to the printing mechanism thereof. The printer is provided with a plurality of cases (1, 2), a printing mechanism (10) housed in said case (1, 2) for printing on the sheet (100), and connecting means (3) for connecting a plurality of said cases (1, 2) with wider parts (1a, 2a) of the outer surfaces thereof opposite and adjacent to each other when printing on the sheets (100) with said printing mechanism (10), and is in such a structure that the positional relation between a plurality of said cases (1, 2) can be changed so that said cases (1, 2) is in an approximate flat arrangement as a whole when printing is not performed. The above structure enables a plurality of cases (1, 2) to be connected by connecting means (3) so as to be adjacent and opposite to each other at wider parts (1a, 2a) of the outer surfaces thereof when printing on the sheet (100) with the printing mechanism (10), whereas, when printing is not performed, the positional relation between a plurality of cases (1, 2) can be changed so that said cases (1, 2) as a whole is in an approximate flat arrangement. In either case, the printing mechanism (10) is housed in the cases and not exposed to the outside.
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The present invention relates to a portable printer able to be carried and transported by hand. The wide-spread use of portable type personal computers and word-processors has led to a growing need for portable printers that can be conveniently carried and transported by hand. To provide a good portability and transportability thereof, a printer able to be carried and transported by hand must have an appropriate spatial configuration, in addition to being made compact and lightweight. Typical conventional printers having detachable printer heads are known, but it is not possible to change the configurations of these printer bodies perse, since the casings of the printer bodies are formed integrally as a one-body construction. A small printer is known, however, in which the casing thereof can be separated into two sections, i.e., upper and lower sections, to be freely openable and closable, and thus can perform a printing of normal papers and of passbooks and bankbooks. A printer head and a first paper feeder roller are provided in the upper casing side, and a platen and a second paper feeder roller are provided in the lower casing side. (Japanese Examined Patent Publication No. 63-238). In EP-A-0 219 624 is disclosed a printer having two housings which normally lie in the same plane and which are rockably connected to each other, so that, in use, the housings are deformed into an inverted generally L-shape. In one of these housings are provided the printing mechanism and paperfeeding mechanism. JP-A-61 112 942 discloses a foldable printer having a printing unit comprising a printing portion and an input unit having an inputting portion. The input unit is connected to the printing unit through cables and is rotatably connected to the printing unit about a horizontal axis. This printer is constructed so that the height of the input unit at the rear end thereof is substantially identical to the height of the printing unit at the front end thereof, so that in an operative position, the input unit is substantially flush with the printing unit. JP-A-56 095 848 discloses a small collapsible and portable printer having two elements which are electrically interconnected through flexible conductors. The printing mechanism and the paper feeding mechanism are both provided in one of the elements. The general type of printers having an overall configuration which cannot be changed must be carried or transported as when used, and therefore, are not suitable for hand-carrying or transporting. Even the openable and closable type printer described above, must be carried or transported in the form similar to that when used for printing, and thus it is not truly convenient for carrying and transporting. Further, in the openable and closable type printer, when the casing is opened, a wide gap exists between the printer head and the platen, allowing an external exposure of the delicate printing mechanism. This creates the possibility that the operator may touch the electronic elements and damage same, or foreign matter may enter therein to cause damage to the mechanism. The present invention is intended to solve the above-mentioned problems of the prior art. Therefore, an object of the present invention is to provide a portable printer which can be easily and conveniently hand-carried or transported and in which the possibility of damage to the printing mechanism thereof is lowered. To accomplish the above-mentioned object, a portable printer according to the present invention, as exemplified in Fig. 1, comprises a plurality of casings 1, 2, a printing mechanism 10 housed within the casings 1, 2 for performing a printing on a paper 100, and a connecting means 3 for connecting the plurality of casings 1, 2 by mating wider surfaces 1a and 2a among the outer surfaces of the respective casings 1, 2, when a printing on the paper 100 by the printing mechanism 10 is performed, and when a printing is not performed, the relative positional relationship to each other of the plurality of the casings 1, 2 can be varied, to thus form an essentially flat configuration thereof overall. The plurality of casings 1, 2 can be connected by the connecting means 3 such that the plurality of casings 1, 2 have an essentially flat configuration overall when a printing on the paper 100 is not performed. Further, the portable printer according to the invention may be constructed such that the connecting means 3 connects the plurality of casings 1, 2 for an opening and closing thereof. Two casings 1, 2 can be provided and these two casings 1, 2 can be connected at the lower ends thereof by the connecting means 3 when a printing is performed. A dummy connecting means 9, which performs essentially the same action as the connecting means 3 with respect to each of the casings 1, 2, can be provided in parallel to the connecting means 3, and a cable 31 for an electrical connection between the plurality of casings 1, 2 inserted through the dummy connecting means 9. The connecting means 3 can comprise a twin axle type hinge pivotally journaled on both of the casings 1, 2 to be connected by the connecting means 3. Also, an elastic body 8 can be disposed between the twin axle type hinge 3 and the casings 1, 2, to restrict a free motion of the twin axle hinge 3. Further, the two casings 1, 2 can be provided with the printing mechanism 10 housed in one of the casings 1 and a paper feed mechanism 20 for feeding the paper 100 housed in the other casing 2. Also, the printing mechanism 10 can be arranged in the casing 1 housing at a downstream side thereof with respect to a feed direction of the paper 100 by the paper feeder mechanism 10, and housing the paper feed mechanism 20 arranged at the upstream side of the casing 2. Furthermore, condition holding means 37, 38 can be provided for maintaining the condition of the wider surfaces 1a, 2a of the outer surfaces of the plurality of casings 1, 2 when mated to each other. The condition holding means 37, 38 can comprise a magnet 37 provided on one of the plurality of the casings 1, 2 and a magnetically conductive member 38 provided on the other casing 1, 2. Further, the magnet 37 can be provided on the one of casings 2 in a recess in the surface thereof, and the magnetically conductive member 38 can be provided on the other casing 1 in such a manner that it can be projected and retracted with respect to the surface thereof. Furthermore, a paper feed path 7 for passing the paper 100 can be extended through the two casings 1, 2. Also, slits 7a, 7b can be formed in the wider surface 1a, 2a of the casings 1, 2 at an intermediate position in the paper feed path 7, in alignment with each other. Among this plurality of slits 7a, 7b, the slit 7a positioned at the downstream side with respect to the paper feed direction has a wider opening than the slit 7b positioned at the upstream side thereof. Also, support means 35, 36 can be provided for supporting the casings 1, 2 when standing, for example, on the floor, at a position in which the wider surfaces 1a, 2a of the plurality of casings 1, 2 are mated to each other. The support means 35, 36 can be projectably and retractably provided in the casings 1, 2. Further, a ribbon cassette 14 can be detachably disposed within the casing 1, in which the printing mechanism 10 is housed, and a lid 44 for opening and closing the side wall of the casing 1 to expose the ribbon cassette 14, pivotally mounted on the casing 1, to thus pivot about the vicinity of the lower end thereof. Also, a power switch 45 can be provided between the casings 1, 2 in such a manner that it is not externally exposed when the casings 1, 2 are formed into the essentially flat configuration overall. Furthermore, a receptacle cover 47 can be provided for receiving the plurality of casings 1, 2 when formed into the flat configuration. Also a partitioning plate 47a can be provided for the receptacle cover 47, for partitioning the casings 1, 2 and other associated materials 48. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a sectional side elevation view of the first embodiment of the present invention when in a condition of use; Fig. 2 is a perspective view of the first embodiment of the invention when in a condition of use; Fig. 3 is a bottom view of the first embodiment of the invention when in a condition of use; Fig. 4 is a sectional side elevation view of the first embodiment of the invention when in a condition for hand-carrying; Fig. 5 is a schematic and transparent front elevation view of the first embodiment of the invention when in the condition for hand-carrying; Fig. 6 is a back elevation view of the first embodiment of the invention when in the condition for hand-carrying; Fig. 7 is a perspective view of a pivot portion in the first embodiment of the invention; Fig. 8 is a sectional view of the pivot portion in the first embodiment of the invention; Fig. 9 is a perspective view of a cable guide in the first embodiment of the invention; Fig. 10 is a sectional view of the cable guide in the first embodiment of the invention; Fig. 11 is a enlarged partial sectional view of the first embodiment of the invention; Fig. 12 is a schematic illustration showing a paper feed path slit in the first embodiment of the invention; Fig. 13 is a perspective view of the first embodiment of the invention when in a condition for exchanging the ribbon cassette; Fig. 14 is a perspective view of a receptacle cover in the first embodiment of the invention; Fig. 15 is a side elevation of the second embodiment of the invention when in a condition of use; Fig. 16 is a side elevation of the second embodiment of the invention when in a condition of hand-carrying; Fig. 17 is a schematic side elevation of the third embodiment of the invention when in a condition of hand-carrying; Fig. 18 is a schematic plan view of the third embodiment of the invention when in a condition of hand-carrying; Fig. 19 is a schematic side elevation of the third embodiment of the invention when in a condition of use. FIRST EMBODIMENTAn embodiment will be discussed with reference to the drawings. Figure 1 through 14 show the first embodiment of the present invention, wherein Figs. 1 to 3 illustrate a condition in which a portable printer is used for printing, and Figs. 4 to 6 illustrate a condition in which the portable printer is not to be used but is to be transported or stored. As shown in the respective figures, the portable printer is externally covered with first and second mutually independent casings 1 and 2. These two casings 1 and 2 are connected to each other by hinges 3, for a relative pivotal motion thereof with respect to each other. As shown in Figs. 1 and 5, a printing mechanism 10 and batteries 50 are disposed within the first casing 1, and a paper feed mechanism 20 and a control circuit board 30 are disposed within the second casing 2. The overall construction of the printing mechanism 10 is housed in the first casing 1. Namely, a platen 11 and a guide shaft 17 parallel thereto are rigidly secured in the first casing 1 and a carriage 13 slidably supported on the guide shaft 17 is driven for a reciprocating motion thereof along the guide shaft 17 by a space motor 15 via a drive belt 16. A printing head 12 is mounted on the carriage 13 in opposition to the platen 11, and a ribbon cassette 14 is detachably mounted on the carriage 13 such that an inked ribbon 14a lies between the printing head 12 and the platen 11. With this construction, when the carriage 13 is driven by the space motor 15, the printing head 12 travels along the platen 11, while maintaining the opposing relationship thereof with the platen 11, to perform a printing of one line. Further, the overall construction of the paper feeder mechanism 20 is housed in the second casing 2. Namely, three pairs of paper feed rollers 21 and 22 are mounted on rotary shafts 21a and 22a in the second casing 2, and among these rollers 21, 22, the primary drive rollers 21 are rotatingly driven by a line feed motor 24 via a gear mechanism 26. Furthermore, idling rollers 22 are rotatably mounted on an arm 28 pivotally supported within the second casing 2 for a pivotal motion about a shaft 27. The arm 28 is biased in a direction represented by the arrow A by a spring 29, and accordingly, the idling rollers 22 are pressed onto the primary drive rollers 21 and rotated therewith. Note, the arm 28 and the spring 29 are not shown in Fig. 5. The control circuit board 30 fixedly secured within the second casing 2, occupies a large space within the second casing 2 and outputs a variety of signals to the space motor 15, the printing head 12, the line feed motor 24 and so forth, through a flexible cable 31. Reference numeral 45 denotes a power switch of the portable printer, arranged in a recess formed in the second casing 2 such that it does not project from the surface of the second casing 2. Reference numeral 46 shown in Fig. 2 denotes various operation switches for a printing intensity control, line feed, on-line/off-line, and so forth. The first and second casings 1 and 2 constructed as set forth above are connected to each other by a pair of the hinges 3, for a relative pivotal movement thereof, whereby the first and second casings 1 and 2 can be opened and closed relative to each other. While in use, i.e., while performing a printing on a paper 100 by the printing mechanism 10, the casings 1 and 2 are placed in a closed position by mating wider surfaces 1a and 2a among the external surfaces thereof, as shown in Figs. 1 to 3. This position will be hereafter referred to as the closed position . At this time, the casings 1 and 2 are connected to each other at the inner sides of the lower ends by the hinges and placed vertically on a desk (floor) 99. Accordingly, even when the casings 1 and 2 are slightly opened as shown by the two dotted line in Fig. 1, the casings 1 and 2 will move in a closing direction (arrow B) thereof under their own weight, to thereby maintain the closed position thereof, as long as the center of gravity of each casing 1 and 2 is maintained inside of the outer end of legs 35 and 36 discussed later. Also, in this closed position, the switches including the power switch 85 are positioned at the upper side thereof. While not in use, i.e., when carried and transported, the casings 1 and 2 can be opened to an angle of 180°, as shown in Figs. 4 to 6. Since the casings 1 and 2 both have substantially the same thickness, when in the flat position they form a construction of an A4 size, for example, overall, and thus can be held in the hand or can be placed in a bag for facilitating a carrying or transporting thereof. Also, this position facilitates a storage thereof requiring less space. This position will be hereafter referred to as the open position . On the external surfaces of the casings 1 and 2, which are mated to each other when in the open position, a permanent magnet 32 is secured to one of the surfaces and a steel plate 33 is secured to the other surface thereof. Therefore, when in the open position, due to an attraction force between the permanent magnet 32 and the steel plate 33, the casings 1 and 2 are maintained in the open position. Thereafter, by exerting a predetermined magnitude of force in the closing direction, the casings 1 and 2 can be folded into the closed position. Even in the open position, the printing mechanism 10 constituted of the platen 11 and the printing head 12 and so forth is not separated but is maintained as one body housed in the first casing 1. Therefore, the opposing faces of the platen 11 and the printing head 12 and so forth, are not externally exposed. For a pivotal connection of the casings 1 and 2 by the hinges, a twin axle hinge, in which two axles 3a and 3b are extended in a parallel relationship as shown in Fig. 7, is employed. As shown in Fig. 8, the hinges 3 are received in recesses 1b and 2b of the casings 1 and 2 such that they do not project from the outer surfaces of the casings 1 and 2. The first axle 3a is supported on the first casing 1 and the second axle 3b is supported on the second casing 2. Accordingly, the hinges 3 are respectively journaled on the casings 1 and 2, for a rotation thereof. Further, in either the closed position or the open position, the hinges 3 hold the casings 1 and 2 in close contact with each other such that a space therebetween is not formed. Furthermore, as shown in Fig. 8, the recesses 1b and 2b of the casings 1 and 2 are provided with pieces of an elastic felt 8, in such a manner that they are sandwiched between the surfaces of the hinges 3. Accordingly, the hinges 3 are constantly biased by the elastic force of the felt 8, to thereby restrict any free movement thereof and prevent play while in motion, and to eliminate noise. As shown in Figs. 3, 5 and 6, a cable guide 9 is provided between the casings 1 and 2, and a flexible cable 31 is passed therethrough. The cable guide 9 is extended in parallel to the hinges 3. As shown in Fig. 9, the cable guide 9 has essentially the same external configuration as the hinges 3 and forms a dummy hinge (dummy connecting means) journaled on each casing by axles 9a and 9b for a rotation thereof, in the same way as the hinges 3. The cable guide 9 is separated into upper and lower parts at a straight line extending through the center of the axles 9a and 9b, and a groove 9c is formed on the separated surface and the cable guide 9 is passed through the inner side thereof. As shown in Fig. 10, holes 1e and 2e are formed in the wall sections of the respective casings 1 and 2 adjacent to the cable guide 9, so that the flexible cable 31 can be passed therethrough. Accordingly, since the flexible cable 31 is not externally exposed, an enhanced external appearance can be provided. Furthermore, during an opening and closing of the casings 1 and 2, the flexible cable 3 will not be subjected to tension or bending by the casings 1 and 2, and thus no stress will be exerted on the flexible cable 31. Also, the flexible cable 31 will not interfere with the opening and closing of the casings 1 and 2. Returning to Fig. 1, on the wider surfaces 1a and 2a of the casings 1 and 2, which are mated to each other in the closed position, a permanent magnet 37 is secured to one of the surfaces and a steel strip 38 is secured to the other surface. In the closed position, the attraction force between the permanent magnet 37 and the steel strip 38 maintains the casings 1, 2 in the closed position, and exerting a predetermined force in the opening direction (opposite direction to the arrow B), the casings 1 and 2 can be placed in the open position. It should be noted that, as shown in Fig. 11, the permanent magnet 37 is provided on the surface of the casing 2 in a recess therein to avoid a direct contact with other items holding magnetically recorded data, such as a cash card, telephone card and so forth. On the other hand, the steel strip 38 is biased inward by a weak spring 39 so that it does not extend from the surface of the casing 1 in the open position. In the closed position, however, the steel strip 38 extends from the surface of the casing 1 against the force of the spring 39, to be engaged with the permanent magnet 37. If the spring 39 has too large a biasing force, and accordingly, the permanent magnet 37 cannot draw out the steel strip 38 for engagement, the steel strip 38 can be moved to the engaged position with the permanent magnet 37 by a push button not shown. As shown in Fig. 3, the legs 35 and 36 are respectively provided on respective bottom surfaces of the casings 1 and 2 in the closed position. The respective legs 35 and 36 are able to rotate by 90°. The casings 1 and 2 are provided with recesses having depths corresponding to the thickness of the legs 35 and 36 at the leg mounting sections, so that the bottom faces of the legs 35 and 36 are positioned flush with the bottom surface of the casings 1 and 2. The legs 35 and 36 are respectively extended outwardly, as shown by the solid line, when the casings 1 and 2 are placed in the closed position. On the other hand, when the casings 1 and 2 are in the open position, they are retracted and do not project from the casings 1 and 2. To maintain the retracted position, click fasteners are formed by projections 35b and 36b on the legs 35 and 36 and recesses 35c and 36c in the casings 1 and 2. Returning to Fig. 1, the paper feed paths 7 for feeding the paper 100 are formed in the casings 1 and 2 such that they are aligned in the closed position of the casings 1 and 2. In this embodiment, a push-in type paper feed, in which the paper 100 is fed from the paper feed mechanism 20 to the printing mechanism 10, is employed. Note, it is possible to employ a draw type paper feed, in which the paper fed mechanism 20 is positioned downstream of the printing mechanism 10 with respect to the paper feed direction. A paper insertion guide plate 43 is provided at the inlet portion of the paper feed path 7 of the second casing 2, for a free opening and closing. Upon printing, the paper 100 can be guided along the paper insertion guide plate 43 in the open position into the paper feed path 7. The paper feed path 7 is designed to pass the paper 100 between the primary drive roller 21 and the idling roller 22 and between the platen 11 and the printing head 12. Slits 7a and 7b having a width allowing the printing paper 100 to pass therethrough are provided in the wider surfaces 1a and 2a, which are positioned adjacent to and mating with each other at an intermediate position of the paper feed paths 7. As shown in Fig. 12, these slits 7a and 7b are shaped such that the slit 7a in the first casing 1, which is positioned downstream with respect to the paper feed direction, has a wider opening than the slit 7b of the second casing 2 positioned at the upstream side. Here, for example, the width of the slit 7a of the first casing 1 is approximately 3 mm and the width of the slit 7b of the second casing 2 is approximately 1 mm. Accordingly, when an offset occurs between the casings 1 and 2 in the closed position, a jamming of the paper 100 in the paper feed path 7 will not occur, and thus a smooth feed of the paper 100 from the second casing 2 to the first casing 1 can be achieved. It should be noted that it is possible to provide no substantial difference in the widths of the slits 7a and 7b, but to provide a greater chamfering for the first slit 7a instead. With the arrangement set forth above, in the closed position, the paper 100 is driven to run through the paper fend path 7 by the paper feed mechanism 20, and printing is performed on the surface of the paper 100 by the printing mechanism 100. Figure 13 shows a closure lid 44 provided on the outer surface of the first casing 1, in the open position. This position is shown by a two dotted line in Fig. 1. The closure lid 44 has a size corresponding to the range of travel of the ribbon cassette 14 and has a pivot at the lower end thereof. Accordingly, when the closure lid 44 is open, the upper portion can be widely opened. The ribbon cassette 14 is exposed within the opening, to thus facilitate an exchange of the ribbon cassette 14. Further, since the lower end of the closure lid 44 forms the paper ejecting opening 5, the printing paper 100 is positioned at the lower side of the closure lid 44 when the closure lid 44 is open. Accordingly, when the ribbon cassette 14 is exchanged midway in the printing operation, the paper 100 will not be touched, and thus will not be shifted from the printing position. Figure 14 shows the receptacle cover 47 for housing the portable printer 1 and 2 in the open position. The receptacle cover 47 has a thin box-shaped A4 size configuration and has one open side face 47a through which the portable printer in the open position can be accommodated therein and removed therefrom. Further, a partitioning plate 47b is provided in the receptacle cover 47, to position the portable printer, and associated items 48, such as an instruction manual and so forth, separately by the partitioning plate 47b. When the portable printer is accommodated in the receptacle cover 47, the carrying and transporting thereof becomes easier and safer. SECOND EMBODIMENTFigure 15 and 16 show the second embodiment of the invention. In contrast to the above-mentioned first embodiment, the hinges 3 are provided on the opposite side. Namely, as shown in Fig. 15, in the closed position when placed vertically, the hinges 3 are located at the upper end. The other portions are the same as in the first embodiment. With such a construction, as shown in Fig. 16, in the closed position, the power switch 45 is located between the casings 1 and 2 and is not externally accessible. Such an arrangement is advantageous as it avoids the possibility of an unintentional power ON/OFF. It should be noted that, in the above-mentioned embodiment, a switching between the use condition (closed portion), in which the wider surfaces 1a and 2a of the casings 1 and 2 are mated, and the carrying condition (open position), in which the casings 1 and 2 are positioned in a flat configuration, is performed by relatively pivoting the cases 1 and 2 about the hinges 3, for an opening and closing thereof. It is possible to connect the casings 1 and 2 by connecting devices other than hinges (for example, a sliding engagement mechanism of the engaging sections), and to change the states of the casings 1 and 2 through actions other than an opening and closing action. THIRD EMBODIMENTFigures 17 and 18 show the third embodiment of the portable printer according to the present invention, when in the open position. It should be noted that the same references numerals as in the first embodiment represent the same components. In the drawing, 1 denotes the first casing receiving therein the printing mechanism 10, and 2 denotes the second casing receiving the paper feed mechanism 20. The platen 11 is rigidly fixed in the first casing 1, and a thermal printing head 12 is arranged in opposition to the platen 11. The printing head 12 is detachably mounted on the carriage 13, as is the ribbon cassette 14. Reference numeral 14a denotes the inked ribbon arranged to run from the ribbon cassette 14 across the front face of the printing head 12. The carriage 12 is driven by the space motor 15, through a drive belt, to travel along the guide shaft 17, and accordingly, the printing head 12 travels along the platen 11, while maintaining a position opposite to the platen 11, to perform a printing of one line. Reference numeral 4 denotes a pair of side frames for supporting the printing mechanism 10 within the first casing 1, and 7a denotes a paper feed opening formed in the first casing 1 for feeding the paper across the portion between the platen 11 and the printing head 12. Further, in the second casing 2, a pair of paper feed rollers 21 and 22 are mounted on the rotary shafts 21a and 22a. Among these rollers 21, 22, the first paper feed roller 21 is driven by the line feed motor 24 through the drive belt 23, and the second paper feed roller 22 is pressed onto the first paper feed roller 21 by a tension coil spring 25. Reference numeral 6 denotes a side frame for supporting the paper feed mechanism 20 within the second casing 2, and to denotes a paper feed path defined within the second casing for feeding the paper across the portion between the pair of paper feed rollers 21 and 22. Numeral 130 denotes a control circuit section housed in the second casing 2. The control circuit section feeds a variety of signals to the space motor 15, the printing head 12, the line feed motor 24 and so forth, through the flexible cable 31, and accordingly, the conductive line will not interfere with the opening and closing of the casings 1 and 2. Also, the conductive line will not be damaged when opening and closing the casings 1 and 2. The first and second casings 1 and 2 constructed as set forth above are pivotally connected by a pair of hinge joints 103, for a relative pivotal movement thereof, whereby a relative pivoting of the casings 1 and 2 enables an opening and closing thereof. In the open position as illustrated in Figs. 17 and 18, the first and second casings 1 and 2 are at 180° from each other and become, in overall construction, a thin flat plate A4 size configuration, for example. Such a configuration facilitates of hand-carrying, carrying in a bag, and a transporting thereof. Also, as it requires less space, a storage thereof becomes easier. Further, as the printing mechanism 10 is housed in the first casing 1 in a non-separated manner, the important portions, such as the mating surfaces of the platen 11 and the printing head 12 and so forth, are not externally exposed. This open position can be maintained by the permanent magnet 32 and the steel plate 33 respectively mounted on the mating portions of the casings 1 and 2 and unless a predetermined force is applied to separate the permanent magnet 32 and the steel plate 33, the open position can be stably maintained. Reference 135 denotes platforms forming legs of the portable printer in the closed position, and two are provided for each of the casings 1 and 2. These platforms 135 may interfere with each other in the open position, and therefore, the casings 1 and 2 are recessed to receive the platforms 135 therein and permit a pivotal motion through an angle of 180°. Numerals 37 and 38 denote the permanent magnet and the steel strip mounted on the first and second casings 1 and 2 for maintaining the closed position, 40 denotes a switch mounted on the second casing 2 for turning OFF the power at a position other than the closed position, and 41 denotes an actuator projected from the first casing 1 for turning ON the switch 40 in the closed position. At a position other than the closed position, the actuator 41 does not depress the switch 40, and thus the power for the device is maintained OFF and the printing head 12, the space motor 15, the line feed motor 24 and so forth are not activated. Figure 19 shows the closed position of the portable printer in a further simplified form than that of Fig. 17. In the closed position, a gap appears between the platen 11 and the printing head, and the contacting portions of the paper feeder rollers 21 and 22 are positioned opposite to each other so that the paper 100 can be fed between the platen 11 and the printing head 12. Thus, the platforms 135 serve as legs for supporting the overall construction of the portable printer. The attracting force between the permanent magnet and the steel strip 37 and 38 stably maintains the closed position unless a predetermined force is applied in the opening direction. Further, as set forth above, the switch 40 is depressed by the actuator 41 to be released from the OFF position. Therefore, by turning ON a separately provided power switch (not shown), the power for the device can be turned ON. It should be noted that the present invention should not be limited to the foregoing embodiments. For example, any suitable retaining means other than the permanent magnet can be employed for maintaining the casings in the open and closed positions. EFFECT OF THE INVENTIONWith the portable printer according to the present invention, the overall structure is separated into a plurality of casings to thereby form a flat configuration convenient for carrying and transporting, which configuration is different from that when the printer is in use, to facilitate the carrying and transporting thereof. Further, during the carrying and transporting of the printer, the printing mechanism is not externally exposed, and therefore, it is not possible to cause damage to or a staining of the printing mechanism, and thus a good printing quality can be reliably maintained for a long time.
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A portable printer comprising: a plurality of casings (1, 2); a printing mechanism (10) housed in the casings (1, 2) for performing a printing operation on paper (100); characterised in that there is provided connecting means (3) for connecting the plurality of casings (1, 2) by mating wider surfaces (1a and 2a) of the outer surfaces of the casings (1, 2) when a printing of the paper (100) by the printing mechanism (10) is performed; and when a printing is not performed, the relative positional relationship of the plurality of the casings (1, 2) to one another can be varied to form an essentially flat configuration overall. A portable printer according to claim 1, wherein the plurality of casings (1, 2) are connected by the connecting means (3) so that the plurality of casings (1, 2) can form the essentially flat configuration overall when a printing of the paper (100) is not performed. A portable printer according to claim 2, wherein the connecting means (3) connects the plurality of casings for an opening and closing thereof. A portable printer according to claim 3, wherein two casings (1, 2) are provided and the two casings (1, 2) are connected at lower ends thereof by the connecting means (3) when a printing is performed. A portable printer according to claim 3 or 4, wherein dummy connecting means (9) performing essentially the same action as the connecting means (3) with respect to each of the casings (1, 2) is provided in parallel to the connecting means (3), and a cable (31) for electrical connection between the plurality of casings (1, 2) is inserted through the dummy connecting means (9). A portable printer according to claim 3, 4 or 5, wherein said connecting means (3) comprises a twin axle type hinge pivotally journaled on both of said casings (1, 2) to be connected by said connecting means (3). A portable printer as set forth in claim 6, wherein an elastic body (8) is disposed between said twin axle type hinge (3) and said casings (1, 2) for restricting a free motion of said twin axle hinge (3). A portable printer as set forth in any one of claims 1 to 7, wherein two casings (1, 2) are provided, said printing mechanism (10) is housed in one of said casings (1), and a paper feed mechanism (20) for feeding said paper (100) is housed in the other casing (2). A portable printer as set forth in claim 8, wherein said casing (1) housing therein said printing mechanism (10) is arranged downstream with respect to a feed direction of said paper (100) by said paper feed mechanism (10), and said casing (2) housing said paper feeder mechanism (20) is arranged upstream thereof. A portable printer as set forth in any one of claims 1 through 9, wherein condition holding means (37, 38) are provided for maintaining a condition when wider surfaces (1a, 2a) among outer surfaces of said plurality of casings (1, 2) are mated to each other. A portable printer as set forth in claim 10, wherein said condition holding means (37, 38) comprises a magnet (37) provided on one of the plurality of adjacent casings (1, 2) and a magnetically conductive member (38) provided on the other casing. A portable printer as set forth in claim 11, wherein said magnet (37) provided on one of said casings (2) is recessed from the surface thereof. A portable printer as set forth in claim 12, wherein said magnetically conductive member (38) is projectably and retractably provided on the other casing (1) with respect to the surface thereof. A portable printer as set forth in any one of claims 1 through 13, wherein a paper feed path (7) for passing said paper (100) therethrough is extended through said two casings (1, 2). A portable printer as set forth in claim 14, wherein slits (7a, 7b) are formed through said wider surface (1a, 2a) of said casing at an intermediate position in said paper feed path (7), in alignment with each other, and among said plurality of slits, a slit (7a) positioned downstream with respect to the paper feed direction has a wider opening than a slit (7b) positioned upstream thereof. A portable printer as set forth in any one of claims 1 through 15, wherein support means (35, 36) are provided for supporting said casing (1, 2) when stood on a floor while said wider surfaces (1a, 2a) of said plurality of casings (1, 2) are mated to each other. A portable printer as set forth in claim 16, wherein said support means (35, 36) is projectably and retractably provided in said casing (1, 2). A portable printer as set forth in any one of claims 1 through 17, wherein a ribbon cassette (14) is detachably disposed in said casing (1), in which said printing mechanism (10) is housed, and a closure lid (44) for opening and closing a side wall of said casing (1), for exposing said ribbon cassette (14), is pivotally mounted on said casing (1) to be pivotable about a vicinity of the lower end thereof. A portable printer as set forth in claim 1, 2 or 3, wherein a power switch (45) is provided at a position between said casings (1, 2) and is not externally exposed when said casings (1, 2) are in said essentially flat configuration overall. A portable printer as set forth in any one of claims 1 through 19, wherein a receptacle cover (47) is provided for receiving said plurality of casings (1, 2) when in said flat configuration. A portable printer as set forth in claim 20, wherein a partitioning plate (47a) is provided for said receptacle cover (47), for partitioning said casings (1, 2) and other associated materials (48).
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FUJITSU ISOTEC LTD; FUJITSU ISOTEC LIMITED
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NAGAMINE TOMOYUKI; NAKAMURA ISAO; OKUYAMA MASAKI; OTSUKA MASAYOSHI; SAITO YUKIO; NAGAMINE, TOMOYUKI; NAKAMURA, ISAO; OKUYAMA, MASAKI; OTSUKA, MASAYOSHI; SAITO, YUKIO
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EP-0489927-B1
| 489,927 |
EP
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B1
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EN
| 19,960,214 | 1,992 | 20,100,220 |
new
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H04L25
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H04B10, H03K5
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H03K5, H03F3, H04B10, H04L25, H03F1
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H03F 1/02T1C1, H04L 25/06A1, H04B 10/158E3, H03F 3/08I
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LIGHT-RECEIVING CIRCUIT
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A circuit for receiving light incorporates an amplifier (12) having a differential output and is so designed that the positive-phase and antiphase output (Vp, - Vp) from the amplifier (12) are inputted to a comparator (34) always at optimum threshold levels respectively. For this purpose, the peak voltage (Vi) of the positive-phase and antiphase outputs from the amplifier (12) is sensed by a peak value sensor (26) and the peak voltage (Vi) is converted into a current by a voltage-to-current converter (28) having a transconductance (gm). The converter (28) has a differential output and outputs a positive-phase output (I+ = gm Vi) and an antiphase output (I₋ = gm Vi) respectively. These currents (I+, I₋) are converted into voltages by resistors (R10, R12) and the resultant voltages are substracted from the positive-phase and antiphase output (Vp, - Vp). Thereby, the outputs (Vp, - Vp) are mutually level-shifted by the same voltage value respectively. The signals thus level-shifted are inputted to the positive-phase and antiphase inputs of the comparator (34) respectively.
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Technical FieldThe present invention relates to a light-receiving circuit, and more particularly to a light-receiving circuit which converts a photo signal into an electric signal and outputs the electric signal. Background ArtA conventional light-receiving circuit, which converts a photo signal into an electric signal and outputs the electric signal, has such a circuit configuration as is shown in the Light Receiver disclosed in Published Examined Japanese Patent Application (PEJPA) No. 63-25738. More specifically, as is shown in Fig. 1, an amplifier 102 has its input terminal 104 connected to a photodiode 100, and has its output terminal 106 connected to the positive input terminal 110 of a comparator 108. A reference potential-generating circuit 112 is provided. The output terminal 114 of this reference potential-generating circuit 112 is connected to the negative input terminal 118 of a peak value-detecting circuit 116 by way of resistor R100, and is further connected to the output terminal 106 of the amplifier 102 by way of resistors R102 and R104. The positive input terminal 120 of the peak value-detecting circuit 116 is connected to node W, which is between resistors R102 and R104. The output terminal 122 of the peak value-detecting circuit 116 is connected to node X by way of diode D100. Node X is connected to a constant current source I100. Node X is further connected to the negative input terminal 124 of the comparator 108 by way of node Y, to which a capacitor C100 is connected. The output terminal 126 of the comparator 108 is connected to the output terminal 128 of the receiver. In the light-receiving circuit of the above circuit configuration, the threshold value is automatically set to have an optimal level, without reference to a change in photo signal E supplied to the photodiode 100. It is proposed that the amplifier 102 to which the photodiode 100 is connected be replaced with an amplifier having differential output terminals of normal and inverted phases. Such a proposal is made, for example, in Japanese Patent Application No. 1-180717 entitled Widely-Dynamic Light-Receiving Circuit and Japanese Patent Application 1-311334 entitled Light-Receiving Circuit . When the amplifier having differential output terminals is employed, it is possible to make the best use of the amplitude of photo signal E, and the amplifier can have a wide band and be widely-dynamic. The amplifier mentioned above has differential output terminals. Thus, even if the amplifier is incorporated in a circuit wherein the threshold value is automatically set to have an optimal level, such as the circuit shown in Fig. 1, only one of its output terminals, a normal-phase one or an inverted-phase one, can be connected to a given circuit. Accordingly, the gain to be obtained is substantially 1/2 of the gain obtained in the case where both output terminals are connected to that given circuit, and the amplifier fails to sufficiently achieve its advantages. As may be understood from the above, the circuit mentioned above is designed on condition that the amplifier 102 to be incorporated has a single-phase output terminal. The circuit is not designed for use with an amplifier having differential output terminals. As mentioned above, an amplifier having differential output terminals is not suitable for incorporation into such a circuit configuration as is disclosed in Published Examined Japanese Patent Application (PEJPA) No. 63-25738 entitled Light Receiver . Accordingly, an object of the present invention is to provide a light-receiving circuit which has a circuit configuration permitting an amplifier with differential output terminals to be suitably incorporated therein, which employs a wide-band, widely-dynamic amplifier, and which constantly maintains the threshold value at an optimal level without reference to a change in the photo signal. Disclosure of InventionTo achieve the above object, the light-receiving circuit of the present invention comprises: an amplifier for amplifying a signal supplied from a light-receiving element, the amplifier having normal-phase and inverted-phase output terminals; a peak value detector for detecting a peak value of an output of the amplifier, the peak value detector having normal-phase and inverted-phase input terminals which are connected to the normal-phase output terminal of the amplifier, respectively; a voltage-current converter having a normal-phase output terminal, an inverted-phase output terminal, and an input terminal which is connected to an output terminal of the peak value detector; a first resistor inserted between the normal-phase output terminal of the voltage-current converter and the normal-phase output terminal of the amplifier; a second resistor inserted between the inverted-phase output terminal of the voltage-current converter and the inverted-phase output terminal of the amplifier; and a comparator for comparing outputs of the amplifier with each other, the comparator having normal-phase and inverted-phase input terminals which are connected to the normal-phase and inverted-phase output terminals of the voltage-current converter, respectively. In the light-receiving circuit having the above circuit configuration, a peak-value voltage of a normal-phase output of the amplifier and a peak-value voltage of an inverted-phase output of the amplifier are detected by the peak-value detector. The peak-value voltages are converted into currents by the voltage-current converter. By this voltage-current converter, a current corresponding to the normal-phase output and a current corresponding to the inverted-phase are output. The current corresponding to the normal-phase output is converted into a first voltage by the first resistor, while the current corresponding to the inverted-phase output is converted into a second voltage by the second resistor. The first and second voltages are subtracted from the normal-phase and inverted-phase outputs of the amplifier, respectively. By this subtraction, the normal-phase and inverted-phase outputs of the amplifier are shifted in level to the degree corresponding to the same voltage. The two level-shifted signals are supplied to the normal-phase and inverted-phase input terminals of the comparator, so that the signals can be compared with each other with an optimal threshold level at all times. Brief Description of DrawingsFig. 1 is a circuit diagram showing a conventional light-receiving circuit; Fig. 2 is a circuit diagram showing a light-receiving circuit according to the first embodiment of the present invention; Fig. 3 is a waveform chart showing the operation of the light-receiving circuit of the first embodiment of the present invention; Fig. 4 is a circuit diagram showing a light-receiving circuit according to the second embodiment of the present invention; and Figs. 5A through 5D are waveform charts each showing the operation of the light-receiving circuit of the second embodiment of the present invention. Best Mode of Carrying Out the InventionEmbodiments of the present invention will be described below, with reference to the accompanying drawings. Fig. 2 is a circuit diagram showing a light-receiving circuit according to the first embodiment of the present invention, and Fig. 3 is a waveform chart showing the operation of the light-receiving circuit of the first embodiment. As is shown in the Figures, the anode of a photodiode 10 is connected to a power supply Vcc, while the cathode thereof is connected to the input terminal 14 of an amplifier 12. The normal-phase output terminal 16 of the amplifier 12 is connected to the normal-phase input terminal 20 of a peak value-detecting circuit 18 by way of node A, and the inverted-phase output terminal 22 of the amplifier 12 is connected to the inverted-phase input terminal 24 of the peak value-detecting circuit 18 by way of node B. The output terminal 26 of the peak value-detecting circuit 18 is connected to the input terminal 30 of a voltage-current converter circuit 28. The normal-phase output terminal 32 of the voltage-current converter circuit 28 is connected to the normal-phase input terminal 36 of a comparator 34 by way of node C. The inverted-phase output terminal 38 of the voltage-current converter circuit 28 is connected to the inverted-phase input terminal 40 of the comparator 34 by way of node D. Nodes A and C are connected to each other by means of resistor R10. Similarly, nodes B and D are connected to each other by means of resistor R12. The output terminal 42 of the comparator 34 is connected to the output terminal 44 of the light-receiving circuit. The operation of the light-receiving circuit having the above circuit configuration will be described, referring to calculation formulas. Upon supply of a light signal E, the photodiode 10 outputs a reception signal IIN. In response to the supply of this reception signal IIN, the amplifier 12 outputs a normal-phase reception signal Vo+Vp and an inverted-phase reception signal Vo-Vp, both determined in accordance with the reception signal IIN. In the present specification, the reference symbol denoting each signal is associated with the voltage or current value of the signal. To be more specific, in the reference symbols Vo+Vp and Vo-Vp respectively denoting the normal-phase and inverted-phase reception signals, Vo indicates a DC voltage component, and Vp indicates a signal voltage component (signal amplitude). Upon supply of the normal-phase reception signal Vo+Vp and inverted-phase reception signal Vo-Vp, the peak value-detecting circuit 18 detects peak values of the voltages of the signals and outputs peak value signals Vi. The peaks of the voltages are, for example, twice as high as a signal amplitude voltage |Vp| (absolute value). Thus, the voltage Vi of the peak value signals produced from the output terminal 26 of the peak value-detecting circuit 18 is expressed as follows: Vi = 2|Vp| Upon supply of the peak value signals Vi, the voltage-current converter circuit 28 outputs a normal-phase peak value signal I+ and an inverted-phase peak value signal I₋, both determined in accordance with the voltage Vi of the peak value signals. Let it be assumed that the mutual conductance of the voltage-current converter circuit 28 is denoted by gm. In this case, the normal-phase peak value signal current I+ produced from the normal-phase output terminal 32 of the voltage-current converter circuit 28 is expressed as follows: I+ = Io + gm·Vi = Io + 2·gm·|Vp| On the other hand, the inverted-phase peak value signal current I₋ produced from the inverted-phase output terminal 38 is expressed as follows: I- = Io - gm·Vi = Io - 2·gm·|Vp| The Io represents an initial current component which may flow through the current-voltage converter circuit 28 before the supply of the peak value signal Vi. Assuming that each of resistors R10 and R12 has resistance R, the normal-phase signal voltage V+ supplied to the normal-phase input terminal 36 of the comparator 34 is given by the following: V+ = Vo + Vp - R·I+ = Vo - R·Io - 2·gm·R |Vp| + Vp Similarly, the inverted-phase signal voltage V₋ supplied to the inverted-phase input terminal 40 is given by the following: V- = Vo - Vp - R D·I- = Vo - R·Io + 2·gm·R|Vp| - Vp In the case where the relationship between the mutual conductance gm and the resistance R is represented by: R·gm = 1/4, formulas (4) and (5) can be respectively transformed as follows: V+ = Vo - R·Io - (1/2) |Vp| + Vp V- = Vo - R·Io + (1/2) |Vp| - Vp In the right side of each of formulas (6) and (7), the first and second terms represent a DC voltage component, and the first and second terms of the right side of formula (6) are equal to those of the right side of formula (7). The third term represents a DC voltage component which varies in accordance with the voltage Vp of the signal amplitude. The fourth term represents the voltage of the signal amplitude itself. As is shown in the waveform chart in Fig. 3, therefore, the voltage Vo+Vp of the normal-phase reception signal output from the amplifier 12 and the voltage Vo Vp of the inverted-phase reception signal also output from the amplifier 12 are shifted in level by the voltage which is half of that of the signal amplitude |Vp|, and are thus converted into a normal-phase signal of voltage V+ and an inverted-phase signal of voltage V₋, respectively. Due to the processing mentioned above, in the circuit of the first embodiment, the comparator 34 can constantly compare the normal-phase signal V+ and the inverted-phase signal V₋ with each other at the level corresponding to the potential half that of the signal amplitude |Vp|, without reference to the value of the signal amplitude |Vp|. Accordingly, the comparator can compare the two signals with each other with an optimal threshold level at all times and produce an output signal Vout. The light-receiving circuit of the second embodiment will now be described. Fig. 4 is a circuit diagram showing the light-receiving circuit of the second embodiment of the present invention, and Figs. 5A through 5D are waveform charts each showing the operation of the light-receiving circuit of the second embodiment. In these Figures, the same reference symbols as those in Figs. 2 and 3 are used to indicate the similar or corresponding structural components, and a description will be given only of the different circuit configurations from those shown in Figs. 1 and 2. As is shown in Fig. 4, in the circuit of the second embodiment, the normal-phase output terminal 16 of an amplifier 12 is connected to node F, where the line branches out. Node F is connected to node G by way of resistor R14. Similarly, the inverted-phase output terminal 22 of the amplifier 12 is connected to node H, where the line branches out. Node H is connected to node G by way of resistor R16. The potential at node G is set to be substantially 1/2 of the voltage applied between the normal-phase and inverted-phase output terminals 16 and 22, for example, by providing resistors R14 and R16 with the same resistance. The inverted-phase input terminal 31 of a voltage-current converter circuit 28 is connected to node G by way of node J. The inverted-phase input terminal 24 of a peak value-detecting circuit 18 is connected to node K. Nodes J and K are connected to each other by means of resistor R18. A capacitor C10 is connected to node K. The normal-phase input terminal 20 of the peak value-detecting circuit 18 is connected to node A, which is connected to node F. The output terminal 26 of the peak value-detecting circuit 18 is connected to the anode of a diode D10. The cathode of this diode D10 is connected to node L. The normal-phase input terminal 30 of the voltage-current converter circuit 28 is connected to node L. Nodes L and K are connected to each other. A constant current source I10 is connected to node L. The operation of the light-receiving circuit having the above circuit configuration will be described, referring to calculation formulas. Let it be assumed that the current value of the constant current source I10 is denoted by Ig. Also, let it be assumed that the resistance of each of resistors R14 and R16 is denoted by R1, that the resistance of resistor R18 is denoted by Rg, and that the relationship between resistance R1 and resistance Rg is given by the following: 1/2(R1) >> Rg Further, let it be assumed that the resistance of each of resistors R10 and R12 is denoted by R, that the mutual conductance of the voltage-current converter circuit 28 is denoted by gm, and that the relationship between resistance R and mutual conductance gm is given by the following: R·gm = 1/2 1. When light signal E is of a small value, i.e., when |Vp| ≦ Ig·Rg, the peak value-detecting circuit 18 does not operate. Thus, the input voltage Vi of the voltage-current converter circuit 28 satisfies the following formula: Vi = Ig·Rg (constant) Output currents I+ and I₋ of the voltage-current converter circuit 28 are given by the following: I+ = Io + gm·Vi = Io + gm·Rg·Ig (constant) I- = Io - gm·Vi = Io - gm·Rg·Ig (constant) Hence, input voltages V+ and V₋ of the comparator 34 are given by the following: V+ = Vo + Vp - I+·R = Vo - Io·R - (1/2)Ig·Rg + Vp V- = Vo - Vp - I-·R = Vo - Io·R + (1/2)Ig·Rg - Vp In the right side of each of formulas (11) and (12), the first and second terms represent a DC voltage component. The third term also represents a DC voltage component, but the DC voltage component of input voltage V+ and that of input voltage V₋ are opposite in polarity. Due to the opposite polarities, the DC voltage components serve as a guard voltage when a small-value light signal is input or no light signal is input. 2. When light signal E is of a large value, i.e., when |Vp| > Ig·Rg, the peak value-detecting circuit 18 operates. Thus, the input voltage Vi of the voltage-current converter circuit 28 satisfies the following formula: Vi = |Vp| By similar calculation to that of the case where a small-value light signal is input, the input voltages V+ and V₋ of the comparator 34 are given by the following: V+ = Vo - Io·R - (1/2) |Vp| + Vp V- = Vo - Io·R + (1/2) |Vp| - Vp As may understood from formulas (14) and (15), as in the first embodiment, normal-phase signal V+ and inverted-phase signal V₋ can be constantly compared with each other at the level corresponding to half of potential |Vp|, i.e., at the level corresponding to (Vo-IR), without reference to the value of signal amplitude |Vp|. Therefore, the normal-phase and inverted-phase outputs of the amplifier 12 can be constantly compared in the comparator 34 with an optimal threshold level, and output signal Vout can be produced as a result of the comparison. Figs. 5A through 5D are waveform charts each showing the operation of the light-receiving circuit of the second embodiment. Fig. 5(A) shows the waveform obtained when |Vp| = 0, i.e., when no signal is input. Fig. 5(B) shows the waveform obtained when the input signal satisfies the relation |Vp| < Ig·Rg. Fig. 5(C) shows the waveform obtained when the input signal satisfies the relation |Vp| = Ig·Rg. Fig. 5(D) shows the waveform obtained when the input signal satisfies the relation |Vp| > Ig·Rg. Industrial ApplicabilityAs has been described, the present invention can provide a light-receiving circuit which compares the outputs of an amplifier at an appropriate threshold level at all times, even if the amplifier has normal-phase and inverted-phase output terminals. Since, therefore, the light-receiving circuit can employ a wide-band, widely-dynamic amplifier, the circuit is suitable for use in a light communication system, for example.
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A light-receiving circuit comprising: an amplifier (12) having an input terminal (14), a normal-phase output terminal (16), and an inverted-phase output terminal (22), said amplifier amplifying an input signal which is supplied from a light-receiving element (10) connected to the input terminal; a peak value detector (18) having a normal-phase input terminal (20), an inverted-phase input terminal (24), and an output terminal (26), said normal-phase input terminal (20) being connected to the normal-phase output terminal (16) of the amplifier, said inverted-phase input terminal (24) being connected to the inverted-phase output terminal (22) of the amplifier, said peak value detector detecting a peak value of an output of the amplifier; a voltage-current converter (28) having an input terminal (30), a normal-phase output terminal (32), and an inverted-phase output terminal (38), said input terminal (30) being connected to the output terminal (26) of the peak value detector (18); a first resistor (R10) inserted between the normal-phase output terminal (32) of the voltage-current converter (28) and the normal-phase output terminal (16) of the amplifier (12); a second resistor (R12) inserted between the inverted-phase output terminal (38) of the voltage-current converter (28) and the inverted-phase output terminal (22) of the amplifier (12); and A light-receiving circuit according to claim 1, wherein said peak value circuit detects a voltage determined by adding an amplitude voltage supplied from the normal-phase output terminal of the amplifier to an amplitude voltage supplied from the inverted-phase output terminal of the amplifier, and supplies the voltage, thus determined, to the voltage-current converter as a peak value. A light-receiving circuit according to claim 1, wherein said voltage-current converter has a mutual conductance of gm, produces currents obtained in accordance with both the mutual conductance gm and the voltage received as the peak value, and outputs the currents as a normal-phase output and an inverted-phase output, respectively. A light-receiving circuit according to claim 1, wherein said first and second resistors convert the currents obtained by the voltage-current converter into voltages, respectively. A light-receiving circuit according to claim 1, wherein said voltage-current converter has a mutual conductance of gm, each of said first and second resistors has a resistance of R, and the mutual conductance gm and the resistance R have a relationship given by gm × R = 1/4. a comparator (34) having a normal-phase input terminal (36), an inverted-phase input terminal (40), and an output terminal (42), said normal-phase input terminal (36) being connected to the normal-phase output terminal (32) of the voltage-current converter (28), said inverted-phase input terminal (40) being connected to the inverted-phase output terminal (38) of the voltage-current converter (28), said comparator comparing outputs of the amplifier with each other and producing an output signal from the output terminal thereof. A light-receiving circuit comprising: an amplifier (12) having an input terminal (14), a normal-phase output terminal (16), and an inverted-phase output terminal (22), said amplifier amplifying an input signal which is supplied from a light-receiving element (10) connected to the input terminal; a first resistor (R14) and a second resistor (R16) which are inserted between the normal-phase and inverted-phase output terminals (16; 22) of the amplifier (12); a peak value detector (18) having a normal-phase input terminal (20), an inverted-phase input terminal (24), and an output terminal (26), said normal-phase input terminal (20) being connected to the normal-phase output terminal (16) of the amplifier (12), said inverted-phase input terminal (24) being connected to a point (G) located between the first and second resistors (R14; R16), said peak value detector (18) detecting a peak value of an output of the amplifier; a voltage-current converter (28) having a normal-phase input terminal (30), an inverted-phase input terminal (31), a normal-phase output terminal (32), and an inverted-phase output terminal (38), said normal-phase input terminal (30) being connected to the output terminal (26) of the peak value detector (18), said inverted-phase input terminal (31) being connected to the point (G) located between the first and second resistors (R14; R16); a third resistor (R10) inserted between the normal-phase output terminal (32) of the voltage-current converter (28) and the normal-phase output terminal (16) of the amplifier (12); a fourth resistor (R12) inserted between the inverted-phase output terminal (38) of the voltage-current converter (28) and the inverted-phase output terminal (22) of the amplifier (12); and a comparator (34) having a normal-phase input terminal (36), an inverted-phase input terminals (40), and an output terminal (42), said normal-phase input terminal (36) being connected to the normal-phase output terminal (32) of the voltage-current converter (28), said inverted-phase input terminal (40) being connected to the inverted-phase output terminal (38) of the voltage-current converter (28), said comparator comparing outputs of the amplifier with each other and producing an output signal from the output terminal thereof. A light-receiving circuit according to claim 6, wherein said peak value detector detects a voltage which is determined by adding an amplitude voltage supplied from the normal-phase output terminal of the amplifier to a voltage obtained by voltage division by the first and second resistors, and supplies the voltage, thus determined, to the normal-phase input terminal of the voltage-current converter as a peak value. A light-receiving circuit according to claim 6, wherein said first and second resistors have an equal resistance. A light-receiving circuit according to claim 6, further comprising a fifth resistor whose one end is connected to the point located between the first and second resistors and whose another end is connected to the inverted-phase input terminal of the peak value detector. A light-receiving circuit according to claim 6, wherein said voltage-current converter has a mutual conductance of gm, produces currents obtained in accordance with both the mutual conductance gm and a voltage difference between the normal-phase and inverted-phase input terminals thereof, and outputs the currents as a normal-phase output and an inverted-phase output, respectively. A light-receiving circuit according to claim 6, wherein said third and fourth resistors convert the currents obtained by the voltage-current converter into voltages, respectively. A light-receiving circuit according to claim 6, wherein said voltage-current converter has a mutual conductance of gm, each of said third and fourth resistors has a resistance of R, and the mutual conductance gm and the resistance R have a relationship given by: gm × R = 1/2. A light-receiving circuit according to claim 9, wherein each of said first and second resistors has a resistance of R1, said fifth resistor has a resistance of Rg, and resistance R1 and resistance Rg have a relationship given by: 1/2 × R1 >> Rg.
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TOSHIBA KK; KABUSHIKI KAISHA TOSHIBA
|
SAKURA SHIGEYUKI; SAKURA, SHIGEYUKI
|
EP-0489928-B1
| 489,928 |
EP
|
B1
|
EN
| 19,970,129 | 1,992 | 20,100,220 |
new
|
F23D1
|
F23D17
|
F23D17, F23D1, F23C99
|
F23D 1/00, F23D 17/00
|
COMBUSTION SYSTEM
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A combustion system provided with a mixture supply tube through which a mixture of pulverized coal and combustion air flows. The mixture is injected into a furnace through the mixture supply tube, and ignited. A flame holding ring which is flared radially outwardly is provided at the forward end portion of the mixture supply tube. The flame holding ring is held under a reducing atmosphere and exposed to high temperature caused by radiant heat from the furnace. With this arrangement, there are possibilities of burning of the flame holding ring and growth of slag on the flame holding ring. To prevent these problems, a projecting body is extended beyond the flame holding ring in the furnace, radiation of heat to the flame holding ring from the interior of the furnace is suitably shut off and excessive temperature rise is prevented. Combustion air is caused to flow on the surface of the projecting body to thereby keep the projecting body under an oxidizing atmosphere. A pulverized coal/air separating member is extended through the mixture supply tube. Portions where the flows are forcedly delaminated are locally provided on a conical portion at the forward end of the pulverized coal/air separating member. With this arrangement, stabilized combustion in the combustion system as a whole can be attained regardless of the unit capacity or the load of the combustion system.
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This invention relates to a combustion apparatus, as disclosed in the first part of claim 1. A prior art apparatus of this kind is known from EP-A-0 280 568. In a pulverized coal firing boiler, a combustion apparatus injects a mixture of pulverized coal and air into a furnace through a mixture feeding pipe. The mixture injected is ignited so as to form a flame in the furnace. As disclosed in USP 4,545,307, a radially outwardly flared flame maintaining ring is provided at an end of the mixture feeding pipe. Vortices of the mixture are formed along the flame maintaining ring so that the pulverized coal is concentrated in the vicinity of the flame maintaining ring. As a result, an ignition takes place from the end portion of the mixture feeding pipe located in the furnace to form a high temperature strong reduction flame, thereby making it possible to suppress the generation of nitrogen oxides NOx. The flame maintaining ring get covered with ashes and is kept under a reduction atmosphere and, further, exposed to high temperatures due to radiant heat from the furnace. These conditions may cause a burnout of the flame maintaining ring or, when the operation is not proper, growth of slag on the flame maintaining ring, that is, promotion of the slagging, under certain circumstances. The burnout of the flame maintaining ring or the growth of the slag results in the deterioration of the effect of the flame maintaining ring, increase of the amount of nitrogen oxides NOx, or the trouble of the apparatus. Accordingly, an object of the present invention is to provide a combustion apparatus capable of effecting a low nitrogen oxide NOx combustion in a stabilised manner regardless of the unit capacity or the operating load of the combustion apparatus. To this end, in the present invention, a radiation from the flame is shut off and one of three factors of occurrence of the slagging (namely, high temperature, reduction and existence of ash) is eliminated. According to the present invention, there is provided a combustion apparatus comprising: a mixture feeding pipe exposed into a furnace for feeding a mixture of powdery fuel and oxygen-containing gas into the furnace; flame maintaining means provided at an exposed peripheral edge portion of the mixture feed pipe; and a gas feeding passage disposed radially outwardly of the mixture feeding pipe; characterised by further comprising a powdery fuel/oxygen-containing gas separating member coaxially disposed inside of the mixture feeding pipe, the separating member including a first portion which cooperates with the mixture feeding pipe to define therebetween a first mixture feeding passage portion, the sectional area of which is constant, and a second portion extending from the first portion toward the downstream side of the flow of the mixture, which second portion cooperates with the mixture feeding pipe to define therebetween a second mixture feeding passage portion,the sectional area of which is increased gradually along the flow of the mixture. Preferably, a projection is also provided to extend into a furnace beyond a flame maintaining means so as to shut off radiation from the inside of the furnace to the flame maintaining means adequately and suppress an excessive temperature rise, thereby restraining the burnout of the flame maintaining means and the occurrence of the slagging on the flame maintaining means. The apparatus in accordance with the present invention and its method of operation will now be described, by way of example, with reference to the accompanying drawings in which: Figure 1 is a sectional view of a combustion apparatus, not within the scope of the present invention; Figure 2 is a front view taken along the lines II-II in Figure 1; Figure 3 is a partly fragmentary sectional view illustrating a projection shown in Figure 1; Figure 4 is a partly fragmentary front view of the projection of Figure 3; Figure 5 is an enlarged fragmentary front view of the projection of Figure 4; Figure 6 is a sectional view taken along the lines VI-VI in Figure 5; Figure 7 is a partly fragmentary front view illustrating a modification of the projection; Figure 8 is a fragmentary sectional view taken along the lines VIII-VIII in Figure 7; Figure 9 is a fragmentary sectional view illustrating another modification of the projection; Figure 10 is a sectional view of combustion apparatus according to an embodiment to the present invention; Figure 11 is a side view illustrating a conical portion of a pulverized coal/air separating member shown in Figure 10; Figure 12 is a front view taken along the lines XII-XII in Figure 11; Figure 13 is a side view illustrating the conical portion of another pulverized coal/air separating member; Figure 14 is a front view taken along the lines XIV-XIV in Figure 13; Figure 15 is a side view illustrating the conical portion of still another pulverized coal/air separating member; Figure 16 is a front view taken along the lines XVI-XVI in Figure 15; Figure 17 to 19 are sectional views illustrating other modifications of the conical portion of the pulverized coal/air separating member, respectively; and Figure 20 is a sectional view of a different combustion apparatus. Figures 1 to 9 show a combustion apparatus which is not within the scope of appendant claim 1, but which is useful for understanding the embodiments of the present invention shown in Figures 10 to 20. Referring to Figure 1, a combustion apparatus has a bent mixture feeding pipe 1. The combustion apparatus serves to burn pulverized coal as powdery fuel in air as oxygen-containing gas. The mixture feeding pipe 1 faces at one end thereof into a furnace 2 through an opening 22 formed in a furnace wall 21 of the furnace 2 and communicates at the other end thereof with a coal mill (not shown). A mixture of the pulverized coal and the primary air flows through the mixture feeding pipe 1. The mixture is ignited to form a flame in the furnace 2. A flame maintaining ring 3 having an L-letter form cross-section is provided at the peripheral end portion of the mixture feeding pipe 1. As shown in detail in Figure 2, an annular flow passage 4 is so disposed radially outward of the mixture feeding pipe 1 to be concentrical therewith. Tertiary air is fed into the furnace 2 through the flow passage 4. An annular projection 6 is disposed between the mixture feeding pipe 1 and the flow passage 4. The projection 6 extends into the furnace 2 beyond the flame maintaining ring 3. An outer peripheral wall 61 of the projection 6 extends in parallel with the mixture feeding pipe 1 and an inner peripheral wall 62 thereof expands radially outwardly at its end portion. Both peripheral walls 61 and 62 are terminated with an end disk 63. Referring to Figures 1 and 3, an interior of the projection 6 is divided into two layers by a partition tube 64. Secondary air flows in a zigzag manner through a passage portion defined by the outer peripheral wall 61 of the projection 6 and the partition tube 64, a passage portion defined by the inner peripheral wall 62 of the projection 6 and the partition tube 64 and a passage portion defined by the inner peripheral wall 62 of the projection 6 and the mixture feeding pipe 1, as indicated by arrows, and then flows into the furnace 2. Since the inner peripheral wall 62 of the projection 6 expands radially outwardly at the end portion thereof, the secondary air is reduced at a speed thereof, so that a part of the secondary air can be consumed for maintaining the flame without disturbing the jet of the mixture. This makes it possible to form a high temperature reduction flame in a stabilized manner. In consequence, it is possible to suppress the production of nitrogen oxides NOx. The flame maintaining ring 3 is under a reduction atmosphere, and the pulverized coal is concentrated in the vicinity of the flame maintaining ring due to vortices. Further, the flame maintaining ring 3 is usually exposed to high temperatures attributable to the radiant heat from the furnace as indicated by broken lines in Figures 1 and 3. However, since the projection 6 extends beyond the flame maintaining ring 3 into the furnace 2 to shut off radiation toward the flame maintaining ring moderately, the flame maintaining ring 3 can be prevented from being an excessively high temperature. In consequence, even when the unit capacity of the combustion apparatus is increased (e.g. above 50 MW thermal), the flame maintaining ring 3 can be prevented from being burnt out or suffered from the production of slag. On the other hand, the projection 6 is now brought into the state where it gets covered with ashes and is disposed in the reduction atmosphere and, further, exposed to high temperatures due to the radiant heat from the furnace 2. For this reason, there is a possibility that the projection 6 is suffered from the slagging. To cope with this, in the present invention, the projection 6 is not disposed in the reduction atmosphere but an oxidation atmosphere. By so doing, one of factors of occurrence of the slagging can be eliminated, thereby making it possible to prevent the occurrence of the slagging. To form the oxidation atmosphere, an end disk 63 is provided with a plurality of radial slits 631 which are equiangularly spaced, as shown in Figures 4 to 6. A part of the secondary air is jetted out of these slits 631 and guided by guide plates 632, so that it flows circumferentially on the surface of the projection 6. In consequence, the projection 6 can be kept under the oxidation atmosphere, resulting in the prevention of the production of slag. It is noted in this embodiment that the secondary air cools the projection 6 while it flows through the passage portion defined by the outer peripheral wall 61 of the projection 6 and the partition tube 64, the passage portion defined by the inner peripheral wall 62 of the projection 6 and the partition tube 64 and the passage portion defined by the inner peripheral wall 62 of the projection 6 and the mixture feeding pipe 1. The flow of the secondary air of about 300°C makes the projection be 950°C or below, at which temperature any slag is hardly produced. In consequence, it becomes possible to make it harder for the slagging to occur in the projection 6 as well as to make the lifetime of the projection longer. On the other hand, since the temperature of the secondary air is increased by about 40°C due to the radiant heat from the furnace 2, the combustion efficiency can be improved. In a modification shown in Figures 7 and 8, a plurality of circumferential slits 633 are provided equiangularly in the end disk 63, so that a part of the secondary air is guided by a guide plate 634 to flow radially outwardly on the surface of the projection 6. As a result, production of slag can be prevented like the above embodiment. In another modification shown in Figure 9, the end disk 63 is partially cut off and inclined. Figure 10 shows a combustion apparatus which is an embodiment of the present invention and in which, in order to make the concentration of the mixture around the mixture feeding pipe 1 higher, a pulverised coal/air separating rod member 7 is disposed inside of the mixture feeding pipe 1 coaxially. The separating member 7 is attached to the mixture feeding pipe 1 at a stem portion 71 thereof. The separating member 7 also has a flare portion 72 which defines a throat portion in cooperation with a projective member 11 provided in the mixture feeding pipe 1. At the throat portion, the mixture is reduced at a speed thereof. Further, the separating member 7 comprises a right circular cylindrical portion 73 and a conical portion 74 which extends from the right circular cylindrical portion so as to be tapered toward the downstream side of the flow of the mixture. The right circular cylindrical portion 73 cooperates with the mixture feeding pipe 1 to define therebetween a mixture passage portion I the sectional area of t which is held constant. The conical portion 74 cooperates with the mixture feeding pipe 1 to define therebetween a mixture passage portion II the sectional area of which is increased gradually along the flow of the mixture. The mixture is increased at a speed thereof in the passage portion I. When the mixture flows through the passageway portion II, the pulverized coal is separated from the mixture due to its inertia and then flows radially outwardly. As a result, the pulverized coal is concentrated in the vicinity of the flame maintaining ring. Therefore, even if the load of the combustion apparatus is reduced (down to about 30% of the load of the mill, for example), it is possible to effect a highly efficient combustion with the less amount of nitrogen oxides NOx produced. However, if the conical portion 74 is tapered uniformly, there is a possibility that the mixture may separate from the conical portion. Once the separation occurs, the pulverized coal once concentrated in the vicinity of the flame maintaining ring is brought back radial inwardly due to separated flow, resulting in the possibility that the concentration of pulverized coal in the vicinity of the flame maintaining ring is lowered. Further, it is impossible to specify the location where such separation is caused. For this reason, it is designed in this embodiment that the separation of the flow occurs exactly or forcibly at the predetermined portions on the conical portion. In addition, these portions where the separation is occurred are circumferentially located. In other words, the portions where the separation is prevented from occurring are circumferentially equiangularly located as well. In consequence, the concentration of the pulverized coal in the vicinity of the flame maintaining ring becomes circumferentially uniform, and therefore, it is possible to effect a stabilized combustion. To this end, in the present embodiment, the conical portion 74 consists of portions 741 each making a tapering angle 1 with respect to the axial direction and portions 742 each making a tapering angle 2 (> 1) with respect to the axial direction, which portions 741 alternate with the portions 742, as shown in Figures 11 to 14. The tapering angle 1 is in the range of 5° to 15°, and the tapering angle 2 is in the range of 25° to 65°. The separation occurs in the portions 742 but it does not occur in the portions 741. Further, the area occupied by the portions 741 is made larger than that occupied by the portions 742. In consequence, the effect of the separation can be minimized, thereby enhancing a stabilized combustion. The portions 741 and 742 may be connected smoothly (as shown in Figure 12) or steeply (as shown in Figure 14). The tapering angle 2 of the portion where the separation is occurred is not limited to be in the range of 25° to 65°. Even when the tapering angle 2 is 90°, that is, even when the portion 742 is a slit as shown in Figures 15 and 16, the same effect can be obtained. Further, as shown in Figures 17 to 19, the portions 741 and 742 may be arranged asymmetrically. Incidentally, although the projection and the pulverized coal/air separating member coexist in this embodiment, these can be provided separately. In addition, the present invention is also applicable to a pulverized coal combustion apparatus shown in Figure 20 which is equipped with a start-up oil burner 8 and an auxiliary gas burner 9. The oil burner 8 extends through within the separating member 7 to the tip end of the conical portion 74. The gas burner 9 extends through the inner peripheral wall 62 into the furnace 2 to the extent that it can be prevented from being exposed to the radiation from the inside of the furnace 2. The present invention can be used in the combustion apparatus of a pulverized coal boiler, for example.
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A combustion apparatus comprising: a mixture feeding pipe (1) exposed into a furnace (2) for feeding a mixture of powdery fuel and oxygen-containing gas into said furnace (2); flame maintaining means (3) provided at an exposed peripheral edge portion of said mixture feed pipe (1); and a gas feeding passage (4,5) disposed radially outwardly of said mixture feeding pipe (1) for feeding an oxygen-containing gas into said furnace (2); characterised by further comprising a powdery fuel/oxygen-containing gas separating member (7) coaxially disposed inside of said mixture feeding pipe (1), said separating member (7) including a first portion (73) which cooperates with said mixture feeding pipe (1) to define therebetween a first mixture feeding passage portion (I), the sectional area of which is constant, and a second portion (74) extending from said first portion (73) toward the downstream side of the flow of the mixture, which second portion (74) cooperates with said mixture feeding pipe (1) to define therebetween a second mixture feeding passage portion (II), the sectional area of which is increased gradually along the flow of the mixture. A combustion apparatus according to claim 1, wherein said first portion is circular cylindrical and said second portion is conical and tapers toward the downstream side of the flow of the mixture. A combustion apparatus according to claim 1 or 2, wherein said second portion has a portion where separation of the flow is caused to occur and another portion where separation of the flow is not caused to occur, which portions alternate circumferentially. A combustion apparatus according to claim 3, wherein the circumferential dimension of said portion where separation of the flow is caused to occur is smaller than that of said another portion where separation of the flow is not caused to occur. A combustion apparatus according to Claim 3 or 4 when dependent on claim 2, wherein said conical portion of said powdery fuel/oxygen-containing gas separating member is provided at a peripheral surface thereof with portions the tapering angles of which are different from each other with respect to the axis of said conical portion. A combustion apparatus according to any one of claims 1 to 6, further comprising: projection means (6) disposed radially between said gas feeding passage (4) and said mixture feeding pipe (1) with and extending into said furnace (2) beyond said flame maintaining means (3) so as to shield said flame maintaining means (3) from radiation from the inside of said furnace. A combustion apparatus according to claim 6, wherein a second gas feeding passage (5) in disposed radially between said first mentioned gas feeding passage (4) and said mixture feeding pipe (1) for feeding an oxygen-containing gas into said furnace (2). A combustion apparatus according to claim 6 or 7, further comprising: means (631,632; 633,634) for forming an oxidising atmosphere around a surface (63) of said projection (b) which is exposed into said furnace. A combustion apparatus according to claim 8 when dependent on claim 7, wherein said oxidising atmosphere is formed by the oxygen-containing gas flowing through said second gas feeding passage (5).
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BABCOCK HITACHI KK; BABCOCK-HITACHI KABUSHIKI KAISHA
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BABA AKIRA; HODOZUKA KUNIO; ISHII KEIJI; JIMBO TADASHI; KOBAYASHI HIRONOBU; KURAMASHI KOUJI; MORITA SHIGEKI; NAKASHITA SHIGETO; BABA, AKIRA; HODOZUKA, KUNIO; ISHII, KEIJI; JIMBO, TADASHI; KOBAYASHI, HIRONOBU; KURAMASHI, KOUJI; MORITA, SHIGEKI; NAKASHITA, SHIGETO
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EP-0489929-B1
| 489,929 |
EP
|
B1
|
EN
| 19,951,213 | 1,992 | 20,100,220 |
new
|
H04N7
| null |
H04N7
|
H04N 7/167, H04N 7/20
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TRANSMITTING DEVICE FOR CATV
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A transmitting device for CATV is provided with a satellite receiver (12) for receiving a scrambled television signal of a specific channel from a communication satellite and for demodulating it, a data decoder (17) for decoding a scramble controlling data in the output video signal of the satellite receiver device (12), and a single or plural scrambling devices (18) for scrambling a single or plural video signals inputted for a different television channel by the scramble controlling data decoded using the data decoder. The scrambler for a different channel from the communication satellite's channel scramble the video signals by the scramble controlling data of the communication satellite's television signal decoded using the data decoder (17). Therefore, the scrambling formats of the scramblers are the same as the one of the communication satellite's television signal.
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TECHNICAL FIELDThe present invention relates to a CATV transmission installation which receives television programs by means of a communications satellite and supplies them to general homes. BACKGROUND ARTAn example of prior art CATV transmission installations will be explained with use of Fig. 2. A program transmission equipment called a heat end in the CATV transmission installation comprises a line controller 1 for controlling the scrambling operation of a pay program, video scramblers 3 and 3′ for performing scrambling operation over video signals a and a′ received from a video source 2 of a pay program on the basis of a control signal b received from the line controller 1 respectively, television modulators 4 and 4′ for converting scrambled video signals c and c′ received from the video scramblers 3 and 3′ into RF television signals d and d′ respectively, and a mixer 5 for mixing the television signals d and d′ received from the respective channels and for sending a mixed signal to a transmission line. When scrambling operation is carried out with respect to a plurality of channels in this manner, the control signal b is sent from the line controller 1 to the video scramblers 3 and 3′ at the same time. These years, pay programs have been supplied to CATV by means of communications satellite and even a television signal to be transmitted through the communications satellite have been able to be subjected to an independent scrambling operation. For this reason, a receiver for the communications satellite and a descrambler for restoring the received signal into an original signal have been installed in the head end. Further, companies for supplying satellite pay programs have conducted the operation of CATV pay programs mainly in Europe. In order to improve the efficiency and rationalization of such program operation, there has been recently employed a method for setting the scrambling format in the scrambler of the communications satellite to be equal to the conventional scrambling format of the scrambler (video scramblers 3 and 3′) of the CATV system. However, since a plurality of programs are supplied from a plurality of pay-program supply companies to the CATV system, it is indispensable to install the scrambler in the head end. Thus, there is a problem that, when it is desired to change the scrambling format of the satellite system, it is also required to change the scrambling format of the video scramblers 3 and 3′ for all pay programs being used in the CATV. At the same time, it is necessary to change a TAG signal indicative of the charging level of the video scramblers 3 and 3′ installed in the head end. Presently, there has been locally employed a method for controlling the video scramblers 3 and 3′ installed in each CATV through telephone line, but this method has been difficult and inefficient in realizing the simultaneous change of the aforementioned scrambling format and TAG signal because the number of CATV head ends, for example, in the overall Europe reaches several thousand. DISCLOSURE OF INVENTIONIt is an object of the present invention to provide a CATV transmission installation which solves the aforementioned problem and which allows simultaneous change of both the scrambling format of a scrambler in a CATV system and a TAG signal. In order to solve the above problem, a CATV transmission installation in accordance with the present invention comprises a satellite receiver for receiving and demodulating a scrambled television signal of a specific channel from a communications satellite, a data decoder for decoding a scramble control data from an output video signal of the satellite receiver, and a single or a plurality of scramblers for scrambling a single or a plurality of video signals received for a different television channel on the basis of the scramble control data decoded by the data decoder. With such an arrangement as mentioned above, the scrambler for a channel different from the communications satellite channel scrambles the video signal with use of the scramble control data for the communications satellite television signal decoded by the data decoder, whereby the scrambling format of the scrambler can be made equal to that of the communications satellite television signal. BRIEF DESCRIPTION OF DRAWINGSFig. 1 is an arrangement of a heat end in a CATV transmission installation in accordance with an embodiment of the present invention; and Fig. 2 is an arrangement of a heat end in a prior art CATV transmission installation. BEST MODE FOR CARRYING OUT THE INVENTIONAn embodiment of the present invention will be explained with reference to the accompanying drawings. Referring to Fig. 1, there is shown an arrangement of a heat end in a CATV transmission installation in accordance with an embodiment of the present invention. When scrambling operation is applied to a satellite system, a scramble control data is simultaneously transmitted in order to control a descrambler installed in a subscriber terminal or a head end. There are two cases where this scramble control data is multiplexed on a video signal and on a subcarrier for transmission. In the case of the CATV transmission installation of Fig. 1, the subcarrier is used for the scramble control data. In the drawing, reference numeral 12 denotes a satellite receiver which receives through a satellite antenna 11 a television signal of a satellite channel having the same format as the scrambling format of a CATV system, demodulates the television signal, and outputs a scramble video signal e and a subcarrier signal f to a scramble controller 13. When it is desired to send the scramble video signal e as an output of the satellite receiver 12 to the CATV system without any change, the scramble video signal e is sent from the satellite receiver 12 through the scramble controller 13 to a television modulator 14, where the scramble video signal e is converted into a television signal r of a specific CATV channel which in turn is sent through a mixer 15 to a transmission line. At this time, the scramble controller 13 outputs to the TV modulator 14 a clamp signal g necessary for television modulation and a key signal h necessary for the descrambling of a subscriber terminal, and also subjects a data signal i for control of the subscriber terminal to an RF modulation and then outputs the signal i to the mixer 15. Reference numeral 16 denotes a data detector which is provided to detect a scramble control data for a channel different from the satellite channel. More specifically, the data detector 16 extracts part of the subcarrier signal f received from the satellite receiver 12 and outputs a signal j to a data decoder 17. The data detector 16 may be incorporated in the scramble controller 13 in some cases. The data decoder 17 decodes the baseband data signal j received from the data detector 16, detects a data necessary for the scramble control therefrom to detect the change of a scrambling format and a TAG signal, and controls a video scrambler 18 on the basis of the detected data. The data decoder 17, which has a specific address for detection of the TAG signal, has a function of judging whether or not the control is for its own channel. The video scrambler 18 scrambles a video signal ℓ received from a video source 19 according to a scramble control data signal k received from the data decoder 17 and sends a video scramble signal m, a clamp signal n and a key signal p to a television modulator 20. The television modulator 20 in turn, converts the received signals m, n and p into a television signal q for the specific CATV channel and sends the signal q via the mixer 15 to the transmission line. With such an arrangement as mentioned above, the data detector 16 and the data decoder 17 enable the simultaneous modification of both the scrambling format of the satellite channel and the scrambling format of the video scrambler 18 and also enable the modification control of the TAG signal. In this way, the scrambling formats of the video scrambles 18 installed in the respective CATVs can be collectively modified. INDUSTRIAL APPLICABILITYAs has been disclosed in the foregoing, in accordance with the present invention, when a scrambler for a channel different from a communications satellite channel scrambles a video signal with use of a scramble control data for a communications satellite television signal decoded by a data decoder, the scrambling format of the scrambler can be modified at the same time as the modification of the scrambling format of the communications satellite television signal to be equal to each other.
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A CATV transmission installation comprising a satellite receiver for receiving and demodulating a scrambled television signal of a specific channel from a communications satellite, a data decoder for decoding a scramble control data from an output video signal of the satellite receiver, and a single or a plurality of scramblers for scrambling a single or a plurality of video signals received for a different television channel on the basis of the scramble control data decoded by the data decoder.
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MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
|
SUGIMOTO AKIHISA; SUGIMOTO, AKIHISA
|
EP-0489930-B1
| 489,930 |
EP
|
B1
|
EN
| 19,950,510 | 1,992 | 20,100,220 |
new
|
D21H23
|
D21H17
|
D21H17
|
D21H 17/37B, D21H 17/43, D21H 17/45
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PAPERMAKING PROCESS AND PAPERMAKING ADDITIVE
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A papermaking additive comprising: (A) a cationic acrylamide polymer prepared by the reaction of an acrylamide polymer with a hypohalite under an alkaline condition in a temperature range of 50 to 110°C for a short time, and (B) either an anionic inorganic substance or a cationic polyacrylamide prepared by the copolymerization of a cationic monomer such as an acrylic ester or acrylamide derivative, an α,β-unsaturated carboxylic acid or its salt, and acrylamide.
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Technical FieldThe present invention relates to a method for papermaking, and more particularly to, a method for papermaking comprising using both a cationic acrylamide polymer obtained by Hofmann decomposition reaction at an elevated temperature for a short time and an anionic inorganic substance or a cationic polyacrylamide produced by copolymerization, and an additive for papermaking comprising a cationic acrylamide polymer produced by Hofmann decomposition reaction and an anionic inorganic substance or a cationic polyacrylamide prepared by copolymerization. Background ArtSince it has recently become difficult to obtain raw materials for paper, the amount ratio of old papers in pulp raw materials has increased. As a result, there are demanded paper strength improvers capable of imparting higher paper strength. On the other hand, in practical operations there are demanded chemicals capable of improving freeness due to requirement of imcreasing the pulp dehydration speed and chemicals capable of improving drying property to meet requirement of decreasing the amount of steam to be used. A Hofmann decomposition reaction product of polyacrylamide (hereinafter referred to as Hofmann PAM ) is a cationic resin having a primary amino group directly bonded to the polymer main chain, and has been conventionally used as a freeness improver and a paper strength improver in a step of papermaking. A feature of Hofmann PAM resides in the high aggregation power, and it not only improves freeness, but also improves the strength between fibers due to the hydrogen bond of the primary amino group which is also a cationic group. However, when the Hofmann PAM is used alone, sometimes an effective fixation to pulp fibers cannot be attained depending on the papermaking conditions and the feature of the Hofmann PAM cannot be fully exhibited. In such a case, problem of freeness can be solved by increasing the amount of Hofmann PAM to be added, but on the other hand, the formation of paper is deteriorated. Therefore, satisfactory results are not always obtained as to paper strength and printing characteristics. It is known from JP-A-62-015391 and JP-A-60-065195 to increase the yield of fillers in papermaking by adding the Hofmann PAM together with additives to the pulp. Disclosure of InventionIn view of the above-mentioned points, the present inventors have investigated various additives capable of exhibiting a desirable effect when used together with Hofmann PAM, and as a result, have found that when an anionic inorganic substance or a cationic acrylamide polymer produced by copolymerization is used together therewith, freeness can be controlled without lowering paper strength characteristics, and the present invention has been completed. That is, the present invention is concerned with a method for papermaking which comprises adding to a pulp slurry a cationic acrylamide polymer produced by reacting an acrylamide polymer with a hypohalogenite at 50 - 110°C for a short time at an alkaline region and an anionic inorganic substance or a cationic polyacrylamide produced by the copolymerization of (a) a cationic monomer of the general formula (I) where R₁ is hydrogen or methyl, R₂ and R₃ are hydrogen or alkyl having 1 - 6 carbon atoms, X is O or NH, n is an integer of 2 - 4, and/or organic or inorganic acid salts thereof, or quaternary ammonium salts produced by the reaction of the compound of the formula (I) with a quaternizing agent, (b) an α,β-unsaturated carboxylic acid and/or salts thereof, and (c) an acrylamide monomer of the general formula (II),CH₂ = C (R₅) - CONH₂ (II) where R₅ is hydrogen or methyl, and an additive for papermaking comprising a cationic acrylamide polymer produced by reacting an acrylamide polymer with a hypohalognite at an alkaline region at 50 - 110°C for a short time and an anionic inorganic substance or a cationic polyacrylamide produced by the copolymerization of (a) a cationic monomer of the general formula (I) where R₁ is hydrogen or methyl, R₂ and R₃ are hydrogen or alkyl having 1 - 6 carbon atoms, X is O or NH, n is an integer of 2 - 4, and/or organic or inorganic acid salts thereof, or quaternary ammonium salts produced by the reaction of the compound of the formula (I) with a quaternizing agent, (b) an α,β-unsaturated carboxylic acid and/or salts thereof, and (c) an acrylamide monomer of the general formula (II),CH₂ = C (R₅) - CONH₂ (II) where R₅ is hydrogen or methyl. In the following, the present invention is explained in detail. The acrylamide polymers used in the present invention include homopolymers of acrylamides (or methacrylamides), copolymers of acrylamides (or methacrylamides) and at least one unsaturated monomer capable of copolymerizing therewith, and further graft copolymers of the acrylamides (or methacrylamides) with water-soluble polymers such as starch and the like. As the copolymerizable monomers, there may be mentioned hydrophilic monomers, ionic monomers, lipophilic monomers and the like, and at least one monomer may be used. Concretely the hydrophilic monomers are, for example, diacetone acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-ethylmethacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorphorine, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol (meth) acrylates, N-vinyl-2-pyrrolidone, and the like. As ionic monomers, there may be mentioned, for example, acids such as acrylic acid, methacrylic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic aicd, styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like, and salts thereof, and amines such as N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, and the like, and salts thereof. As lipophilic monomers, there may be mentioned, for example, N-alkyl (meth)acrylamide derivatives such as N,N-di-n-propyl acrylamide, N-n-butyl acrylamide, N-n-hexyl acrylamide, N-n-hexyl methacrylamide, N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide, N-dodecyl acrylamide, N-n-dodecyl methacrylamide, and the like, N-(ω-glycidoxyalkyl) (meth)acrylamide derivatives such as N,N-diglycidyl acrylamide, N,N-diglycidyl methacrylamide, N-(4-glycidoxybutyl) acrylamide, N-(4-glycidoxybutyl) methacrylamide, N-(5-glycidoxypentyl) acrylamide, N-(6-glycidoxyhexyl) acrylamide, and the like, (meth)acrylate derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate and the like, acrylonitrile, methacrylonitrile, vinyl acetate, vinylidene chloride, olefins such as ethylene, propylene, butene and the like, styrene, divinyl benzene, α-methylstyrene, butadiene, isoprene, and the like. The amount of the unsaturated monomer used for copolymerization varies depending on the types of unsaturated monomers and combination thereof, but is usually 0 - 50 % by weight. As water-soluble polymers to be used for graft copolymerization with the above-mentioned monomers, there may be used both natural ones and synthetic ones. As natural water-soluble polymers, there may be used starches of different origin and modified starches such as oxidized starch, carboxyl starch, dialdehyde starch, cation-modified starch and the like, cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose and the like, alginic acid, agar, pectin, carrageenan, dextran, pururan, arum root, Arabia rubber, casein and gelatin. As synthetic water-soluble polymers, there may be mentioned polyvinyl alcohol, polyvinyl ether, polyvinyl pyrrolidone, polyethylene imine, polyethylene imine, polyethylene glycol, polypropylene glycol, polymaleic acid copolymer, polyacrylic acid, polyacrylamides and the like. The amount of the monomer to be added to the above-mentioned water-soluble polymer is 0.1 - 10.0 times the weight of the water-soluble polymer. Then the above-mentioned monomers are polymerized to prepare polyacrylamide. As the methods for polymerization, free-radical polymerization is preferable, and as the polymerization solvent, polar solvents such as water, alcohols, dimethylformamide and the like are usable, but since Hofmann decomposition reaction is carried out in an aqueous solution. It is preferable to effect the polymerization in an aqueous solution. The concentration of monomers is such a case as above is 2 - 30 % by weight, preferably 5 - 30 % by weight. As the polymerization initiator, there is not any limitation as far as it is water-soluble. The polymerization initiator is usually dissolved in an aqueous solution of monomers and used. Concretely, as peroxide initiators, there may be mentioned, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide and the like. In such a case, the peroxide can be used alone, but may be slso used as a redox polymerization agent by combining with a reducing agent. As the reducing agent, there may be used, for example, sulfites, hydrogen sulfites, salts of low order ionization metals such as iron, copper, cobalt and the like, organic amines such as N,N,N',N'-tetramethyl ethylenediamine and the like, and reducing sugars such as aldose, ketose and the like. As azo compounds, there may be used 2,2'-azobis-2-amidinoprapane hydrochloride, 2,2'-azobis-2,4- dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, salts thereof and the like. Further, two or more of the above-mentioned polymerization initiator may be used in combination. When graft polymerization is effected to a water soluble polymer, other than the above-mentioned polymerization initiator, there may be also used transition metal ions such as ceric ion, ferric ion and the like, and further, such ions may be used in combination with the above-mentioned polymerization initiators. The amount of the initiator to be added may be 0.01 - 10 % by weight based on the weight of monomers, preferably 0.02 - 8 % by weight. In the case of a redox initiator, the amount of the reducing agent to be added may be 0.1 - 100 %, preferably 0.2 - 80 % based on the initiator in terms of mole. The polymerization temperature is as low as 30 to 90°C in the case of a single polymerization initiator, and much lower such as about -5 to 50°C in the case of a redox polymerization initiator. In addition, it is not necessary to keep the temperature at a constant temperature, and the temperature may be changed accordingly as the polymerization proceeds. In general, as the polymerization proceeds, the temperature rises due to the generated polymerization heat. The atomosphere in the polymerization vessel at that time is not particularly limited, but it is desirable to replace the atmosphere with an inert gas such as nitrogen gas for the purpose of accelerating the polymerization. The polymerization time is not critical, but is usually 1 - 20 hours. Then, the polyacrylamide produced by the above-mentioned method is subjected to Hofmann decomposition reaction. When the polyacrylamide as a starting material is prepared in an aqueous solution, it can be directly used or, if necessary, it is diluted and then used for the reaction. In the case of graft copolymerization, there is produced polyacrylamide not grafted as a by-product, but the product is directly used for the reaction without removing the non-grafted one. Hofmann decomposition reaction is effected by acting a hypohalogenite on the amido group of polyacrylamide in the presence of an alkaline substance. As a hypohalogenous acid, there may be mentioned hypochlorous acid, hypobromous acid, and hypoiodous acid. As a hypohalogenite, there may be used metal or alkaline earth metal salts. Concretely, they may be sodium hypochlorite, potassium hydrochlorite, lithium hypochlorite, calcium hypochlorite, magnesium hypochlorite, barium hypochlorite and the like. Similarly, there may be mentioned alkali metal or alkaline earth metal hypobromite and hypoiodite in case of hypobromite and hypoiodite. It is also possible to produce hypohalogenite by blowing a halogen gas into an alkaline solution. On the other hand, as alkaline substances, there may be mentioned alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate and the like. Among them, alkali metal hydroxides are preferable, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are mentioned. The amount of the above-mentioned substance to be added to polyacrylamides is 0.05 - 2.0 mol, preferably 0.1 - 1.5 mol per amido group in the case of hypohalogenous acid, 0.05 - 4.0 mol, preferably 0.1 - 3.0 mol per amido group in the case of alkaline substance. The pH in such a case is usually 11 - 14. The concentration of polyacrylamide in such a case is usually 0.1 - 17.5 % by weight, but preferably 0.1 - 10 % by weight since a high reaction concentration results in difficult agitation or causes gelation. Further, when the reaction concentration is less than 1 %, the reaction speed becomes so slow that it is more preperable that the reaction concentration is 1 - 10 % by weight. The reaction temperature may be 50 - 110°C, preferably 60 - 100°C. The Hofmann decomposition reaction is carried out at the above-mentioned temperature range within a short time. The reaction time varies depending on reaction temperature and polymer concentration in the reaction solution, and therefore, the reaction time can not be definitely mentioned, but, for example, when the polymer concentration is 1 % by weight, it is within ten and several minutes at 50°C and within several minutes at 65°C and sufficiently within several tens sec. at 80°C. Further, when the polymer concentration is high, the reaction time can be shorter. The relation between the reaction time and the reaction temperature may be generally within the range defined by the following two formulas, and when the reaction is carried out within such range, a good result can be obtained, T : Reaction temperature (°C) 50 ≦ T ≦ 110 Cationic polyacrylamides produced under the above-mentioned conditions have a cation eqivalent determined by colloid titration at pH 2 of about 0 - 10.0 meq/g, and said cation equivalent can be controlled by the amount of hypohalogenite added. Since the reaction is carried out in an alkaline region, the amino group is hydrolyzed to produce carboxyl group as a by-product. The amount of the by- production is about 0 - 10.0 meq/g in terms of anion equivalent measured by colloid titration at pH 10. The amount of by- production can be controlled by adjusting the amount of the alkaline substance added. After effecting the reaction under the above-mentioned conditions, it is preperable to stop the reaction so as to suppress the proceeding of a side-reaction. However, when the product is used immediately after the reaction, sometimes it is not necessary to stop the reaction. The procedure of stopping the reaction may be (1) adding a reducing agent, (2) cooling, (3) lowering the pH of the solution by adding an acid, or the like. These procedures may be used alone or in combination. (1) is a method for deactivating the remaining hypohalogenite and the like by the reaction with a reducing agent. In general, when the Hofmann decomposition reaction has completed, there still remain compounds having active chlorine such as unreacted hypohalogenites and the like. When such a reaction solution is used as a paper strength agent, it causes rust on paper-making machines, and therefore, usually the active chlorine is deactivated by using a reducing agent. However, when a hypohalogenite is reacted in an amount of equivalent mol. or less based on mol. of acrylamide unit of the polymer and at a high temperature, after completion of the reaction, unreacted hypohalogenite hardly remains. Therefore, the product can be used as a paper strength agent without deactivating active chlorine by using a reducing agent. (2) is concerned with a method for suppressing the proceeding of reaction. As a procedure thereof, there may be cooling with heat exchanger, diluting with cold water and the like. The temperature is usually 50°C or less, preferably 45°C or less, more preferably 40°C or less. According to (3), Hofmann decomposition reaction is stopped by lowering the pH of the solution after completion of the reaction which is usually alkaline such as pH 12 - 13 by using an acid and the progress of hydrolysis reaction is simultaneously suppressed. At that point, it is necessary only that the pH is neutral or less, preferably 4 - 6. A reaction stopping method may be appropriately selected from (1) - (3) depending on the reaction conditions, and the methods may be used in combination. Anionic inorganic substances which can be used together with Hofmann decomposition PAM produced by the above-mentioned method may be sodium silicate, anionic particule-like inorganic substances and mixtures thereof. Sodium silicate can be produced by melting silicon dioxide with sodium carbonate or sodium hydroxide at an elevated temperature, and commercially available water glass also may be used. The structure is shown by the following general formula:NaO · nSiO₂ · xH₂O where n is 1 - 4. The examples are sodium metasilicate, sodium orthosilicate, No. 1, No. 2 and No. 3 water glasses and the like. The form to be used may be such that flake or powder thereof or the like is dissolved in water, or commercially available aqueous solution products also may be used. As an anionic particle-like inorganic substance, it is necessary only that it is not soluble in water and is anionically charged in water, and various materials can be used. Concretely, the examples may be silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, and oxides such as clay minerals, for example, alminosilicates such as montmorillonite, bentonite, kaolin, activated clay, silica sand, diatomaceous earth and the like, magnesiasilicates such as talc, and further carbonates such as calcium carbonate and the like. When the size of the above-mentioned particles is too large, the composite effect becomes small. The particle size is usually 100 µm or less, preferably 50 µm or less, more preferably 10 µm or less. The ratio of anionic inorganic substance to Hofmann decomposition PAM when both are added may be such that the amount of anionic inorganic substance is 1 - 500 % by weight, preferably 2 - 400 % by weight, more preferably 3 - 300 % by weight based on Hofmann decomposition PAM. When the ratio is too small, the effect due to the combined use is not obtained while when it is too large, the function of Hofmann decomposition PAM is deteriorated. The Hofmann decomposition rate is not particularly critical, but usually 5 - 60 mol %, preferably 10 - 50 mol %. A practical procedure for adding anionic inorganic substances in combination with Hofmann decomposition PAM is such that Hofmann decomposition PAM used in the present invention is produced by the reaction at a high temperature for a short time and the product can be directly used, and since the resulting reaction fluid is strongly alkaline, the combined addition may be effected by any procedure. Concretely, (i) upon effecting Hofmann decomposition reaction, the anionic inorganic substance is added to and dissolved in sodium hydroxide, sodium hypochlorite or mixture solutions thereof in advance and the mixture is used for Hofmann decomposition reaction. (ii) After Hoffmann decomposition reaction, the anionic inorganic substance is added to the reaction fluid. (iii) Both are added separately. The amount of Hofmann decomposition PAM and anionic inorganic substance added to pulp is usually 0.005 - 5.0 %, preferably 0.01 - 2.0 % based on the dry weight of pulp. In such a case, the ratio of Hofmann decomposition PAM to anionic inorganic substance varies depending on papermaking conditions. Concretely, for example, when it is intended to increase freeness so as to accelerate the papermaking speed, the ratio of anionic inorganic substance is rendered small while when it is intended to control the formation and make uniform paper, the ratio of anionic inorganic substance is increased. According to the process of the present invention, sometimes the effect is further enhanced when aluminum sulfate or water-soluble anionic resins is used in combination. The water-soluble anionic resins used here may be water-soluble resins having an anionic substituent such as carboxyl group, sulfonic acid group, phosphoric aicd group and the like, or salts thereof. Examples of said resins are : anionic acrylamide resins, anionic polyvinyl alcohol resins, carboxymethylcellulose, carboxymethylated starch, sodium alginate, and the like. The point when the addition is effected is not critical, that is, the addition may be effected before or after Hofmann decomposition PAM and sodium silicate are added to a pulp slurry, or simultaneously. Further, the addition may be effected to each of Hofmann decomposition PAM and sodium silicate or to a mixture solution thereof. The place where the addition is effected may be anywhere as far as it is before forming a wet sheet. It is preferable to add to a place where chemicals can be sufficiently mixed with and diluted with the pulp slurry and which is near the papermaking wire part, for example, machine chest, mixing box, seed box, white water pit, outlet of screen and the like. As a papermaking machine, there may be used either Fourdrinier paper machine or cylinder paper machine. After the present additive for papermaking is added to a pulp slurry having a concentration of 0.5 - 5.0 %, a pH 4.0 - 9.0 at a temperature of 20 - 70°C, a wet sheet is formed at a wire part and then water is squeezed at a press part. The nip pressure at the press part ranges from 20 to 400 kg/cm. After passing the press part, the wet sheet is transferred to a dry part and dried with steam. The steam pressure is 2 - 15 kg/cm² and the drying is carried out in a drum at 80 - 200°C. After this process, chemical treatments may be effected at a size press or calender so as to improve printing property, surface strength, water resistance, and water repellency. The additive for papermaking in the present invention comprising a Hofmann decomposition PAM and an anionic inorganic substance as effective components. The concentration of the effective components may be 0.001 - 50 %. The amount ratio of anionic inorganic substance to Hofmann decomposition PAM may be 1 - 500 % by weight, preferably 2 - 400 %, more preferably 3 - 300 %. When the mixing ratio is too low, the mixing effect due to the mixing is not obtained while when the ratio is too high, the property of the Hofmann PAM is deteriorated. The Hofmann decomposition rate here is not particularly critical, but usually 5 - 60 mol %, preferably 10 - 50 mol %. As a procedure for mixing a Hofmann decomposition PAM and an anionic inorganic substance, (i) upon carrying out Hofmann decomposition reaction, they may be added to or dissolved in sodium hydroxide, sodium hypochlorite or a mixture solution thereof in advance and the resulting mixture is used for the Hofmann decomposition reaction. (ii) After Hofmann decomposition reaction, they may be mixed with the resulting reaction fluid. The solution after the Hofmann decomposition reaction is usually of pH 12 - 13, but the pH may be lowered wtih an inorganic or organic acid before it is mixed with an anionic inorganic substance, and further, it is possible to lower the pH after mixing with an anionic inorganic substance. The additive for papermaking of the present invention may have pH 2 - 14. According to the present invention, the cationic monomers of the general formula (I) as above are, for example, (meth)acrylic acid ester derivatives represented by dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, and (meth)acrylamide derivatives represented by dimethylaminopropyl (meth)acrylamide and diethylaminopropyl (meth)acrylamide. The organic or inorganic acid salts may be salts of inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and the like, or salts of organic acids such as acetic acid, formic acid and the like. As quaternary ammonium salts obtained by the reaction of the compound of the general formula (I) above with a quaternizing agent, there may be mentioned, for example, vinyl monomers having a quaternary ammonium salt produced by the reaction of a vinyl monomer having a tertiary amino group with a quaternizing agent such as methyl chloride, methyl bromide, methyl iodide, dimethyl sulfuric acid, epichlorohydrin, benzyl chloride and the like. According to the present invention, a vinyl monomer having a tertiary amino group, or organic or inorganic salts thereof may be used in combination with a quaternary ammonium salts obtained by the reaction with a quaternizing agent. The mixing ratio of these components is not critical. The amount of the cationic monomer is usually 0.5 - 70 mol %, preferably 2 - 50 mol %. The α,β-unsaturated carboxylic acids or salts thereof, for example, alkali metal salts or ammonium salt thereof are vinyl monomers having anionicity, for example, unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, (meth)acrylic acid, crotonic acid, citraconic acid, and the like, and alkali metal salts thereof such as sodium salts, potassium salts and the like, and ammonium salts thereof. The amount of the monomer may be 0.5 - 20 mol %, preferably 2 - 20 mol %. The monomer represented by the general formula (II) of the present invention may be acrylamide and methacrylamide, and commercially available such monomers in the form of powder or an aqueous solution may be sufficiently used. The amount of the monomer used may be 10 - 90 mol %. According to the present invention, as a fourth component other than (a) - (c), there may be used a crosslinking monomer (d). The crosslinking monomer may be a monomer having at least two double bonds in the molecule and an N-alkoxymethyl (meth)acrylamide derivative. Concretely, examples of the former include methylene bisacrylamide, diallyl acrylamide, triacrylformal, diacryloylimide, ethylene glycol acrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol methacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane triacrylate, divinylbenzene, diallyl phthalate, and the like. The N-alkoxymethyl (meth)acrylamide derivatives include N-hydroxymethyl (meth)acrylamide, for example, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-butoxymethyl (metha)acrylamide, N-tert-butoxymethyl (meth)acrylamide, and the like. The amount of the cross linking agent varies depending on the type of crosslinking monomer, but is usually 0.0001 - 20 mol %, preferably 0.001 - 10 mol %. When the amount is less than 0.0001 mol %, the paper strength effect can not be sufficiently exhibited. On the contrary, when the amount exceeds 20 mol %, gelation is liable to occur. As methods for obtaining the cationic polyacrylamide (B) of the present invention, there may be used conventional methods for polymerizing such type of water-soluble vinyl monomers. For example, free-radical polymerization is preferable. The concentration of the monomer may be 2 - 30 % by weight, preferably 5 - 30 % by weight. The polymerization initiator is not particularly critical as far as it is water-soluble, and is usually used by dissolving it in an aqueous solution of the monomer. Examples of polymerization initiators are peroxides such as hydrogen peroxide, benzoyl peroxide and the like; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate and the like, bromates such as sodium bromate, potassium bromate and the like, perborates such as sodium perborate, potassium perborate, ammonium perborate, and the like; percarbonates such as sodium percarbonate, potassium percarbonate, ammonium percarbonate and the like; perphosphates such as sodium perphosphate, potassium perphosphate, ammonium perphosphate, and the like; tert-butyl peroxide and the like. The above-mentioned initiators may be used alone or in combination with a reducing agent as a redox type polymerization agent. As the reducing agent, there may be mentioned, for example, sulfites, hydrogensulfites, salts of iron, copper, cobalt and the like of a low order ionization, organic amines such as N,N,N',N'-tetramethyl ethylenediamine and the like, and reducing sugars such as aldose and ketose. As azo compounds, there may be used 2,2'-azobis-4-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, salts thereof and the like. Further, two or more of the above-mentioned polymerization initiator may be used in combination. The polymerization temperature is as low as 30 to 90°C in the case of a single polymerization initiator, and much lower such as about 5 to 50°C in the case of a redox polymerization initiator. In addition, it is not necessary to keep the temperature at a constant temperature, and the temperature may be changed accordingly as the polymerization proceeds. In general, as the polymerization proceeds, the temperature rises due to the generated polymerization heat. The atmosphere in the polymerization vessel at that time is not particularly limited, but it is desirable to replace the atmosphere with an inert gas such as nitrogen gas for the purpose of accelerating the polymerization. The polymerization time is not critical, but is usually 1 - 20 hours. The method of the present invention is used for making paper from pulp, and is effective to improve remarkably freeness for draining water upon papermaking and improve paper strength serving to enhance the mechanical strength of paper. The amount ratio of Hofmann decomposition PAM and cationic polyacrylamide (B) is optional depending on pulp raw material and white water. However, from the standpoint of mixing effect, it may range from 95 : 5 to 5 : 95, preferably from 80 :20 to 20 :80. The cationic polyacrylamide may be added to pulp in such a monner that Hofmann decomposition PAM and cationic polyacrylamide (B) are separately added to pulp slurry, or Hofmann decomposition PAM and cationic polyacrylamide (B) are firstly mixed and then added to pulp slurry. Either may be used. In combination of Hofmann decomposition PAM and cationic polyacrylamide (B), sometimes the effect is further enhanced when aluminum sulfate or water-soluble anionic resins is used in combination. The water-soluble anionic resins used here may be water-soluble resins having an anionic substituent such as carboxyl group, sulfonic acid group, phosphoric acid group and the like, or salts thereof. Examples of said resins are: anionic acrylamide resins, anionic polyvinyl alcohol resins, carboxymethylcellulose, carboxymethylated starch, sodium alginate, and the like. The point where the agents are to be added is not particularly critical. The agents may be added before or after or simultaneously with adding Hofmann decomposition PAM and cationic polyacrylamide (B) to pulp slurry. Further, the agents may be mixed separately with each of Hofmann decomposition PAM and cationic polyacrylamide (B), or may be mixed with a mixture solution of Hofmann decomposition PAM and cationic polyacrylamide (B). The place where the addition is effected may be anywhere as far as it is before forming a wet sheet. It is preferable to add to a place where chemicals can be sufficiently mixed with and diluted with the pulp slurry and which is near the papermaking wire part, for example, machine chest, mixing box, seed box, white water pit, outlet of screen and the like. As a papermaking machine, there may be used either Fourdrinier paper machine or cylinder paper machine. After the present additive for papermaking is added to a pulp slurry having a concentration of 0.5 - 5.0 %, pH 4.0 - 9.0 at a temperature of 20 - 70°C, a wet sheet is formed at a wire part and then water is squeezed at a press part. The nip pressure at the press part ranges from 20 to 400 kg/cm. After passing the press part, the wet sheet is transferred to a dry part and dried with steam. The steam pressure is 2 - 15 kg/cm² and the drying is carried out in a drum at 80 - 200°C. After this process, chemical treatments may be effected at a size press or calender so as to improve printing property, surface strength, water resistance, and water repellency. The additives for papermaking according to the present invention may be in the form of a water-soluble liquid mixture comprising Hofmann decomposition PAM and cationic polyacrylamide (B) as active components. The concentration of the active components may range from 0.001 to 50 %. The amount ratio of Hofmann decomposition PAM to cationic polyacrylamide (B) may range, in terms of weight, from 95 : 5 to 5 : 95, preferably from 80 : 20 to 20 : 80. When the mixing ratio is too small, the effect due to using in combination is not obtained. On the contrary, when the mixing ratio is too large, the function of the Hofmann decomposition PAM is deteriorated. Here, the decomposition rate of Hofmann decomposition is not particularly critical, but is usually 5 - 60 mol %, preferably 10 - 50 mol %. A method for mixing Hofmann decomposition PAM and cationic polyacrylamide (B) may be as shown below. The solution after Hofmann decomposition reaction is usually of pH 12 - 13, but the pH may be lowered with an inorganic or organic acid before or after mixing with cationic polyacrylamide (B). The additives for papermaking according to the present invention may range from 2 to 14. When paper is manufactured by the above-mentioned method, freeness can be improved without deteriorating paper strength such as rupture strength, internal bond strength, compression strength and the like. Therefore, when the method of the present invention is used for manufacturing paper products where the content of waste paper in the raw materials is high, such as corrugated board, newspaper and the like, very good results are obtained and paper of high strength can be produced. Other than corrugated board and newspaper, when the present invention is applied to manufacturing of high strength paper or the case where excellent freeness is required at a papermaking step, there can be produced papers of high strength in a good productivity. Best Mode for Carrying Out the InventionThe present invention is explained referring to the following examples, but is not restricted by the examples. The % in the following is % by weight unless otherwise specified. PREPARATION EXAMPLE 124.0 g of a 10 wt. % aqueous polyacrylamide solution (Brookfield viscosity at 25°C : 3,400 cps) was placed in a 500 ml beaker, diluted with 36.0 g of distilled water, and heated to 80°C with stirring, and to the resulting solution was added 14.8 g of a mixture solution of sodium hypochlorite and NaOH (concentration of sodium hypochlorite : 1.0 mol/kg; concentration of NaOH : 2.0 mol/kg). The reaction was stopped 15 sec. after the addition of the above-mentioned mixture solution, and there was obtained a 1 wt. % acrylamide polymer (Hofmann PAM (A)). A part of the reaction product was added to an aqueous solution of pH 2 and a colloid titration by means of a 1/400 N aqueous solution of potassium polyvinyl sulfonate using toluidine blue as indicator. The resulting cationicity was 4.4 meq./g. In the following tests the Hofmann PAM (A) was used immediately after the preparation. PREPARATION EXAMPLE 224.0 g of a 12.5 wt. % aqueous polyacrylamide solution (Brookfield viscosity at 25°C : 12,400 cp) was placed in a 500 ml beaker, diluted with 36.0 g of distilled water, and to the resulting solution was added with stirring at 20°C 14.8 g of a mixture solution of sodium hypochlorite and NaOH (concentration of sodium hypochlorite : 1.0 mol/kg; concentration of NaOH : 2.0 mol/kg). Two hours later, 225.2 g of a 0.001 % aqueous solution of sodium sulfite was added thereto to stop the reaction and a 1 wt. % acrylamide polymer (hereinafter called Hofmann PAM (B) ). A part of the reaction product was added to an aqueous solution of pH 2 and a colloid titration was carried out using a 1/400 N aqueous solution of potassium polyvinyl sulfonate with toluidine blue as indicator and the cationcity was 4.4 meq./g. EXAMPLE 1To a pulp slurry (concentration of 1.0 %) having Canadian Standard Freeness (hereinafter called CSF ) of 450 ml and 1.0% concentration obtained from waste paper of corrugated board was added a commercially available rosin emulsion sizing agent in an amount of 0.15% based on the dry weight of pulp followed by stirring for two minutes. Then, aluminum sulfate was added thereto in an amount of 1.0 % based on the dry weight and then stirring was effected for one minute. The pH of the resulting pulp slurry was 5.1. Then, No. 3 water glass was added thereto in an amount of 0.30 % based on the dry weight of pulp, and stirring was effected for one minute. Hofmann PAM (A) obtained in Preparation Example 1 was added in an amount of 0.60 % based on the dry weight of pulp, and stirring was continued for further one minute. Part of the resulting pulp slurry was taken to measure CSF according to JIS-P-8121, and the remainder was used to make paper in a TAPPI square sheet machine, and then the resulting paper was dried for two hours at 110°C by a hot air blowing dryer to obtain a hand-made paper with a basis weight of 150 ± 3 g/m². To evaluate the resulting hand-made paper, its specific compression strength was measured according to JIS-P-8126, its specific rupture strength according to JIS-P-8112 and its internal bond strength by a Kumagaya Riki Internal Bond Tester. Table 1 shows the result. EXAMPLE 2The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.60 % based on the dry weight. Table 1 shows the result. EXAMPLE 3The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.90 % based on the dry weight. Table 1 shows the result. EXAMPLE 4The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 1.50 % based on the dry weight. Table 1 shows the result. COMPARISON EXAMPLE 1The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.003 % based on the dry weight. COMPARISON EXAMPLE 2The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 5.00 % based on the dry weight. COMPARISON EXAMPLES 3 and 4The procedures of Examples 2 and 4 were repeated respectively except that Hofmann PAM (B) was used in place of Hofmann PAM (A) used in Comparison Examples 1 and 2. Table 1 shows the results. EXAMPLE 5To a pulp slurry of Canadian Standard Freeness (hereinafter called CSF ) of 543 ml and 1.0 % concentration obtained from waste paper of corrugated board was added aluminum sulfate in an amount of 0.5 % based on the dry weight of pulp, and stirring was effected for a further minute. The pH of the pulp slurry was 5.8. Then, colloidal silica (Snowtex 40, particle size 10 - 20 nm, manufactured by Nissan Kagaku K.K.) was added thereto in an amount of 0.25 % based on the dry weight of pulp followed by stirring for 30 sec, and Hofmann PAM (A) obtained in Preparation Example 1 was added thereto in an amount of 1.50 % based on the dry weight of pulp. The stirring was continued for further 30 sec. A part of the resulting pulp slurry was taken to measure CSF according to JIS-P-8121, and the remainder was used to make paper in a TAPPI square sheet machine. The product was then dried by a hot air blowing dryer at 110°C for two hours to produce a hand-made paper with a basis weight of 150 ± 3 g/m². To evaluate the resulting hand-made paper, the specific compression strength was measured according to JIS-P-8126, the specific rupture strength according to JIS-P-8112, and the internal bond strength by a Kumagaya Riki Internal Bond Tester. Table 2 shows the result. EXAMPLE 6The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 0.50 % based on the dry weight. Table 2 shows the result. EXAMPLE 7The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 1.00 % based on the dry weight. Table 2 shows the result. COMPARISON EXAMPLE 5The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 0.001 % based on the dry weight. Table 2 shows the result. COMPARISON EXAMPLE 6The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 10.0 % based on the dry weight. Table 2 shows the result. PREPARATION EXAMPLE 3In a four-necked flask equipped with stirrer, reflux condenser, thermometer, and nitrogen inlet pipe were placed 675 g (94 mol %) of 40 % acrylamide, 23.1 % (4 mol %) of dimethylaminoethyl methacrylate, 5.8 g (2 mol %) of acrylic acid, 62.3 mg (0.01 mol %) of bismethylene acrylamide and 1.004 g of water, and the pH of the resulting mixture was adjusted to 4.5 with a 10 % aqueous solution of sulfuric acid. Then the inner temperature was raised to 40°C while blowing nitrogen gas thereinto. A 10% aqueous solution of ammonium persulfate and a 10% aqueous solution of sodium hydrogen sulfite were added to the above-mentioned mixture with stirring and polymerization was initiated. Then, the reaction mixture was kept at 85°C, and three hours after the beginning of the polymerization, water was added to stop the polymerization reaction and there was obtained a stable aqueous solution of acrylamide polymer having 15.3 % of non-volatile matter, Brookfield viscosity of 6,800 cps at 25°C and pH 4.3. PREPARATION EXAMPLE 430.0 g of a 10 wt. % aqueous solution of polyacrylamide (Brookfield viscosity at 25°C : 3,400 cp) was placed in a 500 ml beaker, diluted with distilled water, heated to 80°C with stirring, and then 14.3 g of a mixture solution of sodium hypochlorite and NaOH (concentration of sodium hypochlorite : 1.0 mol/kg; concentration of NaOH : 2.0 mol/kg) was added to the resulting solution and 15 sec. later, 225.7 g of cold water at 5°C was added to stop the reaction. As a result, a 1 wt. % acrylamide polymer (Hofmann PAM (C)) was obtained. A part of the reaction product was added to an aqueous solution of pH 2 and a colloid titration was then carried out using a 1/400 N aqueous solution of potassium polyvinyl sulfonate with toluidine blue as indicator and the cationicity was 3.8 meq./g. In the following test, Hofmann PAM (C) was used immediately after the preparation. EXAMPLE 8To a pulp slurry of Canadian Standard Freeness (hereinafter called CSF ) of 400 ml and 1.0 % concentration obtained from waste paper of corrugated board was added a commercially available rosin emulsion sizing agent in an amount of 0.15 % based of the dry weight of pulp followed by stirring for two minutes. Then, aluminum sulfate was added to the resulting mixture in an amount of 1.0 % based on the dry weight of pulp and stirring was effected for a further minute. At this time, the pH of the pulp slurry was 5.1. Further, the acrylamide polymer obtained in Preparation Example 3 was added to the resulting mixture as above in an amount of 0.30 % based on the dry weight of pulp. Stirring was effected for one minute and then Hofmann PAM (C) obtained in Preparation Example 4 was added thereto in an amount of 0.10 % based on the dry weight of pulp. The stirring was continued for a further one minute and then a part of the resulting pulp slurry was taken to measure CSF according to JIS-P-8121, and the remainder was used to make paper in a TAPPI square sheet machine. The resulting product was dried by a hot air blowing dryer at 110°C for 2 hours to obtain a hand-make paper with a basis weight of 125 ± 3 g/m². To evaluate the hand-made paper, the specific compression strength was measured according to JIS-P-8126, the specific rupture strength according to JIS-P-8112 and the internal bond strength by a Kumagaya Riki Internal Bond Tester. Table 3 shows the result. EXAMPLE 9The procedure of Example 8 was repeated to effect the hand-making paper test except that the polyacrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.20 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.20 % based on the dry weight. Table 3 shows the result. EXAMPLE 10The procedure of Example 8 was repeated to effect the hand-making paper test except that the polyacrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.10 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.30 % based on the dry weight. Table 3 shows the result. COMPARISON EXAMPLE 7The procedure of Example 8 was repeated to effect the test except that the acrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.40 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was not added. Table 3 shows the result. COMPARISON EXAMPLE 8The procedure of Example 8 was repeated to effect the test except that Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.40 % based on the dry weight and the acrylamide polymer obtained in Preparation Example 3 was not added. Table 3 shows the result. As shown in Tables 1 - 2, papers manufactured according to the conditions of the present invention exhibit rather a tendency of improved paper strength by the addition of anionic inorganic substances though addition of anionic inorganic substances usually changes the freeness. It appears that when a proper amount of an anionic inorganic substance is present, the aggregation force of Hofmann PAM is lowered to an appropriate level so that the formation is controlled and the paper strength characteristics such as specific rupture strength, specific compression strength, internal bond strength and the like become excellent. This effect is remarkable when the Hofmann decomposition reaction was carried out in a temperature range of 50°C - 110°C for a short time. The mechanism is not yet clarified, but it is clear that the paper strength effect of PAM obtained by the Hofmann decomposition reaction carried out at a high temperature for a short time can be enhanced by using an anionic inorganic substance. Therefore, when it is contemplated that the formation is controlled and a paper of excellent strength is made even if the freeness is adversely affected to some extent, the present invention exhibits a great effect. In addition, as shown in Table 3, papers made under the conditions within the scope of the present invention can exhibit excellent characteristics such as specific rupture strength, specific compression strength, internal bond strength and the like as compared with the case where an acrylamide polymer obtained in Preparation Example 3 or 4 is used alone while the papers made according to the present invention retains the same level of freeness as that in the case where the acrylamide polymer obtained in Preparation Example 4 is used alone. Rate of addition (%/pipe) Freeness (ml) Specific rupture strength Specific compression strength Internal bond strength (kg/cm) Hofmann PAM Colloidal silica Example 51.500.256032.7821.82.40 Example 61.500.506062.8321.72.51 Example 71.501.005923.0322.32.26 Comparison Example 51.50-5502.4820.12.09 Comparison Example 6-10.05422.0718.21.23 Rate of Addition (%/pipe) Freeness (ml) Specific rupture strength Specific compression strength Internal bond strength (kg/cm) Copolymerization PAM Hofmann PAM (C) Example 80.300.106452.7214.52.99 Example 90.200.206452.7014.43.07 Example 100.100.306482.6914.03.15 Comparison Example 70.40-4692.4712.61.92 Comparison Example 8-0.406502.4813.02.78 Industrial ApplicabilityThe paper produced by the method of the present invention exhibits excellent specific rupture strength, specific compression strength, internal bond strength and the like. Addition of the anionic inorganic substance is suitable for controlling the formation and producing a paper of high strength even if the freeness is somewhat adversely affected. When the cationic polyacrylamide is added, the level of freeness attained by using an acrylamide polymer alone can be retained, the formation is not lowered despite of good freeness which usually indicates lowering thereof, and the paper strength characteristic is excellent as compared with that when the acrylamide polymer is used alone.
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A method for papermaking which comprises adding to a pulp slurry both an anionic inorganic substance and a cationic acrylamide polymer produced by reacting an acrylamide polymer with a hypohalogenite under alkaline conditions at 50 - 110°C for a short time, and then forming a wet pulp sheet followed by dehydration with a press and drying with a drier. A method according to claim 1 wherein the cationic acrylamide polymer is produced by reacting the acrylamide polymer with the hypohalogenite under alkaline conditions of at least about pH 11 at a reaction temperature T (°C): 50°C ≦ T ≦ 110°C for a reaction time t (sec) according to the following formulas: An additive for papermaking which comprises an anionic inorganic substance and a cationic acrylamide polymer obtainable by reacting an acrylamide polymer with a hypohalogenite under alkaline conditions at 50 - 110°C for a short time. An additive according to claim 3 wherein the cationic acrylamide polymer is obtained by reacting the acrylamide polymer with the hypohalogenite under alkaline conditions of at least about pH 11 at a reaction temperature T (°C): 50°C ≦ T ≦ 110°C for a reaction time t (sec) according to the following formulas: A method for papermaking which comprises adding to a pulp slurry both a cationic acrylamide polymer (A) produced by reacting an acrylamide polymer with a hypohalogenite under alkaline conditions at 50 - 110°C for a short time and a cationic polyacrylamide (B) produced by copolymerizing (a) a cationic monomer of the general formula (I), where R₁ is hydrogen or methyl, R₂ and R₃ are hydrogen or alkyl having 1 - 6 carbon atoms, X is O or NH, and n is an integer of 2 - 4, and/or organic or inorganic acid salts thereof, or quaternary ammonium salts produced by the reaction of the compound of the general formula (I) with a quaternizing agent, (b) an α,β-unsaturated carboxylic acid and/or salts thereof, and (c) an acrylamide monomer of the general formula (II)CH₂ = C (R₅) - CONH₂ (II) where R₅ is hydrogen or methyl, and then forming a wet pulp sheet followed by dehydration with a press and drying with a dryer. A method according to claim 5 wherein the cationic acrylamide polymer (A) is produced by reacting the acrylamide polymer with the hypohalogenite under alkaline conditions of at least about pH 11 at a reaction temperature T (°C): 50°C ≦ T ≦ 110°C for a reaction time t (sec) according to the following formulas: An additive for papermaking which comprises a cationic acrylamide polymer (A) obtainable by reacting an acrylamide polymer with a hypohalogenite under alkaline conditions at 50 - 110°C for a short time and a cationic polyacrylamide (B) produced by copolymerizing (a) a cationic monomer of the general formula (I), where R₁ is hydrogen or methyl, R₂ and R₃ are hydrogen or alkyl having 1 - 6 carbon atoms, X is O or NH, and n is an integer of 2 - 4, and/or organic or inorganic acid salts thereof, or quaternary ammonium salts produced by the reaction of the compound of the general formula (I) with a quaternizing agent, (b) an α,β-unsaturated carboxylic acid and/or salts thereof, and (c) an acrylamide monomer of the general formula (II)CH₂ = C (R₅) - CONH₂ (II) where R₅ is hydrogen or methyl. An additive according to claim 7 wherein the cationic acrylamide polymer (A) is obtainable by reacting an acrylamide polymer with a hypohalogenite under alkaline conditions of at least about pH 11 at a reaction temperature T (°C): 50°C ≦ T ≦ 110°C for a reaction time t (sec) according to the following formulas:
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MITSUI TOATSU CHEMICALS; MITSUI TOATSU CHEMICALS, INC.
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DOKI HIROTOSHI; ITOH HIROSHI; TAKAHASHI HIDEAKI; TAKAKI TOSHIHIKO; TSUTSUMI HARUKI; DOKI, HIROTOSHI; ITOH, HIROSHI; TAKAHASHI, HIDEAKI; TAKAKI, TOSHIHIKO; TSUTSUMI, HARUKI
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EP-0489932-B1
| 489,932 |
EP
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B1
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EN
| 19,990,210 | 1,992 | 20,100,220 |
new
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C22C19
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H01L23, C22C38, H01J1, H01F1, H01J29
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H01J9, H01J29, C22C38, H01L23, H01F1, C22C19, H01J1
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H01J 1/38, H01J 1/48, H01J 9/14, H01L 23/495M, H01F 1/147N, H01J 29/02, C22C 38/08, C22C 38/12, C22C 19/03
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IRON-NICKEL ALLOY
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An iron-nickel alloy comprising 25 to 50 wt% of nickel, 0.001 to 0.1 wt% of carbon, 0.01 to 6 wt% of at least one element selected from among groups IVa and Va elements, such as niobium or tantalum, and the balance comprising substantially iron and inevitable impurities. This alloy contains particles containing carbides including those of groups IVa and Va elements finely and uniformly dispersed in the alloy structure, thus improving mechanical strengths, thermal resistance and other properties, enhancing punchability, and reducing gas release in a vacuum.
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TECHNICAL FIELDThe present invention relates to a cathode ray tube part produced using a Fe-Ni based alloy having a small thermal expansion coefficient.BACKGROUND ARTA Fe-Ni based alloy, e.g., 42 wt % Ni-Fe and 29 wt % Ni-17 wt % Co-Fe has been hitherto known as an alloy having a low thermal expansion. This kind of Fe-Ni based alloy has been p used in industrial application fields where a metallic material having a low thermal expansion coefficient, e.g., a material for a lead frame used for producing an integrated circuit package or the like, a material for a part constituting a cathode ray tube such as a Braun tube, a sealing material are required.Firstly, description will be described below as to, e.g., a material for a part constituting a cathode ray tube. A plurality of electrodes for converging or deviating an electron beam emitted from a cathode are arranged in the cathode ray tube. With respect to a material required for constituting the electrodes, it is an essential condition that the material has a small thermal expansion coefficient in order to assure that an electron beam from the cathode is emitted without any undesirable disturbance due to thermal expansion during the working of the cathode ray tube. For this reason, the foregoing kind of Fe-Ni based alloy is employed. However, although a conventional Fe-Ni based alloy satisfactorily meets the requirement for a low thermal coefficient, it has the following drawbacks. Accordingly, many strong requests have been raised so as to obviate these drawbacks.One of the drawbacks inherent to the conventional Fe-Ni based alloy is that a burr having a high height appears during a punching operation performed by actuating a press machine. When a material having a burr having a high height formed in a punching region is employed for part constituting a cathode ray tube, there arises a malfunction that electron beam properties are adversely affected. In addition, in the case where this material is employed for forming a lead frame, if a burr formed has a high height, there appear problems that the number of bending the lead pin is reduced, and moreover, a running life of a press die is shortened. Also with respect to the sealing material, when a bur is located, e.g., in the sealing region, cracks readily extend from the sealing region, whereby properties of the part are affected adversely.In recent years, as semiconductor elements are integrated at a larger density, it is increasingly required that each lead frame is designed to have a thinner thickness while using a number of pins. In connection with the foregoing current status, a material for forming a lead frame, composed of the conventional Fe-Ni based alloy, has problems that a fine pattern can not be formed with excellent reproductivity, and moreover, the material has insufficient mechanical strength and heat resistance. Not only with the material for forming a lead frame but also with a material for forming a part constituting a cathode ray tube, when the material for forming a part constituting a cathode ray tube has insufficient mechanical strength and heat resistance, it is remarkably softened by heat treatment carried out before an assembling operation. This leads to problems that a capability of handling is degraded and undesirable deformation is liable to occur during the assembling operation.Generally, the conventional Fe-Ni based alloy has a large quantity of dissolved gas. For this reason, when it is employed as a material for forming a part constituting a cathode ray tube, there appear problems that a quantity of gas release in a vacuum is increased and a degree of vacuum in the cathode ray tube is lowered, resulting in properties of a products being degraded undesirably.The present invention has been made with the foregoing background in mind.An object of the present invention is to provide a Fe-Ni based alloy which assures that mechanical strength, heat resistance and other properties are improved.Other object of the present invention is to provide a Fe-Ni based alloy having excellent working properties such as a performance of punching work.Another object of the present invention is to provide a Fe-Ni based alloy which assures that a quantity of gas release in a vacuum is kept small.DISCLOSURE OF THE INVENTIONThe Fe-Ni based alloy is known as a low thermal coefficient material.Reference GB-A-1137608 discloses an Fe-Ni based alloy, used as tank material, exposed to very low temperature conditions, wherein the Fe-Ni alloy includes less than 0.05 % by weight of S and is produced according to vacuum induction melting and casting, and subsequent annealing in a relatively high temperature range of 980 to 1095°C.Japanese Patent Application Laid Open SH063-14841 discloses a material for a shadow mask consisting of 0.01-1.0 % by weight of one or more than two elements selected from the group of ti, Zr, B, Mo, Nb, N, P, Cu, V, Mg, Co, and W as a particle growth retardant, in addition to less than 0.01 % by weight of C, less than 0.30 % by weight of Si, less than 0.30 % by weight of Al, 0.1-1.0 % by weight of Mn, 34.0-38.0 % by weight of Ni and the balance Fe with inevitable impurities, and annealed at a temperature of 1100°C, which is higher than that utilized in the process of the present invention. Further, there is no mention to the importance of the existence of the carbide particles.Japanese Patent Application Laid Open SH063-14842 also discloses a material for shadow mask consisting of less than 0.10 % by weight of C, not more than 0.30 % by weight of Si, less than 0.30 % by weight of Al, 0.1-1.0 % by weight of Mn, 34.0-38.0 % by weight of Ni, 0.01--1.0 % by weight of V, and the balance Fe with inevitable impurities, wherein the ratio of V/C is preferably regulated to more than 1.5 and the grain size of vanadium carbide is preferably reduced to less than 50 µm. It does not disclose the number of the carbide particles, i.e. the carbide particle distribution, relation between the carbide particle size and the number of the carbide particles and relatively low alloy annealing temperature which the present invention utilizes. According to the present invention, there is provided a cathode ray tube part produced by punching, said part comprising a Fe-Ni based alloy consisting of 25 to 55 % by weight of Ni, 0.001 to 0.1 % by weight of C, 0.01 to 6 % by weight of at least one element selected from the group consisting of Group IVa elements and Group Va elements of the periodic table, and a balance of Fe and unavoidable impurities; wherein said alloy has dispersed carbide particles in a substructure thereof within the range of 1000 to 100,000 particles/cm2, with each of said dispersed carbide particles having a size of not more than 20 µm.Preferred embodiments of the cathode ray tube part, defined in claim 1 are given in the dependent claims.The composition of the Fe-Ni based alloy of the present invention as defined above will be described in more detail below.Nickel is an element which serves to reduce a thermal expansion coefficient. the thermal expansion coefficient is increased wither when a content of the nickel is less than 25 % by weight or when it exceeds 55 % by weight, resulting in an effective feature, derived from the alloy having a low thermal expansion coefficient, being lost undesirably. It is preferable that the content of Ni remains within the range of 36 % by weight to 50 % by weight. A carbon finely and uniformly disperses in the substructure as a carbide of at least a part of one element selected from the Group IVa elements and the Group Va elements. As a result, mechanical strength and heat resistance can substantially be improved while an adequate performance of punching work is given to the Fe-Ni based alloy. The carbon functions as a deoxidizer agent when producing an ingot. In other words, a characteristic of the present invention is that the carbon is intentionally added. According to the present invention, a content of the carbon is determined to remain within the range of 0.001 % by weight to 0.1 % by weight. If the carbon content is less than 0.001 % by weight, strength and heat resistance fail to be improved satisfactorily, and sufficient deoxidation can not be achieved when raw materials for the Fe-Ni based alloy are molten. On the contrary, if the carbon content exceeds 0.1 % by weight, the property of workability is degraded, and moreover, mechanical strength is excessively increased, resulting in a performance of pressing work for forming various kinds of parts to their predetermined contour being degraded remarkably. It is more preferable that the carbon content is determined to remain with in the range of 0.01 % by weight to 0.05 % by weight.At least one element selected from the Group IVa elements and the Group Va elements is precipitated or crystallized in the form of a single element, a compound such as a carbide, nitride or an intermetallic compound of Fe, and it is present in the form of dispersed particles in the substructure. Thus, mechanical strength and heat resistance can be improved while an adequate performance of punching work is obtained. In addition, the foregoing element serves to fixate a dissolved gas component as a carbide or nitride so as to reduce a quantity of gas release in a vacuum. Especially, the Group IVa elements and the Group Va elements are an element which is liable to be precipitated as a carbide or nitride. Since the aforementioned effect can remarkably be obtained when one element selected especially from Nb and Ta is used as the foregoing element, it is desirable that the foregoing element is used.A content of at least one element selected from the Group IVa elements and the Group Va elements is determined to remain within the range of 0.01 % by weight to 6 % by weight. If the content of the foregoing element is less than 0.01 % by weight, the added element is solid-dissolved in a matrix, resulting in a quantity of dispersed particles composed of carbide becoming short. Thus, mechanical strength and heat resistance can not be improved sufficiently. Additionally, a quantity of gas release is undesirably increased. On the contrary, if the content of the foregoing element exceeds 6 % by weight, a property of workability is degraded, and moreover, mechanical strength is excessively increased, resulting in a property of press-working for forming various kinds of parts to their predetermined contour being degraded remarkably. It is more preferable that a content of at least one kind of element selected from the Group IVa elements and the Group Va elements is determined to remain within the range of 0.1 % by weight to 3 % by weight. With respect to the Group IVa elements and the Group Va elements, a plurality of elements may be used. Alternatively, a single element may be used. In the case where a plurality of elements are used, the total content of these elements should be determined to remain within the aforementioned range.In addition, in the Fe-Ni based alloy of the present invention, it is preferable that a content of S as an impurity is less than 0.05 % by weight. This is because if the content of sulfur exceeds 0.05 % by weight, a quantity of gas release in a vacuum is increased. Advantageous effects derived from the present invention are not adversely affected even when Mn, added as a deoxidizing agent is contained by a quantity of not more than 2 % by weight, and moreover, impurities such as P, Si are contained by a quantity of not more than about 0.1 % by weight.As described above, in the Fe-Ni based alloy of the present invention, dispersed particles inclusive of a carbide of the Group IVa elements and the Group Va elements are present in the substructure. Since the carbide is finely and uniformly dispersed in the substructure, mechanical strength, heat resistance, a performance of punching work and other properties of the Fe-Ni based alloy are improved effectively. In other words, an effect derived from dispersion can be improved further, and moreover, mechanical strength can be improved by uniformly dispersing the fine particles of a carbide in the substructure. In addition, since dislocation at high temperatures is suppressed, heat resistance such as softening can be improved. Additionally, since a performance of punching work is improved by the fine crystalline structure due to the dispersed particles, the height of a bur can be reduced.It is preferable that a size of the dispersed particle is not more than 20 µm, and moreover, it is preferable that the dispersed particles having the foregoing size are present within the range of 1000 particles/cm2 to 100000 particles/cm2. It is more preferable that the number of dispersed particles remains within the range of 5000 particles/cm2 to 100000 particles/cm2. If a size of the dispersed particle exceeds 20 µm, mechanical strength and heat resistance fail to be sufficiently improved and a performance of punching work is degraded. As a result, there is a tendency that the height of a bur appearing around a punched hole (hereinafter referred to as a hole bur) is increased. It should be noted that a size of the dispersed particle which has been referred to herein designates a diameter of a smallest circle in which the dispersed particle is included. When the number of dispersed particles is smaller than 1000 particles/cm2, mechanical strength and heat resistance fail to be sufficiently improved. In addition, there is a tendency that a performance of punching work is degraded, the height of the hole bur is increased and a breakage angle becomes small. On the contrary, if the number of dispersed particles exceeds 100000 particles/cm2, a performance of rolling work or the like is degraded.The Fe-Ni based alloy of the present invention is produced, e.g., by way of the following steps. First, alloy components satisfying the requirement for the aforementioned alloy composition are molten and cast within the temperature range of 1400 °C to 1600 °C to produce an ingot. Subsequently, the ingot is subjected to hot forging and/or hot rolling within the temperature range of about 1000 °C to 1200 °C. Thereafter, the resultant plate is repeatedly subjected to cold working at a working rate of 30 to 80 % as well as annealing for a period of time of five minutes to one hour at a temperature of about 800 °C to 1100 °C. As a result, a required Fe-Ni based alloy is obtained.For example, in the case where the Fe-Ni based alloy is employed for forming a lead frame, after the hot working and cold working to produce a sheet material having a predetermined thickness. Subsequently, the sheet is subjected to punching to form a lead frame having a predetermined contour. In the case where the Fe-Ni based alloy is employed as a material for forming a part constituting a cathode ray tube, the aforementioned operations are conducted.BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a view for explaining evaluation method of a performance of punching work, Fig. 3 is a plan view of cathode ray tube part of another embodiment where the Fe-Ni based alloy of the present invention is used.BEST MODE FOR CARRYING OUT THE INVENTIONNow, the present invention will be described in detail which illustrate preferred embodiments of the present invention.First, description will be made below with respect to examples of a Fe-Ni based alloy of the present invention and results derived from evaluation on these examples.EXAMPLE 1 to 23Alloy components each of which composition is shown in Table 1 were molten at a temperature of about 1500 °C and each molten alloy was cast to form ingots. Thereafter, each ingot was forged at a temperature of 1000 °C to 1200 °C to produce a billet having dimensions of 150 mm X 600 mm X L.Thereafter, each billet was subjected to hot rolling at a temperature of 1000 °C to 1200 °C until its thickness was reduced to 3.5 mm. Subsequently, the plate was repeatedly subjected to cold rolling and annealing under conditions of about 950 °C X about 30 minutes until its thickness was reduced to 0.3 mm. After the cold rolled sheet was additionally subjected to cold rolling to reduce its thickness to 0.15 mm, it was annealed at a temperature of about 950 °C for about 30 minutes, whereby a plate-shaped alloy sample was obtained.A size and the number of particles dispersed within several visual fields in each plate-shaped alloy sample obtained in the above-described manner were measured based on structure photographs by a metallurgical microscope having a magnification of 400. Results derived from the measurement are shown in Table 2. It should be noted that the size of particles dispersed shown in the table is represented by an average value. In addition, with respect to the respective plate-shaped alloy samples, the following properties were evaluated. These results are shown also in Table 2.(1) Thermal expansion coefficientNumerals in a column of thermal expansion coefficient show a thermal expansion coefficient measured within the temperature range of 30 °C to 300 °C.(2) Variation of hardness for heat treatmentEach plate-shaped sample was subjected to heat treatment at a temperature of 1050 °C for 10 minutes, and hardness before and after the heat treatment were measured.(3) Performance of punching workA punching operation was performed for each plate-shaped sample with the aid of a press machine so as to form a hole, and a height of a bur appearing around the punched hole and a breakage angle were measured based on the sectional form.(4) Property of gas releaseA quantity of gas release in a vacuum of 1.33x10-5 Pa (10-7 Torr) was measured with respect to each plate-shaped sample.(5) Speed of gas releaseA speed of gas release in the vacuum of 1.33x10-5 Pa (10-7 Torr) was measured with respect to each plate-shaped sample.Evaluation on the performance of punching work as mentioned in the (3) was carried out such that a height h of the bur 3 appearing around the end of a broken surface 1 was measured as a bur height and that an angle defined by the broken surface 1 of the punched part and a punched surface 2 of the same was measured as a breakage angle. The smaller the breakage angle , the larger the height h of the bur 3. In addition, the bur 3 was liable to tilt toward the punched hole side, causing various problems.Additionally, for the purpose of comparison with the present invention, plate-shaped samples were similarly produced, using a Fe-Ni based alloy departing from the scope of the present invention (Comparative Examples 1 to 6). The compositions of the samples are shown in Table 1. Evaluation was carried out on the respective plate-shaped samples in the same manner as the aforementioned examples. The results are additionally shown in Table 2.As is apparent from the results shown in Table 2, the Fe-Ni based alloy in the examples have a low thermal coefficient but exhibit a high hardness. In addition, the hardness of each plate-shaped sample was few reduced after completion of a heat treatment at a temperature of 1050 °C. Additionally, the breakage angle recognized after completion of a punching operation was large, and moreover, the height h of the bur is low. In other words, the Fe-Ni based alloy of the present invention is superior in a performance of punching work. A quantity of gas release in a vacuum is small.As is apparent from the above description, in the case where the Fe-Ni based alloy of the present invention is employed for a material requiring a low thermal expansion coefficient such as a material for forming a lead frame, a material for forming a part constituting a cathode ray tube, sealing material, even if it is a thin plate, the requirements for mechanical strength, heat resistance and other properties can be satisfied and reproductivity of a shape can be improved. For example, when it is employed as a material for forming a lead frame, the above-mentioned advantages are obtained and, moreover, the number of bending a lead can be improved. When it is employed as a material for forming a cathode ray tube part, it becomes possible to prevent its electron beam properties from being adversely affected, whereby a performance of assembling operation can be improved. Additionally, since a quantity of gas release is reduced substantially, properties of each product can be improved.Next, the present invention will be described below with respect to an embodiment wherein the Fe-Ni based alloy of the present invention is employed for forming a lead frame.First, the Fe-Ni based alloy in Example 2 was repeatedly subjected to cold rolling and annealing under conditions of 950 °C X about 30 minutes so as to produce a sheet having a thickness of 0.25 mm. Subsequently, the sheet of the Fe-Ni based alloy was subjected to punching to exhibit a contour of the lead frame as shown in Fig. 2, whereby a required lead frame 11 was obtained.For the purpose of comparison with the present invention, a lead frame was produced in the same manner as mentioned above using the Fe-Ni based alloy in Comparative Example 1.Then, a hardness of each lead frame produced in the above-described manner as well as a running life of a punching die (represented by the total number of punching operations practically performed) were measured. Hardness (Hv) was 203 and the total number of punching operations was 850 X 103 with respect to the lead frame in Comparative Example 1, while hardness (Hv) was 240 and the total number of punching operations 1300 X 103 with respect to the lead frame in Example 2. This means that mechanical strength and a performance of punching work were improved with respect to the lead frame in Example 2 compared with those of the lead frame in Comparative Example 1.Next, the present invention will be described below with respect to an embodiment wherein the Fe-Ni based alloy of the present invention was employed as a material for forming a part constituting a cathode ray tube.First, the Fe-Ni based alloy in Example 1 was repeatedly subjected to cold rolling and annealing under conditions of about 950 °C X about 30 minutes so as to produce a sheet having a thickness of 0.175 mm. Subsequently, the sheet of Fe-Ni based alloy was subjected to punching to exhibit a cathode ray tube part as shown in Fig. 3, whereby a required part 12 for a cathode ray tube was obtained.For the purpose of comparison with the present invention, a cathode ray tube part was produced using the Fe-Ni based alloy in Comparative Example 2.A cathode ray tube was assembled using the part produced in the above-described manner and a rate of rejection due to deformation of the part was then measured. The rate of rejection was 0.6% with respect to the cathode ray tube part in Comparative Example 2, while the rate of rejection was 0.04% with respect to the cathode ray tube part in Example 1. This means that the rate of rejection due to deformation of the part Example 1 was remarkably improved compared with the cathode ray tube part in Comparative Example 2.INDUSTRIAL APPLICABILITYAs described above, the Fe-Ni based alloy of the present invention assures that the requirement for a low thermal expansion coefficient is satisfied, it has a high hardness and excellent heat resistance, it is superior in performance of punching work, and moreover, a quantity of gas release in the vacuum is small. Owing to these advantages, the present invention can provide an alloy material preferably employable for a material for forming a part constituting a cathode ray tube.
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A cathode ray tube part produced by punching, said part comprising a Fe-Ni based alloy consisting of 25 to 55 % by weight, of Ni, 0.001 to 0.1 % by weight of C, 0.01 to 6 % by weight of at least one element selected from the group consisting of Group IVa elements and Group Va elements of the periodic table, and a balance of Fe and unavoidable impurities; wherein said alloy has dispersed carbide particles in a substructure thereof within the range of 1000 to 100,000 particles/cm2, with each of said dispersed carbide particles having a size of not more than 20 µm.A cathode ray tube part according to claim 1, wherein a carbide of said dispersed carbide particles is at least one carbide selected from the group consisting of carbides of Group IVa elements and Group Va elements of the periodic table.A cathode ray tube part according to claim 1 or claim 2, wherein said at least one element selected from the group consisting of Group IVa elements and Group Va elements of the periodic table is at least one element selected from Nb and Ta. A cathode ray tube part according to any one of claims 1 to 3, wherein said alloy has a content of S as an impurity of less than 0. 05% by weight.A cathode ray tube part according to any one of claims 1 to 3, wherein said alloy optionally comprises not more than 2% by weight of Mn, not more than 0.1% by weight of Si, not more than 0.1% by weight of P, less than 0.05% by weight of S.A cathode ray tube part according to any preceding claim, wherein a quantity of gas release in a vacuum of 1.33 x 10-5 Pa (10-7 Torr) of said Fe-Ni alloy is 12.4 Torr·cc (1649 Pa·cc) or less, and a speed of gas release of 1.12x10-3 Torr·cc/s·g or less (1.490·10-1 Pa·cc/s·g or less) in a vacuum of 1.33 x 10-5 Pa (10-7 Torr).
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TOSHIBA KK; KABUSHIKI KAISHA TOSHIBA
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NAKASHIMA NOBUAKI; SUGAI SHINZO; WATANABE EIICHI; NAKASHIMA, NOBUAKI; SUGAI, SHINZO; WATANABE, EIICHI
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EP-0489941-B1
| 489,941 |
EP
|
B1
|
EN
| 19,950,503 | 1,992 | 20,100,220 |
new
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C08F226
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C09D157
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C09D157, C08F226
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C08F 226/06
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Industrial coatings with oxazoline latex
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The incorporation of oxazoline monomers into conventional latexes imparts resistance to flash rust and salt fog of industrial coatings which contain the oxazoline latex.
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The present invention incorporates the use of oxazoline monomers in combination with other monomers typically used in emulsion polymerizations to prepare a copolymer latex that is salt fog and flash rust resistant when used in an industrial coating or paint formulation. Latex polymers are well known in the art to provide binding in paint formulations. However, such aqueous coatings can cause rusting when the formulations are coated on cold rolled steel. EP-A-0 176 609, PATENT ABSTRACT OF JAPAN, vol. 14, no. 322(C-739)[4265], 1990, and CHEMICAL ABSTRACTS, vol. 84, no. 20, 1976, page 102, abstract no. 137329t disclose coating compositions comprising a polymer latex containing oxazoline monomer. Accordingly, the present invention is a method of increasing the resistance of a latex based coating to rusting and salt fog by the addition of oxazoline monomers during the polymerization of the copolymer latex. Specifically, the latex utilized in the present invention is an emulsion polymerized copolymer having (a) a first charge of monomer comprising an effective amount of at least one ethylenically unsaturated monomer and (b) a second charge of monomer comprising (i) an effective amount of an oxazoline monomer represented by the following formula: wherein R¹ is a polymerizable organic group; each R² is independently hydrogen, halogen, alkyl, or an alkylene group of two to four carbons; n is 1 or 2; and (ii) an effective amount of at least one ethylenically unsaturated comonomer. This copolymer latex is admixed with other standard components to form an industrial coating formulation. The present invention is thus an industrial coating formulation which comprises a pigment carrier, a thickener, a defoamer, a wetting agent, a dispersant, a bacteriostat, at least one pigment, a pigment stabilizer and a latex copolymer of (i) an oxazoline monomer represented by the formula: wherein R¹ is a polymerizable organic group; each R² is independently hydrogen, halogen, alkyl, or an alkylene group of two to four carbons; n is 1 or 2; and (ii) an effective amount of at least one ethylenically unsaturated comonomer. Preferably, R¹ is wherein R³ is hydrogen or an alkyl group. Most preferably, R¹ is an isopropenyl group. Each R² is preferably hydrogen or an alkyl group with hydrogen being most preferred; n is preferably 1. Most preferably the oxazoline monomer is 2-isopropenyl-Δ2-oxazoline. The ethylenically unsaturated comonomers and mixtures of comonomers which are suitably employed with oxazoline monomer in the present copolymer latex include monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide or vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, such as vinyl acetate or vinyl stearate, methacrylonitrile and acrylonitrile. A monoethylenically unsaturated carboxylic acid monomer is also preferably included as a monomer in the first charge. The preferred comonomers of the first and second charge are the acrylate monomers. The term monovinyl aromatic monomer , as used herein, is meant to include those monomers with a polymerizable group of the formula (wherein R is hydrogen or a lower alkyl such as an alkyl having from 1 to 4 carbon atoms) attached directly to an aromatic nucleus, including those wherein the aromatic nucleus is substituted with alkyl or halogen substituents. Examples include styrene, alpha methyl styrene, p-methyl styrene, t-butyl styrene, vinyltoluene, and halogenated styrene. The more preferred monomer of the monovinyl aromatic monomers is styrene. Typically an effective amount of monovinyl aromatic monomer present in the copolymer will depend on the monomer chosen, however, the typical range will be from 10 to 90 weight percent based on the total weight of monomer. The term aliphatic conjugated diene , as used herein, is meant to include monomer compounds such as isoprene, 1,3-butadiene, 2-methyl-1,3-butadiene, piperylene (1,3-pentadiene), and other hydrocarbon analogs of 1,3-butadiene. Typically the amount of aliphatic conjugated diene monomer present in the copolymer will depend on monomer chosen, however, the typical range will be from 0 to 70 weight percent based on the total weight of monomer. Vinylidene halide and vinyl halide monomers suitable for this invention include vinylidene chloride and vinyl chloride, which are highly preferred. Vinylidene bromide and vinyl bromide can also be employed. Typically an effective amount of vinylidene halides and vinyl halides present in the copolymer will depend on monomer chosen, however, the typical range will be from 10 to 90 weight percent based on the total weight of monomer present. The term acrylate , as used herein, is meant to include acrylate or methacrylate monomers. The acrylates can include acids, esters, amides, and substituted derivatives thereof. Generally, the preferred acrylates are C₁-C₈ alkyl acrylates or methacrylates. Examples of such acrylates include butyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, tert-butyl acrylate, methylmethacrylate, butylmethacrylate, ethyl methacrylate, hexylmethacrylate, isobutylmethacrylate, and isopropylmethacrylate and mixtures thereof. The preferred acrylates are butyl acrylate and methylmethacrylate. Typically an effective amount of acrylate present in the copolymer will depend on monomer chosen, however, the typical range will be from 10 to 98 weight percent based on the total weight of the monomer. The term monoethylenically unsaturated carboxylic acid monomer , as used herein, is meant to include those monocarboxylic monomers such as acrylic acid, and methacrylic acid; dicarboxylic monomers such as itaconic acid, fumaric acid, maleic acid, and their monoesters. Typically an effective amount of monoethylenically unsaturated carboxylic acid monomer present in the copolymer is that amount necessary to stabilize the copolymer particle. A typical example of such an amount is from 0.5 to 6 weight percent based on the total weight of monomer present. The oxazoline monomer employed herein is as represented by the general structure: wherein R¹ is a polymerizable organic group; each R² is independently hydrogen, halogen, alkyl, or alkylene group of two to four carbons; n is 1 or 2. Preferably, R¹ is wherein R³ is hydrogen or an alkyl group. Most preferably, R¹ is an isopropenyl group. Each R² is preferably hydrogen or an alkyl group with hydrogen being most preferred; n is preferably 1. Most preferably the oxazoline monomer is 2-isopropenyl-Δ2-oxazoline. The effective amounts of oxazoline monomer present are from 0.25 to 5.0 weight percent based on total amounts of monomer present in the copolymer. Preferably, the amounts of oxazoline monomer present are from 0.5 to 2.0 weight percent based on total amounts of monomer present in the copolymer. Most preferably the amounts of oxazoline monomer present are about 1.0 weight percent based on total amounts of monomer present in the copolymer. A conventional crosslinking agent is also added during the polymerization of the monomers. Examples of conventional crosslinking agents include allyl acrylate, crotyl methacrylate or acrylate, ethylene glycol dimethacrylate and the like. The monomers of the present invention can be polymerized by conventional emulsion polymerization processes. The more preferred method of polymerization is by a semi-continuous process. The polymerization is a two step process wherein a first charge of ethylenically unsaturated monomer, preferably a combination of acrylate monomers, and a monoethylenically unsaturated carboxylic acid is continuously added and allowed to polymerize; at the conclusion of the addition of the first monomer charge is added a second monomer charge typically comprised of the oxazoline monomer and at least one ethylenically unsaturated monomer preferably a combination of acrylate monomers. Prior to the addition of the second monomer charge of oxazoline monomer, the pH of the polymerization medium should be adjusted to greater than about 8. The industrial coatings are typically formulated from a conventional pigment grind which is a mixture of: a pigment carrier such as water, a thickener, a defoamer, a wetting agent, a dispersant, a bacteriostat, pigments, a pigment stabilizer, a coalescent and a latex or a blend of latexes. For some applications it may be desirable to use a blend of one or more oxazoline containing latexes and one or more latexes which do not contain oxazoline. These components are conventionally known components of industrial paint formulations. The flash rust resistance of either the latex or the paint formulation is determined by drawing the mixture down on clean cold-rolled steel such as matte finish Q-panels. The mixture is dried at cool temperatures and elevated humidity such as in a Forma Scientific Environmental Chamber to allow the latex film or the paint film to dry slowly and thereby optimizing the conditions in which rusting will occur. Example 1Butyl acrylate/methylmethacrylate/methacrylic acid monomers in a ratio of 48/48/4.5 parts by weight are continuously added with stirring over a period of 2.0 hours at 66 parts by weight (per 100 parts by weight of the total monomer charge) into an initial aqueous medium containing .01 part by weight of the pentasodium salt of diethylenetriaminepentacetic acid and 0.52 parts by weight of a styrene/acrylic acid (96/4) copolymer seed latex. In addition, an aqueous stream containing (based on 100 parts by weight of the total monomer charge) 40 parts of deionized water, 1.0 part of sodium dodecyldiphenyl ether disulfonate and 0.2 part of sodium persulfate is added over a period of 3.5 hours commencing at the same time the acrylate monomer charge is started. After the butyl acrylate/methylmethacrylate/methacrylic acid charge has been added, the pH is adjusted from 3.0 to 8.0 using ammonium hydroxide. Following the pH adjustment, a butyl acrylate/methylmethacrylate/isopropenyl oxazoline (47.5/47.5/3.0) monomer charge is continuously added with stirring over a 1.0 hour period at 34 parts by weight per 100 parts total monomer charge. A paint formulation is then prepared as follows. A paint grind is prepared by mixing, at 3000 rpm in a Cowles disperser for 15 to 20 minutes: 510 grams of diethylene glycol monomethyl ether, 120 grams of a polycarboxylic acid salt which acts as a dispersant, 30 grams of octylphenoxypolyethoxyethyl benzyl ether which acts as a surfactant, 37.5 grams of a defoamer made from petroleum derivatives, and 2550 grams of a titanium dioxide pigment. Comparative Sample A and Sample A are prepared by mixing for each sample: 60 grams of the paint grind with 5.5 grams of diethylene glycol monobutyl ether; 2.2 grams of a rheology modifier of methane polymers: propylene glycol and water; 9.6 grams of a coalescent of 2,2,4-trimethyl-1,3-pentandiol monoisobutyrate; latex; and water. The latexes used are Comparative Latex A, prepared similarly to the latex prepared above, comprising 47 percent styrene, 50 percent butylacrylate and 3 percent acrylic acid, and Latex A which is prepared similarly to the latex prepared above comprising 47 percent styrene, 49 percent butylacrylate, 3 percent acrylic acid and 1 percent isopropenyl oxazoline. The amount of latex added to the formulation is calculated such that 63.3 grams of latex solids are added to each sample. The total water added to the formulation is 122.9 grams. Ammonium hydroxide is then added to adjust the pH to about 10. Drawdowns of each sample are then prepared on cold-rolled steel Q panels. Panels to be tested for salt fog in the salt fog chamber are drawn down using a 20 mil draw down bar at room temperature and allowed to air dry for a minimum of one week. The paint film thickness for each sample is 1.2 to 1.3 mil dry. After 190 hours of exposure to salt fog as detailed in ASTM B-117, the results are evaluated as described in ASTM D-610. Sample A exhibits a rust reading of 9-2 (the 9 indicates the relative amount of surface area with rust and the 2 indicates the blisters formed) compared to a 7-2 (the 7 indicates the relative amount of surface area with rust and the 2 indicates the blisters formed) rating for Comparative Sample A. Example 2A sample of butyl acrylate/methylmethacrylate/acrylic acid/isopropenyl oxazoline (48/48/2.0/2.0 by weight) is prepared similarly to the polymer latex prepared in Example 1. The sample is tested for flash rust resistance by drawing the latex alone down onto a R-36 Q panel using a 20 mil draw down bar and is immediately placed into a Forma Scientific Chamber set at 19°C and 93 percent relative humidity. The film is permitted to dry for approximately 24 hours. The final film thickness is 5 mils. The film is visually inspected by the naked eye for flash rust; the sample showed no rust on the majority of the surface. Whereas, for the comparative film prepared using a similar polymer but without the isopropenyl oxazoline, and exposed to the same conditions, rust appeared on the majority of the surface. Such data indicate a significant improvement in rust resistance when isopropenyl oxazoline is incorporated into the latex polymer.
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Use of an oxazoline monomer represented by the following formula: wherein R¹ is a polymerizable organic group; each R² is independently hydrogen, halogen, alkyl, or alkylene group of two to four carbons; n is 1 or 2; in combination with other monomers typically used in emulsion polymerisations to prepare a copolymer latex for improving the resistance of said latex coatings to salt fog and rust when used in industrial coating formulations. Use of an oxazoline monomer as defined in Claim 1 in an industrial coating formulation having improved resistance to salt fog and rust, said coating formulation comprising: a pigment carrier, a thickener, a defoamer, a wetting agent, a dispersant, a bacteriostat, at least one pigment, a pigment stabilizer and a latex copolymer wherein the latex copolymer is prepared from (i) an oxazoline monomer as defined in Claim 1; and (ii) at least one ethylenically unsaturated comonomer, wherein the oxazoline monomer is present in an amount of from 0.25 to 5.0 weight percent based on total amounts of monomer present in the copolymer. The industrial coating formulation of Claim 2 wherein the latex copolymer is prepared from (a) a first charge of monomer comprising an effective amount of at least one ethylenically unsaturated monomer and (b) a second charge of monomer comprising (i) the oxazoline monomer as defined in Claim 1; and (ii) an effective amount of at least one ethylenically unsaturated comonomer, wherein the oxazoline monomer is present in an amount of from 0.25 to 5.0 weight percent based on total amounts of monomer present in the copolymer. The industrial coating formulation of Claim 2 or Claim 3 wherein the ethylenically unsaturated monomer is selected from the group consisting of monovinyl aromatic monomers; aliphatic conjugated diene monomers; acrylate monomers; vinylidene halide or vinyl halide monomers; vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, such as vinyl acetate or vinyl stearate; methacrylonitrile; and acrylonitrile. The industrial coating formulation of Claim 4 wherein the ethylenically unsaturated monomer is selected from acrylate monomers. The industrial coating formulation of Claim 3 wherein the oxazoline monomer is present in an amount of from 0.5 to 2.0 weight percent based on total amounts of monomer present in the copolymer. The industrial coating formulation of any of Claims 2-6 comprising a blend of latexes.
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DOW CHEMICAL CO; THE DOW CHEMICAL COMPANY
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GALLOWAY JAMES G; KESKEY WILLIAM H; RICE DANIEL B; GALLOWAY, JAMES G.; KESKEY, WILLIAM H.; RICE, DANIEL B.
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EP-0489946-B1
| 489,946 |
EP
|
B1
|
EN
| 19,940,803 | 1,992 | 20,100,220 |
new
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C04B28
|
C04B24
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C04B24, C04B28
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C04B 24/26F, C04B 28/02
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Process for producing molded articles
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Provided is a process for producing molded articles having excellent flexural strength, flexibility and dimensional stability, which comprises autoclave-curing at not lower than 100°C an aqueous composition comprising a hydraulic material (A) and a polyvinyl alcohol (B) powder, said polyvinyl alcohol (B) powder being contained in an amount of 0.1 to 20% by weight based on the weight of said hydraulic material (A). Also provided are molded articles comprising a hydraulic material (A) and a polyvinyl alcohol (B), said polyvinyl alcohol (B) being contained in an amount of 0.1 to 20% by weight based on the weight of said hydraulic material (A), said molded article having a structure comprising said polyvinyl alcohol (B) having once dissolved and then solidified being dispersed therein in the form of islands. These molded articles have excellent flexural strength, flexibility and dimensional stability.
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The present invention relates to a process for producing molded articles comprising hydraulic material and used as materials for construction, civil engineering, shipbuilding and the like, and also to molded articles comprising hydraulic materials. The addition of polyvinyl alcohol (hereinafter referred to as PVA) is known for improving mechanical properties and moldability of molded articles comprising hydraulic materials such as cement, gypsum and granulated slag. For example, JP-A-45934/1974 discloses incorporation of PVA into pulp cement for the purpose of improving the flexural strength and impact strength of pulp cement boards, and JP-A- 77655/1986 and 209950/1986 disclose the use of PVA to increase the flexural strength, impact strength and dimensional stability and to prevent generation of cracks of slag boards or gypsum boards. JP-A- 50017/1974 and 239377/1985 disclose the use of PVA for cement molded articles, and JP-A-137719/1976 discloses the use of PVA for light-weight concrete, each for the purpose of improving the mechanical properties and surface appearance and preventing generation of cracks. The reason why PVA is used for these purposes is that PVA is stable even in systems with high pH, does not hinder hydration reaction of hydraulic materials, is water-soluble and dispersible into matrices of for example cement, and improves the properties of the hydraulic compositions by bonding particles of the hydraulic materials with each other or forming tough film of PVA in the molded articles. JP-A- 13628/1972 discloses that addition of boron compounds to aqueous slurry compositions comprising cement and PVA powder can reduce the amount of PVA used. JP-A- 184754/1984 discloses that, in aqueous slurry compositions comprising cement and PVA powder, replacement of the PVA powder by silyl group-modified PVA improves the strength of the molded articles. JP-A-149 152/1980 discloses a process for producing hydraulic cured articles which comprises adding to a mixture comprising a hydraulic powder such as gypsum or cement, a PVA powder and a fibrous reinforcing material, an aqueous solution of a gelling agent for the PVA, to obtain a mud-like matter and then curing and drying the mud-like matter. In recent years, molded articles from hydraulic materials and having the same specification have been commercially produced by autoclave-curing on a large scale. Requirements for the mass-production of molded articles from hydraulic materials are: firstly, that the product articles have high mechanical strength and dimensional stability and do not generate cracks and, secondly, high productivity. There has not been established any process for producing molded articles from hydraulic materials or any molded article from hydraulic materials that satisfies all of the above requirements. Accordingly, an object of the present invention is to provide a process for efficiently producing molded articles having high flexural strength, deflection in bending (flexibility) and dimensional stability, by autoclave-curing aqueous compositions comprising hydraulic materials. Another object of the present invention is to provide a molded article comprising a hydraulic material and having high flexural strength, deflection in bending (flexibility) and dimensional stability. These objects are achieved by the present invention. The subject matter of the invention therefore is a process for producing molded articles comprising hydraulic materials, which comprises autoclave-curing at not lower than 100°C an aqueous composition comprising a hydraulic material (A) and a polyvinyl alcohol (B) powder, said polyvinyl alcohol (B) powder being contained in an amount of 0.5 to 20% by weight based on the weight of said hydraulic material (A). A further subject matter of the invention is a molded article comprising a hydraulic material (A) and a PVA (B), said PVA (B) being contained in an amount of 0.5 to 20% by weight based on the weight of said hydraulic material (A), said molded article having a structure comprising said PVA (B) having once dissolved and then solidified being dispersed therein in the form of islands. Any hydraulic material can be used as the hydraulic material (A) in the process of the present invention insofar as it solidifies by reaction with water, and its examples are inorganic substances such as Portland cement of various types, gypsum, granulated slag, rock fiber, magnesium carbonate and calcium silicate. The PVA (B) powder used in the present invention includes unmodified conventional PVA, silyl group-modified PVA and other various modified PVA's. The PVA (B) can be of any degree of polymerization, and preferably has one of at least 500, more preferably at least 1,500. With a degree of polymerization of at least 500, the PVA (B) provides, upon autoclave-curing at not lower than 100°C, molded articles having markedly improved properties such as mechanical strength, perhaps because its powder has high bonding strength and the strength of PVA film is high. The PVA (B) powder must have a degree of hydrolysis, of at least 90 mol%, preferably at least 95 mol%. In the present invention, where no substance causing the viscosity of aqueous PVA (B) solution to increase is used, the degree of hydrolysis of the PVA (B) is preferably, in particular, at least 98 mol%. With a degree of hydrolysis of at least 90 mol%, the PVA (B) in its powder form uniformly disperses into aqueous compositions, whereby autoclave-curing of an aqueous composition gives molded articles with markedly high flexural strength due to high bonding strength of the PVA (B) powder and high strength of PVA (B) film. The PVA (B) powder may be of any average particle size, and preferably has one of <1 mm (16-mesh pass), more preferably <0,35 mm (42-mesh pass), the smaller being the better. The aqueous composition used in the present invention comprises a hydraulic material (A) and PVA (B) powder, the PVA (B) powder being incorporated in an amount of 0.5 to 20% by weight based on the weight of the hydraulic material (A), more preferably 0.5 to 5% by weight on the same basis. If the amount of PVA (B) incorporated is less than 0.1% by weight, the PVA (B) will not produce effect of reinforcing molded articles. On the other hand if the amount exceeds 20% by weight, the water resistance and flame retardency of the obtained molded articles will decrease. For the purpose of developing still higher strength of molded articles, it is preferred to add a reinforcing fiber (C) to the aqueous composition used. The reinforcing fiber (C) is added in an amount of 0.1 to 10% by weight based on the weight of total solid, more preferably 0.5 to 5% by weight on the same basis. Addition of at least 0.1% of a reinforcing fiber (C) markedly reinforces the obtained molded article and increases the effect of connecting green sheets. An addition exceeding 10% by weight, however, is associated with a problem in dispersibility and sometimes impairs the reinforcing effect. Conventional reinforcing materials used for cement and the like can be used for this purpose, but preferably used are those having given actual results in the reinforcement of molded articles comprising hydraulic materials (A). Examples of these preferred materials are fibers of polyvinyl alcohol, acrylics, olefins, carbon and aramids, and pulps such as synthetic pulp, wood pulp and highly crushed wood pulp, all of which are included in the term fiber in the present invention. These fibers may be used singly or in combination. It is also preferred, for the purpose of still enhancing the effect of PVA (B), to add a substance (D) increasing the viscosity of aqueous PVA (B) solution. The substance (D) increasing the viscosity of aqueous PVA (B) solution herein means a substance which, when added in an amount of 5% by weight based on the weight of PVA (B) on dry base, causes the viscosity of the aqueous PVA (B) solution to become at least double, preferably at least 4 times that of blank, and more preferably causes the aqueous PVA (B) solution to gel. Among such substances (D), particularly preferred are those crosslinking agents of PVA (B) that form, while crosslinking PVA (B), a water-insoluble crosslinked matter at lower than 100°C, the water-insoluble crosslinked matter dissolving in water by autoclave-curing at not lower than 100°C, and increase the viscosity of the aqueous PVA (B) solution obtained by this autoclave-curing. Examples of the substance (D) increasing the viscosity of aqueous PVA (B) solution are boric acid, borax, calcium borate, magnesium borate, aluminates, zirconium salts, 3-valent chrome forming when an alkali metal chromate or dichromate is reduced, 4-valent titanium forming when titanium trichloride is oxidized, vanadates and copper ion. Dyes such as Congo red and organic substances such as gallic acid can also be used. Preferred among these substances (D) increasing the viscosity of aqueous PVA (B) solution are boric acid and derivatives thereof, among which particularly preferred is calcium borate. Where the hydraulic material (A) used generates calcium ion, it is most preferred to use one of those crosslinking agents of PVA (B) that form with PVA (B) a water-insoluble crosslinked matter at lower than 100°C, said water-insoluble crosslinked matter dissolving in water by autoclave-curing at not lower than 100°C, and increase the viscosity of the aqueous PVA (B) solution obtained by this autoclave-curing, such as boric acid, borax or calcium borate. Thus, in the present invention, the substance (D) increasing the viscosity of aqueous PVA (B) solution has functions of suppressing the dissolution of PVA (B) powder during processes before autoclave-curing and permitting the PVA (B) powder to dissolve in water upon autoclave-curing at not lower than 100°C. In the present invention, the PVA (B) is used in powder form, which is hardly soluble in water when present in aqueous compositions. The marked reinforcement effect of the PVA (B) is therefore considered to be due to that the undissolved PVA (B) powder does not, even when an aqueous composition is used in the form of aqueous slurry, increase the viscosity of the aqueous slurry, whereby almost all PVA (B) powder remains in the aqueous composition when it has been prepared by wet lamination process and, upon autoclave-curing at not lower than 100°C (under wet heat) dissolves to develop reinforcement effect. In particular, where a substance (D), particularly one that crosslinks PVA (B) is used in combination, the reinforcement effect is still more enhanced, perhaps because that the PVA (B) dissolved during autoclave-curing will not migrate to a large extent into the molded article but stay at original positions and develop high bonding force. The effect of addition of a substance (D) increasing the viscosity of aqueous PVA (B) solution increases with the amount of its addition. The addition is at least 1% by weight based on the weight of PVA (B), preferably 1 to 50% by weight, more preferably 5 to 20% on the same basis. The process for producing molded articles of the present invention can be any one of wet lamination process, flow-on process, extrusion process, dry process and the like. The aqueous composition used in the present invention may incorporate any additives that are usually added to conventional aqueous compositions comprising hydraulic material (A), e.g. inorganic fillers such as silica powder and fly ash, and other fillers such as sand, ballast and light-weight aggregate. The aqueous composition may also contain bubbles. The aqueous composition used in the present invention can be of optional solid concentration, depending on the process employed, and for example solid concentrations of 2 to 90% by weight are appropriately used. The production process of the present invention comprises autoclave-curing of the above aqueous composition at not lower than 100°C. The temperature must be 100°C or above, and is preferably 120 to 180°C, more preferably 140 to 170°C. There is no particular limitation to the time of autoclave-curing, but it is preferably 1 to 30 hours, more preferably 8 to 20 hours. With an autoclave-curing time of not more than 1 hour, the hydraulic reaction may remain immature; while PVA (B) may deteriorate if the time exceeds 24 hours. The molded articles obtained by the process of the present invention are excellent in, particularly, mechanical strength and dimensional stability. There are no particular restrictions with respect to the conditions of any pre-curing before autoclave-curing (hereinafter referred to as primary curing ) if it is ever conducted. Thus, autoclave-curing may directly be conducted without any primary curing, or the primary curing is conducted at lower than 100°C. It is preferred to conduct primary curing at not lower than 10°C and lower than 100°C, more preferably at not lower than 70°C and lower than 100°C. There are no particular restrictions either with respect to the vapor pressure in the gas phase when primary curing is conducted, but higher vapor pressure is preferred, saturated vapor pressure being most preferred. Steaming or like processes is employed for controlling the vapor pressure in the gas phase. The primary curing can be conducted for an optional time period, preferably until the composition hardens to an extent that permits ready removal of the mold used. Examples of the primary curing are from 1 day to about 1 week for room temperature curing and 5 to 48 hours for curing with heating at lower than 100°C. Molded articles with markedly high strength can, surprisingly, be obtained when a primary curing is conducted at a specific temperature selected among the above-mentioned conditions, i.e. not lower than 70°C and lower than 100°C, and then autoclave-curing is, preferably in combination with the use of a substance (D) increasing the viscosity of aqueous PVA (B) solution, conducted under a wet heat condition of not lower than 100°C (that assures dissolution of PVA (B) powder). The process for producing molded articles of the present invention can readily provide by autoclave-curing molded articles comprising hydraulic materials and having excellent mechanical properties and dimensional stability. Accordingly, the process is of excellent industrial value. The molded article of the present invention is now described. The hydraulic material (A) and PVA (B) are the same as described hereinbefore for the aqueous composition used in the process of the present invention. It is preferred that the molded article of the present invention contain the reinforcing fiber (C) and/or the substance (D) increasing the viscosity of aqueous PVA (B) solution, described hereinbefore, which will provide the molded articles with higher strength. The reinforcing fiber (C) is contained in an amount of preferably 0.1 to 10% by weight based on the weight of total solid. The substance (D) is contained in an amount of preferably at least 1% by weight based on the weight of PVA (B), and more preferably 1 to 50% by weight, most preferably 5 to 20% by weight on the same basis. The molded article of the present invention is characterized by its structure comprising the PVA (B) that has once dissolved and solidified being dispersed in the molded article in the form of islands, and it is preferred that the islands of the PVA (B) be dispersed as uniformly as possible. The islands of PVA (B) can assume any shape, and its examples are spherical, deformed spherical, spherical or deformed spherical with hollow part therein and spherical or deformed spherical in which the concentration of PVA (B) is highest in the center and decreases with the distance from the center. The islands can be of any size, but the average maximum diameter is preferably 0.05 to 3 mm, more preferably 0.1 to 1 mm. Only insufficient strength is obtained with the molded articles having no structure comprising PVA (B) dispersed therein in the form of discontinuous islands, e.g. those with a structure comprising PVA (B) extending continuously, or comprising PVA (B) that remains solid without having dissolved or PVA (B) that has insufficiently dissolved. Where in the present invention the hydraulic material (A) comprises cement, the molded articles contain tobermorite gel, which can be observed with a scanning electron microscope. Those molded articles that contain tobermorite gel have excellent strength and dimensional stability. The molded articles of the present invention can be produced by optional process, for example by the afore-described process for producing molded articles of the present invention. The molded articles of the present invention are used as boards for roofing, external walls, inside walls and the like, as blocks for road construction and bank protection, and as like materials. Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof. In the Examples and Comparative Examples that follow, % and parts mean % by weight and parts by weight , respectively, unless otherwise indicated. EXAMPLESExamples 1 through 14 and Comparative Examples 1 through 10(1) Preparation of samples (wet process)There were used ordinary Portland cement as hydraulic material, powder of 60-mesh pass of a PVA having a degree of polymerization of 1,700 and degree of hydrolysis of 98 mol% and other additives shown in Table 1. Aqueous compositions were prepared using these components in the incorporation ratios shown in Table 1 (Examples 1 through 14) and Table 2 (Comparative Examples 1 through 10). The aqueous compositions were formed into aqueous slurries having a solid concentration of 40%, which were then fed into a mold and squeezed by pressing therein to a solid concentration of 70 to 80% (wet base) to be formed into boards having a thickness of 0.8 cm. This method corresponds to the usual long-net one-layer wet process for producing conventional cement boards. The boards thus obtained were cured under the conditions shown in Table 1 (Examples 1 through 14) and Table 2 (Comparative Examples 1 through 10). (2) EvaluationsBulk specific densityIn accordance with JIS A 5413, specimen pieces were dried in a hot air drying oven at 105± 5°C for 24 hours, and then measured for the weight and volume, to calculate the bulk specific density. Flexural strength and deflection in bendingFlexural strength was determined in accordance with JIS A 1408 Method of Bending Test for Boards of Buildings with a span length of 5 cm, where the maximum deflection at the center was taken as the deflection in bending. Larger deflection in bending indicates higher flexibility and higher usefulness as a molded article of the specimen tested. Length change ratio (dimensional stability)JIS A 5416 was applied. A unit length each of specimens dried at 60°C for 1 day was taken as the base length. The specimens were then immersed in water for 1 day to absorb water and tested for the length, to give the length change ratio. (3) ResultsThe evaluation results are shown in Table 1 (Examples 1 through 14) and Table 2 (Comparative Examples 1 through 10). (4) Microscopic observationObservation with a scanning electron microscope of the cross-sections of the molded articles obtained in Examples 1 through 14 revealed that PVA's that had once dissolved and then solidified in the molded articles dispersed uniformly in the form of discontinuous islands having a shape of deformed spheres. The molded articles were also confirmed to contain tobermorite gel. The dispersion state of the PVA in each of the molded articles was, after coloration of the PVA by iodine, also confirmed by observation with a stereomicroscope. Observation with a scanning electron microscope of the cross-sections of the molded articles obtained in Comparative Examples 1 through 4 revealed that PVA's had dissolved only incompletely, while they dispersed in the form of islands though. Comparative Examples 11 through 14(1) Preparation of samples (wet process)Examples 1, 2, 4 and 5 were repeated except that aqueous compositions were prepared using aqueous solution of the PVA instead of the PVA powder. The use of aqueous PVA solution increased the viscosity of the water compositions, and hence there occurred some troubles such as low filterability in the process. (2) EvaluationsSame as for Examples 1 through 14. (3) ResultsThe evaluation results are shown in Table 2. (4) Microscopic observationObservation of the cross-section of the molded articles obtained in Comparative Examples 11 through 14 with a scanning electron microscope revealed that the PVA's did not disperse in the form of islands in the molded articles. Examples 15 and 16 and Comparative Examples 15 through 20(1) Preparation of samples (dry process)Aqueous compositions were prepared using the same PVA powder as used in Examples 1 through 14, boric acid, ordinary Portland cement and Toyoura standard sand in compositions as shown in Table 3 and in a water/cement ratio of 40%. The aqueous compositions thus prepared were each flown into a mold having a size of 25 cm x 25 cm x 0.8 cm and cured under the conditions shown in Table 3 to give a board. (2) EvaluationsSame as for Examples 1 through 14. (3) ResultsThe evaluation results are shown in Table 3. (4) Microscopic observationObservation of the cross-section of the molded articles obtained in Examples 15 and 16 with a scanning electron microscope revealed that PVA's that had once dissolved and then solidified in the molded articles dispersed uniformly in the form of discontinuous islands having a shape of deformed spheres. The molded articles were also confirmed to contain tobermorite gel. The dispersion state of the PVA in each of the molded articles was, after coloration of the PVA by iodine, also confirmed by observation with a stereomicroscope. Observation with a scanning electron microscope of the cross-sections of the molded articles obtained in Comparative Examples 15, 17, 19 and 20 revealed that PVA's had dissolved only incompletely, while they dispersed in the form of islands though. Comparative Examples 21 and 22(1) Preparation of samples (dry process)Aqueous compositions were prepared following the same procedure as that in Examples 15 and 16 except for using aqueous solutions of the PVA instead of the PVA powder. (2) EvaluationsSame as for Examples 15 and 16. (3) ResultsThe evaluation results are shown in Table 3. (4) Microscopic observationObservation of the cross-section of the molded articles obtained in Comparative Examples 21 and 22 with a scanning electron microscope revealed that the PVA's did not disperse in the form of islands in the molded articles. Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
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A process for producing molded articles, which comprises autoclave-curing at a temperature of at least 100°C an aqueous composition comprising a hydraulic material (A) and a polyvinyl alcohol (B) powder having a degree of hydrolysis of at least 90 mol%, said polyvinyl alcohol (B) powder being contained in an amount of 0.5 to 20% by weight based on the weight of said hydraulic material (A). A process for producing molded articles according to Claim 1, wherein said hydraulic material (A) is cement. A process for producing molded articles according to Claim 1 or 2, wherein said aqueous composition further comprises a reinforcing fiber (C). A process for producing molded articles according to any one of claims 1 to 3, wherein said aqueous composition further comprises a substance (D) increasing the viscosity of the aqueous solution of said polyvinyl alcohol (B) in an amount of at least 1% by weight based on the weight of said polyvinyl alcohol (B) powder. A process for producing molded articles according to any one of claims 1 to 4, curing said aqueous composition at a temperature lower than 100°C and then autoclave-curing the aqueous composition thus cured at a temperature of at least 100°C. A process for producing molded articles according to Claim 5, wherein said substance (D) increasing the viscosity of the aqueous solution of said polyvinyl alcohol (B) is a cross-linking agent for said polyvinyl alcohol (B) which forms with said polyvinyl alcohol (B) a water-insoluble crosslinked matter at a temperature lower than 100°C, said water-soluble crosslinked matter dissolving in water by autoclave-curing at a temperature of at least 100°C, and increasing the viscosity of the aqueous solution of said polyvinyl alcohol (B) resulting from this autoclave-curing. A process for producing molded articles according to Claim 6, wherein said substance (D) increasing the viscosity of aqueous solution of said polyvinyl alcohol (B) is a boric acid or derivatives thereof. A molded article comprising a hydraulic material (A) and a polyvinyl alcohol (B) having a degree of hydrolysis of at least 90 mol%, said polyvinyl alcohol (B) being contained in an amount of 0.5 to 20% by weight based on the weight of said hydraulic material (A), said molded article having a structure comprising said polyvinyl alcohol (B) having once dissolved and then solidified being dispersed therein in the form of islands. A molded article according to Claim 8 further comprising a reinforcing fiber (C). A molded article according to Claim 9 further comprising a substance (D) increasing the viscosity of aqueous solution of said polyvinyl alcohol (B) in an amount of at least 1% by weight based on the weight of said polyvinyl alcohol (B). A molded article according to Claim 9 comprising tobermorite gel.
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KURARAY CO; KURARAY CO., LTD.
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ITADANI SOTARO; MIZOBE AKIO; SAIMEN KENJI; YUKI KEN; ITADANI, SOTARO; MIZOBE, AKIO; SAIMEN, KENJI; YUKI, KEN
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EP-0489951-B1
| 489,951 |
EP
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B1
|
EN
| 19,960,110 | 1,992 | 20,100,220 |
new
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D01F6
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C08J5, C08G69
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C08G69
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C08G 69/32
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High strength fibers or films of aromatic copolyamides with pendant carboxyl groups
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The reactivity of aromatic copolyamide fiber and film is enhanced by incorporation of small amounts of 4,4'-diaminodiphenic acid units in the polymer chain.
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BACKGROUND OF THE INVENTIONThis invention relates to high strength fibers of p-aramids having pendant carboxyl groups. The presence of these pendant groups imparts properties to the polymer and fibers or films thereof such as would enhance their reactivity, improve adhesion to matrix materials in reinforced composite structures or provide other characteristics. The commercial importance of fiber reinforced composites has long been recognized. While the adhesion between certain reinforcing fibers and matrix polymer is excellent, others require the use of so-called coupling agents in order to improve the level of strength achieved through reinforcement. In some instances the use of coupling agents has not been satisfactory. Poly(p-phenylene terephthalamide) fiber finds extensive use as a reinforcement in composite structures. In accordance with this invention, the introduction of certain monomeric units in specified proportions in the polymer chain may reduce or eliminate the need for coupling agents in particular applications. SUMMARY OF THE INVENTIONThis invention provides a novel polymer of fiber-forming molecular weight consisting essentially of the following repeat units in the indicated molar proportions: and where X is 1,4-phenylene and where Z is from about 2 to 15 mole % and fibers and films thereof. Also included is a process for preparing the fibers. DETAILED DESCRIPTION OF THE INVENTIONThe present invention has for its purpose, the incorporation of small amounts of carboxyl groups along an aromatic polyamide chain in a way that they do not interfere with the amide linkages. Carboxyl groups are known to enhance adhesion to rubber, epoxides, etc. It has now been found that fibers formed from certain aromatic polyamides bearing limited numbers of carboxyl groups on the chain suffer no significant reduction in tensile properties. The carboxyl groups may be incorporated by polymerizing a mixture of paraphenylene diamine and 4,4'-diaminodiphenic acid with terephthaloyl chloride. As shown in concurrently filed, copending coassigned U.S. Application Serial No. (QP-4365) the diphenic acid should be employed as the dihydrochloride. The novel copolymers of the invention are of fiber-forming molecular weight, having an inherent viscosity of at least 3.5 measured as described below, and consist essentially of the following repeating units: and where X is 1,4-phenylene and Z is from 2 to 15 mole %, preferably from 2 to 10 mole %. The copolymer may be made into a spin dope by dissolution in concentrated sulfuric acid. The spin dope should preferably contain at least 15% by wt. of the copolymer. The dope may be spun through an inert fluid layer, preferably air, into a coagulating bath such as water. Preparation of spin dopes and spinning procedures are similar to those employed in Blades U.S. Patent No. 3,767,756 with poly (p-phenylene terephthalamide). Test ProceduresInherent viscosity, I.V., is defined by the following equation: I.V. = 1n RVC where RV is the relative viscosity and C is the concentration in grams of polymer per deciliter of solvent, typically 0.5g in 100 ml. (Thus, the units for inherent viscosity are dl/g.) The relative viscosity is determined by dividing the flow time of the dilute solution in a capillary viscometer by the flow time for the pure solvent. The flow times are determined at 30°C. The solvent employed is 100% H₂SO₄. Tensile measurements were made on single filaments following the test procedure found in ASTM D 2101-82. The filaments were conditioned at 21°C (70°F) and 65 percent relative humidity and tested on a conventional tensile tester using flat clamps with rubber facing and a 2.5 cm (1 ) gauge length at a 10%/min strain rate (for low elongation, 0-8%). T is tenacity at break in gpd, M is the initial modulus in gpd and E is the break elongation in %. The following examples are illustrative of the present invention and are not to be construed as limiting. Example 1In a flame-dried resin kettle, fitted with cage-type stirrer, thermometer, dry nitrogen purge, and external cooling bath a slurry of 4,4'-diaminodiphenic acid dihydrochloride (3.54 g; 0.0103 mole) with a solution of p-phenylene diamine (21.03 g; 0.195 mole) in anhydrous N-methyl pyrrolidone (407 ml; 420 g)/anhydrous CaCl₂ (31.57 g; 0.287 mole) was treated, at room temperature, with anhydrous diethylaniline (3.054 g; 0.0205 mole). To the resulting solution, at 10°C, was added quantitatively, terephthaloyl chloride (41.62 g; 0.205 mole). The initially clear solution in a very sort time gave way to a broken-up gel or crumb. After standing 2 hr at room temperature, this was treated with excess cold water in a blender to precipitate polymer, which was filtered, washed with cold water, then treated in boiling water with stirring for 15 min to remove residual solvent, refiltered and dried at 100°C/15 hr. I.V. in 100% H₂SO₄ was 4.08. Thermogravimetric analysis indicated retention of a few percent residual solvent to about 180°C. A 20% (w/w) solution of the polymer at 68°C was extruded through a single hole spinneret, with hole diameter 0.13 mm (0.005 in) and length 0.38 mm (0.015 in), via a 6.35mm (0.25 in) air gap, into a water coagulating bath at 0°C. Fiber was wound up at 256 m/min and spin-stretch factor (S.S.F.) of 9.0X. The well washed, air-dried fiber had T/E/Mi/dpf = 17.3 gpd/4.2%/634 gpd/1.5 den. Wide angle X-ray diffraction showed these as-spun fibers to be essentially amorphous. By passing the never-dried fibers through a tube at 200°C in a nitrogen atmosphere, during 15 sec. under tension, T/E/Mi changed to 20.3/2/8/840. By passage over a hot plate, under tension, at 500°C, T/E/Mi was 18.6/3.2/700 (best break, 21.2/3.9/680). Example 2A copolymer with an inherent viscosity of 4.68 was prepared in the same way as in Example 1 but with the 4,4'-diaminodiphenic acid dihydrochloride concentration increased to 6 mole %. Fiber was spun similarly from sulfuric acid solution at 60°C, with a wind-up speed of 221 m/min and spin-stretch of 8.1X. The air-dried as-spun fiber had T/E/Mi/dpf = 15.1/4.3/578/1.8. The fiber was amorphous. Never-dried fiber, heat treated under tension at 200°C/15 sec. had T/E/Mi = 20.0/2.5/790. Air-dried fiber, heat treated under tension at 450°C, had T/E/Mi - 18.1/4.0/647 (best break, 20.6/4.5/667). Fibers remained amorphous. Heat treatment tended to smooth out the distinct knee in the stress-strain curve of the as-spun fiber. Example 3A copolymer with an inherent viscosity of 4.53 was prepared in the same way as in Example 1 but with the 4,4'-diaminodiphenic acid dihydrochloride concentration increased to 12.5 mole %. Fiber was spun from a dope at 79°C at a wind-up speed of 86 m/min and S.S.F. = 2.9X. Air-dried fiber had T/E/Mi/dpf = 10.3/5.1/404/11.2; fibers were amorphous. Never-dried fiber, heated under tension at 200°C for 15 sec. had a T/E/M = 11.0/2.2/600. Air-dried fibers, passed over a hot plate at 400-500°C under tension, showed no changed in stress-strain behavior or properties, and no development of crystallinity or improvement in orientation. The stress-strain curve showed a distinct knee or yield point, beyond which modulus dropped by more than 50%.
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Aromatic polyamide of fiber-forming molecular weight consisting essentially of the following repeat units in the indicated molar proportions: and where X is 1,4-phenylene and where Z is from about 2 to 15 mole percent. A polymer according to claim 1 where Z is from about 2 to 10 mole percent. A process for preparing high strength fibers comprising preparing a spin dope of the polymer of claim 1 and concentrated sulfuric acid at a concentration of at least 15% by wt. and spinning it through an inert fluid layer into a coagulating bath and withdrawing the coagulated fiber from the bath. A high strength fiber formed by the process of claim 3.
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DU PONT; E.I. DU PONT DE NEMOURS AND COMPANY
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IRWIN ROBERT SAMUEL; IRWIN, ROBERT SAMUEL
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EP-0489956-B1
| 489,956 |
EP
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B1
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EN
| 19,980,325 | 1,992 | 20,100,220 |
new
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H01S3
| null |
H01S3
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H01S 3/08D, H01S 3/081D
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Narrow-band laser apparatus
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A laser apparatus comprises an optical resonator including first 2 and second mirrors 3, and laser medium 1. An wavelength selection element 6 is provided in the resonator for narrowing band-width. A polarizing conversion element (4) for changing ratio of S to P components and polarizing beam splitter 5 are provided for amplifying laser beam to output after wavelength selection and for reducing light load of the wavelength selection element (6). The polarizing conversion element 4 is provided in the resonator light path. In another embodiment, the polarizing conversion element 4 is provided in a branch light path formed by a second polarizing conversion element and a third mirror 8, where the second polarizing conversion element reflects and transmits P component at a given ratio and reflects S component. The wavelength selection element comprises a Fabry-Perot etalon, grating, or prism. The polarizing conversion element comprises a quarter-wave plate or a phase retarder mirror. The polarizing beam splitting element comprises a polarizing beam splitter or polarizing beam splitting prism. Such laser apparatus is suited for an exposure light source for photolithography.
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This invention relates to a narrow-band laser apparatus.The excimer laser has attracted attention as a light source for photolithography. The excimer laser can output a laser light beam having efficient power for exposing a photoresist film on a semiconductor wafer at several wavelengths between 353 nm to 193 nm through a laser medium comprising a noble gas, such as krypton and xenon gases, and halogen gas, such as fluorine and chlorine gases. Gain-band width of the excimer laser is approximately one nm which is too large for the exposure light source for photolithography. Band width output laser light of the excimer laser is about 0.5 nm (full width at half maximum). If such relatively broad band laser light is used as an exposing, an achromatic exposing optical system is necessary in exposing apparatus for photolithography. However, in ultraviolet region, less than 350nm, achromatization is difficult because there are few types of optical materials which can be used for a focusing lens system. It is desired to narrow band width of the excimer laser used for the exposure light source whose band-width is around 0.005 nm. Such exposure light source enables a focusing lens system without achromatization to be used, so that simplification of the optical system of the exposing apparatus for photolithography and miniaturization and lowering cost of the exposing apparatus can be realized.A laser apparatus for exposure which comprises an wavelength selection element provided in its optical resonator for narrowing bandwidth of laser light without attenuation of output power is described in JP-A-63-160287 which is described below.Fig. 23 is a front view of the narrow-band excimer laser of the above-mentioned prior art. In Fig. 23, this prior art laser apparatus comprises an optical resonator including a total reflection mirror 102, a half mirror 103 and a discharge tube 101 provided in a light path of the optical resonator, and a Fabry-Perot etalon 104 as an wavelength selection element. In this laser apparatus, only light whose wavelength is selected by Fabry-Perot etalon 104 is amplified and oscillates, so that an extremely narrow-band laser light beam is obtained.However in such excimer laser apparatus, there is a drawbacks that because there is high energy light continuously exists in the optical resonator, the wavelength selection element is deteriorate or deformed, so that the selection wavelength will change or output power will decrease. If such excimer laser apparatus is used as a light source for exposure, defected products of integration circuits are manufactured. In other words, maximum power of the excimer laser is limited by high-energy-light resistivity of the selection element. Further narrow band laser apparatuses are known from FR-A-2 402 320 and EP-A- 0 383 586 WO-A-8 603 066 discloses a laser comprising an optical rotator, a polarising beam splitter and a Pockets cell. The EP-A-0 402 570 as prior art according to Art. 54(3) EPC shows a still a further narrow band laser apparatus.It is the object of the present invention to provide a narrow band laser apparatus with which a high output power can be achieved.This object is achieved by the invention as defined in the independent claims 1 to 20.Advantageous further developments are set out in the dependent claims. The wavelength selection element comprises one or more Fabry-Perot etalons, gratings, or prisms. The beam polarizing conversion element comprises a quarter-wave plate, a phase retarder prism or a phase retarder mirror. The polarizing beam splitting element comprises a polarizing beam splitter or polarizing beam splitting prism. An echelle grating or echelon grating may be used in replace with the first reflection mirror and the Fabry-Perot etalon. A phase retarder mirror may be used in place with the second mirror and the wavelength phase plate. A polarizing beam splitting prism may be used as a polarizing beam splitting element and wavelength selection element in combination with a Fabry-Perot etalon.The object and features of the present invention will become more readily apparent from the following detailed description taken in conjunction with the accompanying drawings in which: Fig. 1 is a front view of a first embodiment of a laser apparatus of the invention;Fig. 2 is a front view of a second embodiment; Fig. 3 is a front view of a third embodiment;Fig. 4 is a front view of a fourth embodiment;Fig. 5 is a front view of an embodiment not according to the invention;Fig. 6 is a front view of a fifth embodiment;Fig. 7 is a front view of a sixth embodiment;Fig. 8 is a front view of an seventh embodiment;Fig. 9 is a front view of a eighth embodiment;Fig. 10 is a front view of a ninth embodiment;Fig. 11 is a front view of an tenth embodiment;Fig. 12 is a front view of an embodiment not according to the invention;Figs 13A to 13C show a first group of equivalent element throughout embodiments;Figs 14A to 14C show a second group of equivalent element throughout embodiments;Figs 15A and 15B show a third group of equivalent element throughout embodiments;Figs 16A to 16C show a fourth group of equivalent element throughout embodiments;Figs 17A and 17B show a fifth group of equivalent element throughout embodiments;Fig. 18 is a perspective view of Fig. 13C;Fig. 19 is a front view of an alternative element of the polarizing beam splitter;Fig. 20 is a front view of an alternative element of the polarizing beam splitter; Fig. 21 is an explanatory chart of the first embodiment;Fig. 22 is an explanatory chart of the tenth embodiment;Fig. 23 is a front view of a prior art laser apparatus;Fig. 24 is an explanatory chart of the prior art; andFig. 25 is another explanatory chart of the prior art.The same or corresponding elements or parts are designated at like references throughout the drawings.Referring now to the drawings, Fig. 1 is a front view of a first embodiment of a narrow-band excimer laser apparatus of the invention.In Fig. 1, a discharge tube 1 comprises a mixed gas of noble and halogen gases as a laser medium. An optical resonator comprises total reflection mirrors 2 and 3 and the discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3 via a polarizing beam splitter 5. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the polarizing beam splitter 5 and the total reflection mirror 2, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation of the laser apparatus of the first embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is transmitted through the polarizing beam splitter 5 and outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is reflected by the polarizing beam splitter 5. The light beam 9 is subjected to wavelength selection by Fabry-Perot etalon 6, and then it is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the Fabry-Perot etalon 6 and reflected by the polarizing beam splitter 5 again and is amplified by the laser medium. The amplified light beam 11 enters the quarter-wave plate 4. The light beam 11 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3 to produce a reflection light beam 12. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. Generally, it is possible to set a ratio between both polarization components of the reflected light beam 12 by changing rotational position of the quarter-wave plate 4 around the center of the axis of the light path. The reflected light 12 is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 8 is transmitted through the polarizing beam splitter 5 as the output light beam 7. Another component is reflected at the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. Here, lasing coupling ratio of the output light beam 8 can be changed by varying ratio between intensities of the output light beam 7 and reflected light beam 9 by rotation of the quarter-wave plate 4. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 9 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is considerably reduced.Fig. 21 shows an experimental result showing a relationship between output laser light intensity Iout and light intensity IE at the Fabry-perot etalon 6 of the first embodiment with respect to ratio of the light beam 9 to the light beam 8, i.e., coupling factor for laser oscillation. The result is obtained using KrF excimer laser of Fig. 1. The mixed gas of laser medium comprises 0.22% of F2, 4.4% of Kr, and remains of He. Full pressure is 1800 mb. Laser oscillation is performed by application of a supply voltage of 28 KV to the discharge tube 1. The resultant shows Iout and Fabry-Perot etalon load IE per one pulse under this condition. Fig. 24 shows another experimental result under the same condition, which shows the same relation with respect to reflectance R of a half mirror 103 of the prior art of Fig. 23. In Fig. 21, the maximum output laser light intensity Iout is about 44 mJ and at the same time, Fabry-Perot etalon load IE is about 10 mJ. On the other hand, in Fig. 24 of prior art, the maximum output laser light intensity Iout is about 14 mJ and at the same time, etalon load IE is about 23 mJ. Therefore, output light intensity Iout of the first embodiment is about three times that of the prior art of Fig. 23, on the other hand, Fabry-Perot etalon load IE is about 58% of the prior art.Hereinbelow will be described a second embodiment. Fig. 2 is a front view of the second embodiment of a laser apparatus of the invention. In Fig. 2, an optical resonator comprises total reflection mirrors 2 and 3. A discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the discharge tube 1 and the quarter-wave plate 4, so that only specified narrow-band light beam is oscillated in the optical resonator. This embodiment readily provides S polarized component light because the polarizing beam splitter for reflecting S polarizing component can be provided readily.Hereinbelow will be described operation of the laser apparatus of the second embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is transmitted through the polarizing beam splitter 5. The light beam 9 is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the polarizing beam splitter 5 again and is amplified by the laser medium. The amplified light beam is transmitted through the Fabry-Perot etalon 6 where an wavelength selection is performed. The light beam 11 from the Fabry-Perot etalon 6 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3 to produce a reflection light beam 12. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. Generally, it is possible to set a ratio between both polarization components of the reflected light beam 12 by changing rotational position of the quarter-wave plate 4 around the center of the axis of the light path. The reflected light 12 is transmitted through the Fabry-Perot etalon 6. The light beam 113 from the Fabry-Perot etalon 6 is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 8 is reflected at the polarizing beam splitter 5 as the output light beam 7. Another component is transmitted through the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 113 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is reduced. The light load of the Fabry-perot etalon 6 used in the second embodiment is slightly larger than that of the first embodiment. This embodiment readily provides P polarizing component.Hereinbelow will be described a third embodiment. Fig. 3 is a front view of the third embodiment of a laser apparatus of the invention. Basic structure of the third embodiment is the same as that of the second embodiment. There is a difference that the Fabry-Perot etalon 6 is provided between the quarter-wave plate 4 and the total reflection mirror 3. Basic operation of the third embodiment is the same as that of the second embodiment. Thus, a detailed description is omitted.Hereinbelow will be described a fourth embodiment. Fig. 4 is a front view of the fourth embodiment of a laser apparatus of the invention. In Fig. 4, an optical resonator comprises total reflection mirrors 2 and 3. A discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the discharge tube 1 and the quarter-wave plate 4, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation of the laser apparatus of the fourth embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is reflected at the polarizing beam splitter 5. The light beam 9 is reflected at the total reflection mirror 2. The reflected light beam 10 is reflected at the polarizing beam splitter 5 again and is amplified by the laser medium. The amplified light beam is transmitted through the Fabry-Perot etalon 6 where an wavelength selection is performed. The light beam 11 from the Fabry-Perot etalon 6 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3 to produce a reflection light beam 12. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. The reflected light 12 is transmitted through the Fabry-Perot etalon 6. The light beam 113 from the Fabry-Perot etalon 6 is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 7 is transmitted through the polarizing beam splitter 5 as the output light beam. Another component is reflected at the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 113 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is reduced. The light load of the Fabry-perot etalon 6 used in the fourth embodiment is slightly larger than that of the first embodiment. This embodiment readily provides P polarized light because the polarizing beam splitter for transmitting P polarizing component can be provided readily.Hereinbelow will be described an embodiment not according to the invention. Fig. 5 is a front view of this embodiment of a laser apparatus. In Fig. 5, a discharge tube 1 comprises a mixed gas of noble and halogen gases as a laser medium. An optical resonator comprises total reflection mirrors 2 and 3 and the discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirrors 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and an Wollaston prism 111 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the Wollaston prism 111.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the Wollaston prism 111 and the total reflection mirror 2, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation of the laser apparatus of this embodiment not according to the invention.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is transmitted through the Wollaston prism 111. The light beam 9 is subjected to wavelength selection by Fabry-Perot etalon 6, and then it is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the Fabry-Perot etalon 6 and the Wollaston prism 111 again and is amplified by the laser medium. The amplified light beam 11 enters the quarter-wave plate 4. The light beam 11 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3 to produce a reflection light beam 12. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. The reflected light 12 is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 8 is transmitted through the Wollaston prism 111 as the output light beam 7. Another component is transmitted through the Wollaston prism 111 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 9 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is considerably reduced.Hereinbelow will be described a fifth embodiment. Fig. 6 is a front view of the fifth embodiment of a laser apparatus of the invention. In Fig. 6, an optical resonator comprises total reflection mirrors 2 and 3. A discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and an Wollaston prism 111 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the Wollaston prism 111.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the discharge tube 1 and the quarter-wave plate 4, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation bf the laser apparatus of the fifth embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is splitted and outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is splitted and bended by the Wollaston prism 111. The light beam 9 is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the Wollaston prism 111 again which returns the light beam 10 to a light path to the discharge tube 1. The light beam from the Wollaston prism 111 is amplified by the laser medium. The amplified light beam is transmitted through the Fabry-Perot etalon 6 where an wavelength selection is performed. The light beam 11 from the Fabry-Perot etalon 6 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3 to produce a reflection light beam 12. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. The reflected light 12 is transmitted through the Fabry-Perot etalon 6. The light beam 113 from the Fabry-Perot etalon 6 is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 8 is bended in one direction by the Wollaston prism 111 is outputted as output light beam 7. Another component is bended in another direction as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 113 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is reduced. The light load of the Fabry-perot etalon 6 used in the second embodiment is slightly larger than that of the first embodiment.Hereinbelow will be described a sixth embodiment. Fig. 7 is a front view of the sixth embodiment of a laser apparatus of the invention.In Fig. 7, a discharge tube 1 comprises a mixed gas of noble and halogen gases as a laser medium. An optical resonator comprises total reflection mirrors 2 and 3 and the discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is transmitted through the quarter-wave plate 4 and is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the polarizing beam splitter 5 and the total reflection mirror 2, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation of the laser apparatus of the sixth embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components. One polarized component is outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is transmitted through the polarizing beam splitter 5. The light beam 9 is subjected to wavelength selection by Fabry-Perot etalon 6, and then it is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the Fabry-Perot etalon 6 and the polarizing beam splitter 5 again and is amplified by the laser medium after transmission through quarter-wave plate 4. The light beam 11 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. The reflected light at the total reflection mirror is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 12 is reflected at the polarizing beam splitter 5 as the output light beam 7. Another component is transmitted through the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 9 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is considerably reduced. Light load of the quarter-wave plate 4 is lager than that would be in the case that the quarter-wave plate 4 is locate between the discharge tube 1 and the total reflection mirror 3. However, output efficiency is equivalent. Hereinbelow will be described an seventh embodiment. Fig. 8 is a front view of the seventh embodiment of a laser apparatus of the invention.In Fig. 8, a discharge tube 1 comprises a mixed gas of noble and halogen gases as a laser medium. An optical resonator comprises total reflection mirrors 2 and 3 and the discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3 via a polarizing beam splitter 5. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5 after transmission through the quarter-wave plate.A Fabry-Perot etalon 6 as an wavelength selection element is provided between the polarizing beam splitter 5 and the total reflection mirror 2, so that only specified narrow-band light beam is oscillated in the optical resonator. Hereinbelow will be described operation of the laser apparatus of the seventh embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components after transmission through the quarter-wave plate 4. One polarized component is transmitted through the polarizing beam splitter 5 and outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is reflected by the polarizing beam splitter 5. The light beam 9 is subjected to wavelength selection by Fabry-Perot etalon 6, and then it is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the Fabry-Perot etalon 6 and reflected by the polarizing beam splitter 5 again and is amplified by the laser medium after transmission through the quarter-wave plate 4. The light beam 11 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the light beam 12 having both polarization components. The light beam 12 is amplified by the laser medium of the discharge tube 1. One polarization component of the light beam 12 is transmitted through the polarizing beam splitter 5 as the output light beam 7. Another component is reflected at the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 9 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is considerably reduced. Light load of the quarter-wave plate 4 is lager than that would be in the case that the quarter-wave plate 4 is locate between the discharge tube 1 and the total reflection mirror 3. However, output efficiency is equivalent. This embodiment readily provides P polarized component light.Hereinbelow will be described a eighth embodiment. Fig. 9 is a front view of the eighth embodiment of a laser apparatus of the invention.In Fig. 9, a discharge tube 1 comprises a mixed gas of noble and halogen gases as a laser medium. An optical resonator comprises total reflection mirrors 2 and 3 and the discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirror 2 and 3. When the discharge tube 1 is excited a laser beam of ultraviolet is generated there. A quarter-wave plate 4 as a polarizing conversion element for changing ratio of P to S polarizing components and a polarizing beam splitter 5 as a polarizing beam splitting element are provided in the light path of the optical resonator, as shown. An output light beam 8 amplified by the laser medium of the discharge tube 1 is transmitted through the quarter-wave plate 4. A Light beam from the quarter-wave plate 4 is separated into one polarized light beam 7 outputted externally and another polarized light beam 9 by the polarizing beam splitter 5.A Fabry-Perot etalon 6 as an wavelength selection element is-provided between the discharge tube 1 and the total reflection mirror 3, so that only specified narrow-band light beam is oscillated in the optical resonator.Hereinbelow will be described operation of the laser apparatus of the eighth embodiment.The light beam 8 amplified by the laser medium of the discharge tube 1 is splitted in accordance with polarized components after transmission through the quarter-wave plate 4. One polarized component is outputted as the output light beam 7. Another component light beam, i.e., a light beam 9, is transmitted through the polarizing beam splitter 5. The light beam 9 is reflected at the total reflection mirror 2. The reflected light beam 10 is transmitted through the polarizing beam splitter 5 again and is amplified by the laser medium after transmission through the quarter-wave plate 4. The light beam 11 is transmitted through the quarter-wave plate 4 twice via the total reflection mirror 3. This twice transmission through the quarter-wave plate 4 is equivalent to one transmission through a half wavelength plate. Thus, the light beam 11 polarized in one direction is converted into the reflection light beam 12 having both polarization components. The light beam from the quarter-wave plate 4 is amplified by the laser medium and then transmitted through the fabry-Perot etalon 6. The amplified light beam and reflected light at the total reflection mirror 3 is subjected to wavelength selection by the Fabry-Perot etalon 6. A light beam after wave-length selection is amplified by the laser medium of the discharge tube 1 to produce the light beam 8. One polarization component of the light beam 12 is reflected at the polarizing beam splitter 5 as the output light beam 7. Another component is transmitted through the polarizing beam splitter 5 as the light beam 9 which maintains oscillation. As mentioned above, an intensity of the output light beam 7 is larger than that of the light beam 9 to the extent of a gain of the laser medium so that deformation and deterioration of the Fabry-Perot etalon 6 is considerably reduced. The light load of the Fabry-perot etalon 6 used in the ninth embodiment is slightly larger than that of the first embodiment.Herein below will be described a ninth embodiment of the invention with referring to Fig. 10.Fig. 10 is a front view of ninth embodiment of a narrow-band laser apparatus. In Fig. 10, an optical resonator comprises total reflection mirrors 2 and 3 and a discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirrors 2 and 3 which includes a mixed gas of noble and halogen gases as a laser medium. When the discharge tube 1 is excited, a laser beam of ultraviolet is generated there. In a light path of the resonator a polarizing beam splitter 81 is provided between the discharge tube 1 and the first total reflection mirror 2. A polarizing beam splitter 5 is provided between the discharge tube 1 and the second total reflection mirror 3. The polarizing beam splitter 81 separates propagation directions of light beams having different polarizing components. However, a portion of one polarizing component is reflected at the polarizing beam splitter 81 and other portion is transmitted through the polarizing beam splitter 81. For example, the polarizing beam splitter 81 reflects 100% of S polarizing component but transmits a ratio T of P polarizing component and reflects a ratio (1-T) of P polarizing component. The ratio T ranges from 0.005 to 0.8 approximately. The polarizing beam splitter 5 separates propagation direction of light beams of different polarizing directions. For example, it transmits 100% of S polarizing light and reflects 100% of P polarizing light. Therefore, S polarizing light 99 is outputted. A Fabry-Perot etalon 6 is provided between the polarizing beam splitter 81 and the first total reflection mirror 2 as an wavelength selection element. A quarter-wave plate 4 and a third total reflection mirror are provided in the light path separated at the polarizing beam splitter 81, i.e., the light path other than the light path of the resonator for maintaining oscillation.Hereinbelow will be described operation of the ninth embodiment.The polarizing beam splitter 81 transmits amplified P polarizing beam 94 incident thereto partially. The transmitted P polarizing light beam 89 enters the Fabry-Perot etalon 6 as an wavelength selection element, which selects only a given wavelength component from the light beam 89. Then the light beam transmitted through the Fabry-Perot etalon 6 is reflected at the first total mirror 2. The polarizing beam splitter 81 transmits a portion of the light beam 90 (a light beam 91) because the light beam 90 is a P polarizing beam. The discharge tube 1 amplifies the light beam 91 to output a light beam 92. The polarizing beam splitter 5 reflects the light beam 92 because the light beam 12 is polarized. The transmitted light beam is reflected at the second total reflection mirror 3 and then is reflected at the polarizing beam splitter 5 again as a light beam 93. The light beam 93 is amplified by the discharge tube 1 to output a light beam 94. A portion of the light beam 94 transmits the polarizing beam splitter 81 as a light beam 89 which maintains oscillation in the similar manner mentioned earlier. Other portion of the light beam 94 is reflected at the polarizing beam splitter 81 as a light beam 95. The light beam 95 is transmitted through the quarter-wave plate 4. The transmitted light beam is reflected at the third total mirror 88 and transmits the quarter-wave plate 4 again where P polarizing beam is converted into S polarizing beam, i.e., a light beam 96. This twice transmitting through the quarter-wave plate 4 is equivalent to one transmitting though a half-wave plate. It is known that if an optical axis of the quarter-wave plate 4 is set such that its optical angle has an inclination angle of 45° with respect to polarizing plane of the incident light, the P polarizing incident light is converted into S polarizing light totally. The polarizing beam splitter 81 reflects 100% of S polarizing light beam 96 to produce S polarizing light beam 97 which is amplified by the discharge tube 1. The amplified S polarizing light beam 98 is transmitted through the polarizing beam splitter 5 entirely to output S polarizing output light beam 99.As mentioned above, deformation and deterioration of the Fabry-Perot etalon 6 decreases considerably because an intensity of the output light beam 99 is larger than that of the light beam 89 incident to the Fabry-Perot etalon 6 by the gain of the laser medium, i.e., the output light beam is taken out after amplifying by the discharge tube 1. Deformation and deterioration of the Fabry-Perot etalon 6 in this embodiment decrease further compared with the first embodiment because the light beam 90 whose wavelength is selected is amplified by the discharge tube 1 three times, on the other hand, the light beam 10 in Fig. 1 whose wavelength is selected is amplified twice.Fig. 22 shows calculation results showing relationship between light intensity of output light beam 99 and light intensity of the beam 89 as light load of the Fabry-Perot etalon 6 with respect to transmittance of P component in the polarizing beam splitter 81. This result is obtained by modified equations described at Saturation Effects in High-Gain Lasers by W.W. RIGROD, Journal of Applied Physics, Vol. 36, No8, P2487-p2490, August 1965(Eqs. 7 and 11 of the document). The results show output light intensity Iout/Is and etalon load light intensity IE/Is which are normalized by saturation light intensity Is with respect to transmittance of P polarizing light beam of polarizing beam splitter 8.Fig. 25 shows calculation results showing relationship between light intensity of output light beam and light intensity of the beam 108 as light load of the Fabry-Perot etalon 104 of the prior art of Fig. 23. This result is obtained by the equations of the above-mentioned document. The results show output light intensity Iout/Is and etalon load light intensity IE/Is which are normalized by saturation light intensity Is with respect to reflectance R of the half mirror 103.Comparing the result shown in Fig. 22 of the embodiment of the invention with the result shown in Fig. 25 of the prior art, it is clear that the embodiment of the invention can output the same Iout with smaller value IE than that of the prior art of Fig. 23. In other words, in Fig. 22, when Iout/Is = 0.3, IE/Is = 0.004, on the other hand, in Fig. 25, IE/Is = 0.41 where the later is more than hundred times the former. Therefore, light intensity of incident light to the Fabry-Perot etalon 6 is reduced considerably. Moreover, there is a remarkable feature as follows:In Fig. 25 of the prior art, when a value of R is 0.15, the maximum output value Iout/Is = 0.31 is obtained. On the other hand, in the embodiment of the present invention, when T= 0.58, the maximum output Iout/Is= 0.83 is obtained. Thus, the output power of the invention is 2.7 times that of the prior art. That indicates the laser apparatus of the invention is excellent as a laser apparatus.As mentioned above, in this embodiment, light energy transmitted through the Fabry-Perot etalon 6 is largely reduced and a narrow-band laser apparatus showing an excellent characteristic of output efficiency.Herein below will be described an tenth embodiment of the invention with referring to Fig. 11.Fig. 11 is a front view of the tenth embodiment of a narrow-band laser apparatus. In Fig. 11, an optical resonator comprises total reflection mirrors 2 and 3 and a discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirrors 2 and 3 which includes a mixed gas of noble and halogen gases as a laser medium. When the discharge tube 1 is excited, a laser beam of ultraviolet is generated there. In a light path of the resonator a polarizing beam splitter 81' is provided between the discharge tube 1 and the first total reflection mirror 2. A polarizing beam splitter 5 is provided between the discharge tube 1 and the second total reflection mirror 3. The polarizing beam splitter 81' separates propagation directions of light beams having different polarizing components at different ratio. For example, the it reflects 30% and transmit 70% of P component and totally transmit S component. However, these ratios can be changed. The polarizing beam splitter 5 separates propagation direction of light beams of different polarizing directions. For example it reflects S component and transmit P component. A quarter-wave plate 4 and a third total reflection mirror are provided in the light path separated at the polarizing beam splitter 81', i.e., the light path other than the light path of the resonator for maintaining oscillation. A fabry-Perot etalon 6 is provided between the polarizing beam splitter 81' and the total reflection mirror 2 in the light path of the resonator.Hereinbelow will be described operation of the tenth embodiment.The polarizing beam splitter 81' transmits amplified P polarizing beam 94 incident thereto partially. The transmitted P polarizing light beam 89 enters the quarter-wave plate 4 where P polarizing component is converted into S polarizing component by twice passing therethrough via the third total mirror 88. The polarizing beam splitter 81' transmits a portion of the light beam 90 (a light beam 91) because the light beam 90 is a S polarizing beam. Some portion of S component is reflected at the polarizing beam splitter 81'. The discharge tube 1 amplifies the light beam 91 to output a light beam 92. The polarizing beam splitter 5 reflects the light beam 92 because the light beam 92 is S polarized. On the other hand, P component partially reflected by the polarizing beam splitter 81' is transmitted through a Fabry-Perot etalon 6 and reflected back by the total reflection mirror 2. A light beam whose wave-length is selected by the Fabry-Perot etalon 6 is reflected by the polarizing beam splitter 81' again and amplified by the discharge tube 1. This P component is transmitted through the polarizing beam splitter 5 and is reflected at the second total reflection mirror 3, this component is used for maintaining oscillation.Herein below will be described a further embodiment not according to the invention with referring to Fig. 12.Fig. 12 is a front view of the embodiment of a narrow-band laser apparatus. In Fig. 12, an optical resonator comprises total reflection mirrors 2 and 3 and a discharge tube 1 is provided in the light path of the optical resonator between the total reflection mirrors 2 and 3 which includes a mixed gas of noble and halogen gases as a laser medium. When the discharge tube 1 is excited, a laser beam of ultraviolet is generated there. In a light path of the resonator a polarizing beam splitter 81 is provided between the discharge tube 1 and the first total reflection mirror 2. An wollaston prism 111 as a polarizing beam splitting element is provided between the discharge tube 1 and the second total reflection mirror 3. The polarizing beam splitter 81 separates propagation directions of light beams having different polarizing components. However, a portion of one polarizing component is reflected at the polarizing beam splitter 81 and other portion is transmitted through the polarizing beam splitter. The wollaston prism separates propagation direction of light beams of different polarizing directions by bending the light paths of P and S components in different directions, as shown. A Fabry-Perot etalon 6 is provided between the polarizing beam splitter 81 and the first total reflection mirror 2 as an wavelength selection element. A quarter-wave plate 4 and a third total reflection mirror are provided in the light path separated at the polarizing beam splitter 81, i.e., the light path other than the light path of the resonator for maintaining oscillation.Hereinbelow will be described operation of the embodiment not according to the invention.The polarizing beam splitter 81 transmits amplified P polarizing beam 14 incident thereto partially. The transmitted P polarizing light beam 89 enters the Fabry-Perot etalon 6 as an wavelength selection element, which selects only a given wavelength component from the light beam 89. Then the light beam transmitted through the Fabry-Perot etalon 6 is reflected at the first total mirror 2. The polarizing beam splitter 81 transmits a portion of the light beam 90 (a light beam 91) because the light beam 90 is a P polarizing beam. The discharge tube 1 amplifies the light beam 91 to output a light beam 92. The wollaston prism 111 transmits and bends the light beam 92 in one direction because the light beam 92 is P polarized. The transmitted light beam is reflected at the second total reflection mirror 3 and then is transmitted through the polarizing beam splitter 5 again as a light beam 93 to return the light beam 93 to the discharge tube 1. The light beam 93 is amplified by the discharge tube 1 to produce a light beam 94. A portion of the light beam 94 transmits the polarizing beam splitter 81 as a light beam 89 which maintains oscillation in the similar manner mentioned earlier. Other portion of the light beam 94 is reflected at the polarizing beam splitter 81 as a light beam 95. The light beam 95 is transmitted through the quarter-wave plate 4. The transmitted light beam is reflected at the third total mirror 88 and transmits the quarter-wave plate 4 again where P polarizing beam is converted into S polarizing beam, i.e., a light beam 96. This twice transmitting through the quarter-wave plate 4 is equivalent to one transmitting though a half-wave plate. It is known that if an optical axis of the quarter-wave plate 4 is set such that its optical angle has an inclination angle of 45° with respect to polarizing plane of the incident light, the P polarized incident light is converted into S polarizing light totally. The polarizing beam splitter 81 reflects 100% of S polarizing light beam 96 to produce S polarizing light beam 97 which is amplified by the discharge tube 1. The amplified S polarizing light beam 98 is transmitted through the Wollaston prism 111 to output S polarizing output light beam 99.As mentioned above, deformation and deterioration of the Fabry-Perot etalon 6 decreases considerably because an intensity of the output light beam 99 is larger than that of the light beam 89 incident to the Fabry-Perot etalon 6 by the gain of the laser medium, i.e., the output light beam is taken out after amplifying by the discharge tube 1. Deformation and deterioration of the Fabry-Perot etalon 6 in this embodiment decrease further compared with the first embodiment because the light beam 90 whose wavelength is selected is amplified by the discharge tube 1 three times, on the other hand, the light beam 10 in Fig. 1 whose wavelength is selected is amplified twice.The above-mentioned embodiment is described using Fabry-Perot etalon 6, quarter-wave plate 4, polarizing beam splitters 5, 81 and Wollaston prism 111. However, other elements can be applied to this invention. Hereinbelow will be described other embodiments using such elements.Fig 13A shows an arrangement of the quarter-wave plate 4 and the total reflection mirror 3. Figs. 13B and 13C show equivalent arrangements using equivalent elements to these elements. Combination of a phase retarder mirror 140 with the total reflection mirror 3 acts as the that of the quarter-wave plate 4 with the total reflection mirror 3. One type of phase retarder prism 40 is equivalent to those combination. Therefore, these combination and the element can be replaced with each other.Fig. 18 is a perspective view of the phase retarder prism 40. In Fig. 18, the phase retarder prism 40 is made of high-transmittance material, such as, synthesized quartz and CaF2. Anti-reflection coat surface (AR coat surface) is formed on a surface 43 where a light beam 29 enters the phase retarder prism 40 and a light beam 26 exits. Further, this surface 43 is inclined by about 2° so that the incident light beam 29 directly reflected at this surface 43 is not mixed with the output light beam 26. Thus, this prism 40 has apex angles 45°, 47°, and 88° unlike the normal type 45° prism. A surface 42 reflects the light beam at a right angle. A dielectric multilayer is formed on the surface 42, which produces P and S polarizing components having 90° phase difference therebetween in accordance with structure and thickness of dielectric layers and is optically equivalent to the quarter-wave plate 4. The light beam reflected at the surface 42 is reflected at a total reflection surface 41 at aright angle and outputted (light beam 26) in the opposite direction. The total reflection mirror surface 41 can be formed easily by a dielectric multilayer.As mentioned above, the phase retarder prism 40 functions as the quarter-wave plate 4 and the second total reflection mirror 88 and thus, it makes the structure of the apparatus simple and adjustment easy.Fig 14A shows the Fabry-Perot etalon 6. Figs. 14B and 14C show equivalent elements to these elements. A prism 30 can select a given wavelength component from incident light thereto. A grating 20 also can select a given wavelength component from incident light thereto. Therefore, these elements can be replaced with each other.Fig 15A shows an arrangement of the grating 20 and the total reflection mirror 2. Fig. 15B shows an element equivalent to that arrangement. The Littrow type grating or echelle grating 60 can separate a given wavelength component and reflect in the direction opposite to incident light thereto. Therefore, these combination and the element can be replaced with each other.Fig 16A shows the polarizing beam splitter 5. Figs. 16B and 16C show elements equivalent to the polarizing beam splitter 5. A cube type polarizing beam splitter can separate incident light into two polarizing components. The Wollaston prism 111 also can separate incident light into two polarizing components. Therefore, these elements can be replaced with each other.Fig 17A shows an arrangement of the polarizing beam splitter 5 and the prism 30. Fig. 17B shows an element equivalent to that arrangement. A polarizing beam splitting prism 116 can separate two polarizing components and can separate a given wavelength component from light transmitted there through. The reflective surface thereof comprises dielectric multilayer. Therefore, these combination and the element can be replaced with each other.In the above-mentioned embodiments of laser apparatus, lasing oscillation is performed with P polarizing component, and then P polarizing component is converted into S component which is amplified to output laser beam. In contrast with this, it is possible that lasing oscillation is performed by S polarizing component, and then S polarizing component is converted into P component which is amplified to output laser beam. Therefore, it is possible to select either polarizing components for oscillation or amplifying in order to make easier carrying out above-mentioned embodiments. As mentioned above, there are various types of polarizing conversion element for producing polarizing components such as Fresnel rhomboid prism, thee-time total reflection ultra-achromatic quarter-wave plate, etc. In order to obtain a large-diameter beam for exposure, a first-order or multiple-order quarter-wave plate using a crystal quartz plate is suitable. Moreover, it is not necessary that a quarter-wavelength plate is not accurate. In other words, a phase plate capable of changing the ratio between polarized components S and P can be used.Further, a multilayer cube polarizing element, a transparent plate of Brewster's angle, a Wollaston prism, etc., can be used as the polarizing beam splitter mentioned above. In order to obtain large diameter beam for exposure, a polarization beam split mirror is excellent.Fig. 19 is a front view of the polarizing beam splitter 81, for example. It comprise a combination of a perfect polarizing beam splitter 50 with a half mirror 51 for the same function as that of the polarizing beam splitter 81. As shown in Fig. 20, the polarizing beam splitter 81 may also comprise a polarizing beam splitting film 52 made of dielectric layer formed on a plate 53 of quartz or CaF2 whose other surface is covered with semi-transparent film 54.Further, a multilayer cube polarizing element, a transparent plate of Brewster's angle, a Wollaston prism, etc., can be used as the polarizing beam splitter mentioned above. In order to obtain large diameter beam for exposure, a dielectric multilayer polarization beam splitter is excellent.Moreover, in the above-mentioned embodiments, the wavelength selection element is provided between the polarization beam splitter and the total mirror 2. However, the wavelength selection element can be provided to other position except the light path from the laser medium to the polarization beam splitter via which the output light outputted externally where the output laser beam is the most powerful light beam.Plural Fabry-Perot etalons 6, gratings 20, or prisms 30 used in the above-mentioned embodiments can be used as an wavelength selection element or combination between the above-mentioned elements may be used. Moreover, an element combing of an wavelength selection element with a total reflection mirror, such as echelle grating or echelon grating for utilizing wavelength selection function of gratings. In the prism used in above-mentioned embodiment, a total reflection mirror may be formed on one surface thereof. Further, the number of elements can be reduced by combing function of the quarter-wave plate with that of the total reflection mirror 2, i.e., a total reflection surface is formed on one surface of a plate of MgF2 or quartz phase plate. In other words, the number of elements can be reduced by using an element combining function between these elements for the above-mentioned wavelength selection element, a total reflection mirror, a quarter-wave plate, polarizing beam splitter, etc.It is not necessary that the total reflection mirrors used in the above-mentioned embodiment have 100% reflectance but it may be a reflectance which maintains optical resonating.As mentioned above, according to this invention, a portion polarized light beam is taken out by polarizing beam splitter from one polarized light beam; the beam taken out is subjected to polarizing direction conversion by a polarizing conversion element and then it is amplified by the laser medium; and then amplified beam is outputted by a polarizing beam splitter. Therefore, light energy transmitted through the wavelength selection element is reduced by an inverse number of the gain of the laser medium, so that deformation or deterioration of the wavelength selection element is reduced. As a result, a narrow-band laser apparatus suitable for an exposure light source for photolithography is provided without variation of selection wavelength or decrease in output power. A laser apparatus comprises an optical resonator including first and second mirrors, and laser medium. An wavelength selection element is provided in the resonator for narrowing band-width. A polarizing conversion element for changing ratio of S to P components and polarizing beam splitter are provided for amplifying laser beam to output after wavelength selection and for reducing light load of the wavelength selection element. The polarizing conversion element is provided in the resonator light path. In another embodiment, the polarizing conversion element is provided in a branch light path formed by a second polarizing conversion element and a third mirror, where the second polarizing conversion element reflects and transmits P component at a given ratio and reflects S component. The wavelength selection element comprises a Fabry-Perot etalon, grating, or prism. The polarizing conversion element comprises a quarter-wave plate or a phase retarder mirror. The polarizing beam splitting element comprises a polarizing beam splitter or polarizing beam splitting prism. Such laser apparatus is suited for an exposure light source for photolithography.
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A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said first reflecting means (2) and to transmit said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said first reflecting means (2) and said polarizing beam splitting means (5; 111; 115) in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said second reflecting means (3) in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to transmit said second polarized component (9) toward said first reflecting means (2) and to reflect said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said second reflecting means (3) and said laser medium in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said selection means (6; 20; 30) and said second reflecting means (3) in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to transmit said second polarized component (9) toward said first reflecting means (2) and to reflect said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said second reflecting means (3) and said laser medium in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said selection means (6; 20; 30) and said laser medium in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said first reflecting means (2) and to transmit said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said second reflecting means (3) and said laser medium in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said selection means (6; 20; 30) and said second reflecting means (3) in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (111) provided between said first reflecting means (2) and said laser medium in said light path for bending and transmitting a first polarized component (7) as an output light and for bending and transmitting a second polarized component (9) toward said first reflecting means (2),a selection means (6; 20; 30) provided between said second reflecting means (3) and said laser medium in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said selection means (6; 20; 30) and said second reflecting means (3) in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to transmit said second polarized component (9) toward said first reflecting means (2) and to reflect said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said first reflecting means (2) and said polarizing beam splitting means (5; 111; 115) in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said laser medium in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said first reflecting means (2) and to transmit said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said first reflecting means (2) and said polarizing beam splitting means (5; 111; 115) in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said laser medium in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for remitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to transmit said second polarized component (9) toward said first reflecting means (2) and to reflect said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said second reflecting means (3) and said laser medium in said light path for selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said laser medium in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including an echelle or echelon grating (60) and second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said echelle or echelon grating (60) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said echelle or echelon grating (60) and to transmit said first polarized component (7) as output light,said echelle or echelon grating (60) selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said second reflecting means (3) in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including echelle or echelon grating (60) and second reflecting means (3), a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said echelle or echelon grating (60) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said echelle or echelon grating (60) and to transmit said first polarized component (7) as output light,said echelle or echelon grating (60) selecting a given wavelength component from said light, anda polarizing conversion means (4; 140) provided between said polarizing beam splitting means (5; 111; 115; 116) and said laser medium in said light path for producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and a phase retarder prism (40) whose one surface is covered with a reflection layer,a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said first reflecting means (2) and to transmit said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said first reflecting means (2) and said polarizing beam splitting means (5; 111; 115) in said light path for selecting a given wavelength component from said light, andsaid phase retarder prism (40) producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and a phase retarder prism (40) whose one surface is covered with a reflection layer,a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to transmit said second polarized component (9) toward said first reflecting means (2) and to reflect said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said phase retarder prism (40) and said laser medium in said light path for selecting a given wavelength component from said light, andsaid phase retarder prism (40) producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and a phase retarder prism (40) whose one surface is covered with a reflection layer,a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means, a polarizing beam splitting means (5; 111; 115; 116) provided between said first reflecting means (2) and said laser medium in said light path for splitting said light into a first polarized component (7) as an output light and a second polarized component (9), said polarizing beam splitting means (5) being arranged so as to reflect said second polarized component (9) toward said first reflecting means (2) and to transmit said first polarized component (7) as output light,a selection means (6; 20; 30) provided between said phase retarder prism (40) and said laser medium in said light path for selecting a given wavelength component from said light, andsaid phase retarder prism (40) producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first reflecting means (2) and a phase retarder prism (40) whose one surface is covered with a reflection layer,a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a polarizing beam splitting means (111) provided between said first reflecting means (2) and said laser medium in said light path for bending and transmitting a first polarized component (7) as an output light and for bending and transmitting a second polarized component (9) toward said first reflecting means (2),a selection means (6; 20; 30) provided between said phase retarder prism (40) and said laser medium in said light path for selecting a given wavelength component from said light, andsaid phase retarder prism (40) producing said first polarized component and said second polarized component in response to said light.A narrow-band laser apparatus comprising an optical resonator including first and second reflecting means (2, 3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said first reflecting means (2) and said laser medium for transmitting a first polarized component (89) partially and reflecting a second polarized component (95),selection means (6; 20; 30) provided between said first reflecting means (2) and said first polarizing beam splitting means for selecting a given wavelength component from said first polarizing component (89),a third reflecting means (88) for reflecting back a light ray from said first polarizing beam splitting means,a polarizing conversion means (4; 40) provided between said first polarizing beam splitting means and said third reflecting means in said light path for converting said first polarized component into said second polarized component in response to said light, anda second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for transmitting a first polarized component (99) as output light and for reflecting a second polarized component (98) toward said second reflecting means (3).A narrow-band laser apparatus comprising an optical resonator including first and second reflecting means (2, 3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said first reflecting means (2) and said laser medium for reflecting a first polarized component (95) partially and transmitting a second polarized component (89),selection means (6; 20; 30) provided between said first reflecting means (2) and said first polarizing beam splitting means for selecting a given wavelength component from said first polarized component (95),a third reflecting means (88) for reflecting back a light ray from said first polarizing beam splitting means,a polarizing conversion means (4; 40) provided between said first polarized beam splitting means and said third reflecting means in said light path for converting said first polarized component into said second polarized component in response to said light, anda second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for splitting said light into a first polarized component and a second polarized component.A narrow-band laser apparatus comprising an optical resonator including an echelle or echelon grating (60) and a second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said echelle or echelon grating (60) and said laser medium for transmitting a first polarized component (89) partially and reflecting a second polarized component (95),said echelle or echelon grating selecting a given wavelength component from said light,a third reflecting means (88) for reflecting back a light ray from said first polarizing beam splitting means,a polarizing conversion means (4; 40) provided between said first polarizing beam splitting means and said third reflecting means in said light path for converting said first polarized component into said second polarized component in response to said light, and a second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for transmitting a first polarized component (99) as output light and for reflecting a second polarized component (98) toward said second reflecting means (3).A narrow-band laser apparatus comprising an optical resonator including an echelle or echelon grating (60) and a second reflecting means (3),a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said echelle or echelon grating (60) and said laser medium for reflecting a first polarized component (95) partially and transmitting a second polarized component (89),said echelle or echelon grating selecting a given wavelength component from said light,a third reflecting means (88) for reflecting back a light ray from said first polarizing beam splitting means,a polarizing conversion means (4; 40) provided between said first polarizing beam splitting means and said third reflecting means in said light path for converting said first polarized component into said second polarized component in response to said light, anda second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for splitting said light into a first polarized component and a second polarized component (99).A narrow-band laser apparatus comprising an optical resonator including first and second reflecting means (2, 3), a laser medium provided in a light path of said optical resonator for emitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said first reflecting means (2) and said laser medium for transmitting a first polarized component (89) partially and reflecting a second polarized component (95),selection means (6; 20; 30) provided between said first reflecting means (2) and said first polarizing beam splitting means for selecting a given wavelength component from said first polarized component (89),a phase retarder prism (40) whose one surface is covered with a reflection layer for reflecting back a light ray from said first polarizing beam splitting means, and for converting said first polarized component into said second polarized component in response to said light, anda second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for transmitting a first polarized component (99) as output light and for reflecting a second polarized component (98) toward said second reflecting means (3).A narrow-band laser apparatus comprising an optical resonator including first and second reflecting means (2, 3),a laser medium provided in a light path of said optical resonator for remitting light, said laser medium including an exciting means,a first polarizing beam splitting means (81) provided between said first reflecting means (2), and said laser medium for reflecting a first polarized component (95) partially and transmitting a second polarized component (89),selection means (6; 20; 30) provided between said first reflecting means (2) and said first polarizing beam splitting means for selecting a given wavelength component from said first polarized component (95),a phase retarder prism (40) whose one surface is covered with a reflection layer for reflecting back a light ray from said first polarizing beam splitting means, and for converting said first polarized component into said second polarized component in response to said light, anda second polarizing beam splitting means (5) provided between said laser medium and said second reflecting means (3) for splitting said light into a first polarized component and a second polarized component.A narrow-band laser apparatus according to any of claims 1 to 14, characterized in that said polarizing beam splitting means comprises a Wollaston prism.A narrow-band laser apparatus according to any of claims 1 to 8 or 11 to 16, 19 or 20, characterized in that said selection means comprises a Fabry-Perot etalon (6).A narrow-band laser apparatus according to any of claims 1 to 8 or 11 to 16, 19 or 20, characterized in that said selection means comprises a grating (20).A narrow-band laser apparatus according to any of claims 1 to 8 or 11 to 16, 19 or 20, characterized in that said selection means comprises a prism (30).A narrow-band laser apparatus according to any of claims 1 to 14, characterized in that said polarized beam splitting means comprises a cube type of polarizing beam splitter (115).A narrow-band laser apparatus according to any of claims 1 to 14, characterized in that said polarizing beam splitting means comprises a polarizing beam splitting prism (116), a dielectric multilayer being formed on said polarizing beam splitting prism (116).A narrow-band laser apparatus according to any of the preceding claims, characterized in that said laser medium comprises an excimer including noble and halogen gas.A narrow-band laser apparatus according to any of claims 1 to 10 or 15 to 18, characterized in that said polarizing conversion means (4) comprises a quartz plate. A narrow-band laser apparatus according to any of claims 1 to 10 or 15 to 18, characterized in that said polarizing conversion means comprises a phase retarder mirror (40).A narrow-band laser apparatus according to any of claims 15 to 20, characterized in that said first polarizing beam splitting means (81) comprises a polarizing beam splitter and a half mirror.
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MATSUSHITA ELECTRIC IND CO LTD; MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
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FURUYA NOBUAKI; HORIUCHI NAOYA; MIYATA TAKEO; ONO TAKUHIRO; YAMANAKA KEIICHIRO; FURUYA, NOBUAKI; HORIUCHI, NAOYA; MIYATA, TAKEO; ONO, TAKUHIRO; YAMANAKA, KEIICHIRO
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EP-0489964-B1
| 489,964 |
EP
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B1
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EN
| 19,950,201 | 1,992 | 20,100,220 |
new
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B21B27
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B21B1
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B21B3, B21B45, B21B27, B21B1, B21B28, B23K26
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B21B 27/00R, B21B 1/22R
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Improvements in or relating to rolling metal products
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A method for rolling material between rotating rolls utilizing a lubricant, at least one of the rolls (10) having an anisotropic working surface that comprises a topography of smooth bearing areas (52) spaced apart by at least one micron-size groove (40) extending around and along the face of the roll in the general direction of rolling. The groove receives and conducts lubricant freely therealong during the rolling process, i.e., as the material to be rolled is directed through the rotating rolls, and is compressed between the rolls, the smooth-bearing areas force lubricant from the areas to the location of the groove in the roll. In this manner, the material is rolled under boundary lubrication conditions.
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The present invention relates generally to rolling metal products and particularly to providing such products with an anisotropic engineered surface texture that provides improved uniform brightness. A surface appears bright to the human eye when the surface reflects incident light specularly, i.e., when the light striking the surface is not significantly diffused. Specular reflection, in turn, requires a non-random surface finish so that light is reflected from the surface at the same angle it was incident to the surface (which is the definition of specular reflection). A random surface diffuses incident light and thus makes the surface appear dull to the human eye, i.e., incident light is reflected randomly in many directions because of the random orientation of surface roughness; the internal order of the incident light is hence not preserved. In providing a rolled sheet product with a bright surface, the surface of the work roll employed to produce the product must also have a topography that is engineered to provide a high degree of regularity. Traditional methods of finishing work rolls involve one or more grinding operations. Grinding, however, does not provide roll surfaces with uniform textures since grinding is very much a stochastic process which results in a ground texture height, measured from an average datum line from which average roughness can be measured, that follows a normal or Gaussian distribution. The distribution of roughness is influenced by the abrasive particle size in the grinding medium (wheel), the feed rate of the roll in relation to the grinding medium, depth of cut and the number of grinding passes. In manufacturing aluminum can end stock, for example, the customer desires the stock (sheet) to have a uniformly bright, highly reflective surface, with a certain composite surface roughness that is smooth to the human touch and appears shiny to the human eye. This requires the rolling operation to be conducted in the boundary lubrication regime, which means that there is significant metal-to-metal contact. The texture of the roll surface may then be faithfully imprinted onto the sheet surface. With present state-of-the-art roll grinding, the rolling of aluminum sheet in the boundary lubrication regime to create a bright surface at high speeds (e.g. 1220 m (4000 ft.) per minute) is difficult with relatively large (typically 55,9 cm (22 inch) diameter) work rolls. There are three primary reasons for this: 1) the grinding process generates variable depth grooves, i.e., the depths of two successive grooves may be quite different in the roll surface, which results (locally) in partial or total separation of the roll surface from the sheet surface due to the generation of thick lubricant films, 2) a ground roll surface produces a non-uniform texture height on the sheet surface due to the Gaussian distribution of surface roughness, as discussed above, resulting in diffuse reflection of light, and 3) a ground roll surface has non-uniform wear characteristics, which result in inconsistencies in the rolling operation, i.e., rolling speed must be changed (lowered) to accommodate the worst case condition on the roll surface. (Ground rolls, in addition, require frequent regrinding, which adds cost to the rolling process.) It is well known that the thickness of a lubricating film is a function of the square root of roll diameter such that larger work rolls are more of problem than smaller work rolls. In reference to rolling speed, film thickness is a linear function of velocity. EP-A-371946 is concerned with the marking of a mill roll with an intermittent laser beam for the purpose of providing textured undersurface to ensure a good bond with a subsequently applied metal plating. EP-A-255501 is also concerned with the provision of a receptive surface for coating, in that case with paint. Whereas the present invention seeks to avoid fissures or undesirable topography on rolled metal material, EP-A-255501 aims to provide a textured surface having facets and valleys in the rolled product. As explained earlier, a bright, highly specularly reflective surface is one that reflects light primarily at the angle at which the light strikes the surface, i.e. the angle of incidence, rather than reflecting the light in a diffuse manner. The ratio of diffuse to specular reflection, which is the amount of reflected light measured at the angle of incidence compared to the amount of light measured at two degrees from incidence, is a good measure of surface brightness. The lower this ratio the greater is the surface brightness. Diffuse reflection may also occur in the presence of micro-size cracks or fissures. Fissures are generally created when a product is rolled under hydrodynamic lubricating conditions which means that roll and product surfaces are either locally or entirely separated by a lubricant film. This is especially true for the high speeds at which aluminum sheet is rolled. If fissures pre-exist in the product surface, they may be enhanced since the hydrodynamic pressure in the lubricant film forces lubricant into such cracks to widen and deepen them. Fissures generally extend in a direction that is transverse to the direction of rolling, and can occur in both steel and aluminum products. The result, then, of a ground roll surface is a random, stochastic texture imparted to a rolled product's surface, including fissures, such that the surface appears dull to the human eye. The present invention is directed to the consistent, repeatable production of bright metal surfaces. This is accomplished by rolling the product under primarily boundary lubrication conditions. According to the present invention there is provided a method of reducing the thickness of metal material including the steps of passing the material to be reduced through work rolls of a rolling mill, rotating said rolls and maintaining a compressive force on the material by said rolls, characterized in that at least one of said rolls has a polished finish and a rolling surface of smooth-bearing areas spaced by at least one continuous minute groove extending around the roll by several revolutions in the general direction of rolling, said polished surface and the banks of said groove being free of any material deposits, in that said polished finish and groove have a coat of hard, dense material, and in that a lubricant is introduced against the rolling surfaces of said work rolls and forced into the minute groove by said compressive force maintained against the material between the rotating rolls whereby the thickness of the material between the rolls is substantially reduced under boundary lubrication conditions such that fissures are not created or enlarged in the surface of the material, and imparting the polish finish of said at least one roll to the surface of the metal material contacting the polished finish of said roll. According to a further aspect of the invention there is provided for carrying out such a method a roll for a rolling mill, characterized in that said roll has a polished finish, in that at least one continuous groov extends around the roll by several revolutions in the general direction of rolling, in that both the polished surface and the banks of the groove are free of material deposits and in that a coat of hard dense material cover said polished finish and groove. Hence, between the minute grooves are the mirror finished areas, which are planar, and which provide smooth bearing surfaces that bear against the product, as it is rolled, to force lubricant from the bearing surfaces to the grooves so that the lubricant flows in the grooves at the entry of the roll bite. The results are (1) no thick layer of lubrication is available to open up the surface of the product bearing against the roll to create and/or enhance microcracks in the product surface, and (2) the bearing areas smear the surface of the product which enhances product brightness. The surface of the rolled product appears uniformly bright to the human eye. With a diffuse to specular reflection ratio on the order of 0.005 in the rolling direction. Such a grooved surface is anisotropic, which means the surface does not exhibit properties having the same measured values along all measuring axes in all directions. A rolled metal product may thus be provided with improved brightness over metal rolled with conventionally ground rolls and the invention makes it possible to provide the working surface of a mill roll with a texture that produces such an improvement in brightness The groove is of micron size in width and depth; - the multiple encircling grooves are spaced from each other by a distance on the order of five to 300 microns. In this manner, a roll surface may have extended life and wear characteristics such that frequent regrinding of the rolls is not necessary and therefore the cost of grinding and the manufacturing process as a whole is reduced. Generation of a minimum of debris is also possible so that neither the roll surface nor the product surface is significantly marred by debris and the filtration load on the mill oil house is greatly reduced (rolling lubricants used in large mills are generally recycled through filtering apparatus located in oil houses, physically separated from the mills but connected in fluid communication with the mills to receive dirty lubricant from the mill and return clean lubricant to the mill.). The shape of the groove in the work roll surface that receives material undergoing substantial reduction in thickness is such that the groove does not retain or seize the material. Such a roll results in the production of a rolled product with a surface texture having uniformly consistent ridges or plateaus spaced apart by planar areas or valleys which are mirror finished. Unlike the prior art which discloses the use of continuous-type lasers to score roll surfaces, the present invention employs pulsed-type lasers, such as carbon dioxide (CO ), Neodymium:Yittrium-Aluminum-Garnet (Nd:YAG) or Excimer lasers, which afford maximized peak powers yet minimize the average heat input into a roll surface while providing superior control over the shape of the texture scored in the roll surface. Further, pulsed lasers require no external mechanical manipulation of the laser beam prior to its impingement against the surface to be machined. The preferred embodiment involving a laser device is the Nd:YAG laser since its output is more focusable thereby enhancing the precision of the scoring work and it is generally easier to maintain compared to a CO₂ laser. The grooved profile can also be produced by a cubic boron nitride or diamond tool that has been precisely shaped to a desired profile by a diamond grinding tool, for example, or by wire or ion-beam machining. The use of a continuous wave CO₂ laser to inscribe a texture on a mill roll is shown in U.S. Patent 4,322,600 to Crahay. Crahay employs the laser to form, i.e., burn perforations and microcavities in the roll surface, such a surface being used to roll steel sheet. A flow of oxygen gas is employed to enhance the burning process. Another patent directed to the use of lasers for machining a roll surface is U.S. Patent 4,628,179, again to Crahay. Crahay here employs a laser or electron beam to provide an isotropic surface roughness by overlapping and substantially filling grooves formed in the roll surface by the laser or electron beam. Crahay states that the desired isotropy of roughness can only be obtained if two successive paths of the beam have sufficient overlap. This means that the second pass is required over the course of the first pass such that material of the roll is fused and displaced (again using oxygen for a burning process) into the first pass thereby essentially filling and covering the first pass altogether. Hence, the patentee states that the spot size of the beam is 120 microns and successive spots overlap in 100 micron intervals, as they trace a helical course around the roll. Crahay's isotropy is said to be achieved by the ratio of the pitch of a helical course to the width of a beam path being less than one. It is anticipated that the use of the technique of the second Crahay patent, as discussed above, will lead to significant wear debris generation during high speed rolling of non-ferrous metals such as aluminum. This would lead to a product surface having a higher concentration of wear debris as well as a coating of the roll surface with the debris, i.e. metal transfer, since the roll roughness and subsequent lubricant flow are not controlled in the manner described herein. The invention, along with its objectives and advantages, will be best understood from consideration of the following detailed description and the accompanying drawings in which: Fig. 1 shows schematically a laser device for precision texturing of the surface of a steel roll in accordance with the principles of the present invention; Fig. 2 is a photomicrograph of an AISI 52100 steel roll surface magnified 200 times, the surface being provided with micron size grooves by the laser of Fig. 1. (Material displacement on the roll surface caused by deposition of vaporized surface material has been removed and the surface coated with a layer of chrome). Fig. 3 is a photomicrograph of a AISI 52100 steel roll surface (magnified 200 times) that has been textured in the manner of Fig. 2 but which contains material deposition along the banks of the grooves; Fig. 4 is a photomicrograph of a surface of a sheet of aluminum alloy 5182 magnified 200 times. The sheet undervent a 17% reduction in thickness with a ground roll surface. The photomicrograph shows a surface texture littered with fissures, which are small microcracks extending in a direction generally transverse to the direction of rolling; Fig. 5 shows the mechanism by which the fissures of Fig. 4 are generated during rolling; Fig. 6 shows schematically diffuse reflection of light from a surface having random crests and valleys; Fig. 7 is a photomicrograph of the surface of a second sheet of 5182 alloy magnified 200 times, the sheet having been rolled by a roll whose working surface was prepared by electric discharge machining; Fig. 8 is a photomicrograph of another aluminum sheet, magnified 200 times, showing the substantial absence of transverse fissures or microcracks; Fig. 9 shows diagrammatically the surface of a sheet as rolled by the textured roll of Figure 1; and Fig. 10 shows a work roll in partial section provided with minute grooves formed by a micron size cutting insert mounted in a tool holder. Referring now to Fig. 1 of the drawings, a tool steel work roll 10 of a rolling mill (not otherwise depicted in the drawings) and a Nd:YAG laser 12 are shown schematically in the process of machining micron size helical grooves 14 in the roll surface. The grooves extend continuously in the general direction of rolling. As depicted (in plan view) grooves 14 are disposed in a side-by-side manner, though they may, in fact, comprise a single continuous groove that extends helically about and along the length of the roll. The number of grooves or revolutions of a single groove depends upon the width of the strip to be rolled. The Nd:YAG laser incorporates a Q switch which provides a high intensity (pulsed) beam of energy 16 having a wavelength primarily of 1.064 microns which is in the invisible portion (near infrared) of the electromagnetic spectrum. Q-switching is described in some detail in Solid State Engineering , Second Edition by Walter Koechner, Springer-Verlag, 1988. Basically, it involves the collection of the energy of the laser's pump lamp in the lasing element, and then dumping the collected energy into short pulses of 100 nanoseconds or so. With Q-switching, the peak powers of the beam can be increased significantly yet can be maintained in minute bundles or pulses of energy, sufficient enough to score metal surfaces. The width of beam 16 is five to ten microns (depending on the focusing optics within the device) such that, with the above intensity (pulsed power) of the beam, each pulse of the beam vaporizes a spot on the surface metal of a tool steel roll at a width or diameter corresponding to the beam width when the beam strikes the roll surface without substantial melting of the steel. A discrete, minute groove 14 is thereby formed in the surface of roll 10 when the beam and roll are moved relative to one other. Preferably, the roll is rotated about its axis and is moved longitudinally, lengthwise of the roll. The frequency and wavelength of a Nd:YAG or Excimer laser is such that their beams can micromachine a groove in a working surface on the order of the width or cross section of the beams, the wavelength of the YAG or Eximer laser being more efficient in penetrating (coupling to) the metal of a workpiece than that of a CO₂ laser. If the frequency of the laser is doubled (which yields a beam at the 1.064 micron wavelength) or tripled (which yields a beam at one-third the 1.064 micron wavelength), or quadrupled (which yields a beam at one-fourth the 1.064 micron wavelength) a groove is formed that is respectively half, one-third or one-fourth the size of the groove formed without frequency doubling, tripling or quadrupling. For example, the Nd:YAG laser can form a groove having a width of eight microns in a steel workpiece. Doubling the laser frequency will form a four micron wide groove due to the smaller emitted wavelength. The beam produced by frequency doubling couples more efficiently to steel surfaces than the original 1.064 micron wavelength of the laser such that the machining effected by the pulsed beam is finer in cross section. Frequency doubling can be effected by having the laser end-pump a Lithium Iodate (LiIO₃) crystal. The desired output of the LiIO₃ crystal lies in the green portion (0.532 micron) of the electromagnetic spectrum. A groove width of four to twenty microns is suitable for rolling aluminum sheet, with a groove depth in the range of 0.5 to five microns. Depth is controlled by the power of the pulsed beam and the time a given section of steel surface is exposed to the beam. Generally, the lower the wavelength of the laser beam, the finer the cut effected by the beam. In forming groove 14, the vaporized metal is moved ahead of beam 16 by directing a flow of air from a nozzle 18 located behind the beam. (As depicted in Fig. 1, nozzle 18 is shown in perspective and off-center of beam 16 for purposes of illustration only.) The source of the air can be plant air, which is ordinarily available in factories and shops. The flow of air from 18 is effective to move vaporized metal ahead of the laser beam to preheat the roll surface just ahead of the beam. The flow from 18 is also effective to limit the amount of vaporized metal depositing on the banks of the groove (Fig. 3) and on the optics (not visible in Fig. 1) that focus beam 16 on the roll surface. In the case where metal deposits reach the banks of the groove, the roll is lightly polished to remove such deposits after the machining process has been completed. This is the case of the photomicrograph of the roll surface shown in Fig. 2 of the drawings. In Fig. 2, the grooves are the dark lines that extend nearly perpendicular to the roll axis. The grooves are 15.0 microns wide and are spaced from each other by a distance of 113.0 microns. The beam of a Nd:YAG laser characteristically produces generally wedge or truncated triangular shaped grooves (in cross section transverse of the width of the grooves) in the surface of a roll. When rolling a strip 20, such as shown in partial section in Fig. 9, with such wedge-shaped grooves, a small fraction of the strip surface material flows into the grooves partially filling them. This is a plastic deformation process known as micro-backwards extrusion. The effect of the grooves is thus to produce narrow wedge-shaped raised portions or ridges 22 (Fig. 9) on the strip surface. Between the ridges are substantially smooth areas 26 that reflect incident light 28 in a specular manner 30 such that strip 20 is bright to the human eye. The ridges 22, being only a few microns wide, are not clearly visible to the human eye. An instrument capable of producing continuous grooves in a working surface that are other than wedge shaped is a cutting tool 35, as shown schematically in Fig. 10 in elevation. The tool includes an insert 36 having a hard, very minute, micron size cutting edge 38 of a predetermined shape in cross section. The cutting edge is capable of cutting a groove 40 in roll 10 of a size and cross sectional shape corresponding to the size and shape of 36 when it engages the roll surface under appropriate force, as indicated by arrow 42 in Fig. 10 and the insert and roll relatively moved. The cross section of the insert can be substantially triangular (as shown), semi-circular or Gaussian (bell shaped) and hence is not limited to the wedge shape provided by the beam of laser 12. The insert 36 can be sized to provide grooves in roll 10 of a depth in the range of 0.25 to five microns and a width in the range of 2.5 to 25 microns. In the cases of triangular, semi-circular or Gaussian-shaped grooves, the width is measured at the base of the grooves, which is in the plane of the surface of the roll. The width of the areas (52) between the grooves lies in the range of five to 300 microns. When such a groove in the roll engages material 20 (Fig. 9) in the rolling, thickness reduction process, the material of 20 extrudes into the groove to form a ridge configuration approximating the transverse cross section of the insert. The material of insert 36 is preferably cubic boron nitride. Such material is commercially available and used as a metal cutting (severing) tool. The cutting surface of such a nitride material is appropriately shaped to a micron size configuration by a diamond grinding tool or by ion-beam machining. In Fig. 10, the roll and tool are relatively moved to form grooves 40. If the grooves (in elevation) are formed as a single continuous helical groove, the roll can be rotated about its rolling axis and the tool translated laterally. Any of the groove shapes provided by insert 36 and laser beam 16 are such that when a strip of metal is reduced in thickness in passing between the work rolls of a rolling mill, which reduction occurs under massive, compressive forces, as discussed above, the metal of the strip extrudes into the grooves but is not retained in the grooves such that the roll remains clean and uncoated with the metal of the strip. This may be ensured through the use of a roll coating, such as chrome. In any case, the surface of the strip is not marred by debris clinging to the surface of the roll. After grooves 14 are formed in the surface of a roll by laser 12, the roll is polished to remove any deposition of roll material that may not have been cared for by the stream of air from nozzle 18. Fig. 3 of the micrographs shows a situation where material deposition 10a of the roll has not only not been removed but which forms jagged edges on and along the banks of the grooves in the roll. The jagged edges pick up or seize material of strip 20 and embed the same (20a) in the surface grooves. (The embedded material 20a shown in Fig. 3 is a 5182 aluminum alloy, the strip of the material having undergone a twenty percent reduction in thickness.) Once embedded, the strip material is virtually impossible to remove from the grooves. It is therefore imperative that any material deposition on the groove banks be removed from the roll before it is used. Such deposits can be removed by a light polishing operation that does not otherwise affect the roll topography. A suitable polishing procedure involves manually buffing the roll surface with a cloth and a fine diamond paste, though other procedures can be used to remove deposits. The life of the polished roll can be further extended by plating the roll with a coating of material such as chrome. Fig. 4 of the micrographs shows a sheet surface texture 44 that is seemingly oriented in one direction yet is actually quite random and literally littered with small micro cracks or fissures 46. These fissures generally extend transverse to the direction of rolling. They are the result of thick films of lubricant 47 locally entrapped and confined in random, narrow and discontinuous depressions 48 in a ground roll surface 10b, as depicted in exaggerated form in Fig. 5, i.e., Fig. 5 shows a ground roll surface greatly enlarged to depict random roughness. Between the depressions are narrow discontinuous peaks that engage and form elongated, discontinuous depressions 49 in the surface of sheet 44, as the sheet is reduced in thickness. The lubricant trapped in depressions 48 thereby becomes highly pressurized, as it cannot escape the depressions, and is forced against the sheet surface. The pressure is sufficient to open (crack) the surface of the sheet. This is the problem in Figs. 4 and 5, the sheet in the micrograph of Fig. 4 having undergone a reduction in thickness of 17%. Such a surface and texture is also shown diagrammatically and in cross section in Fig. 6 of the drawings. In Fig. 6, the sectional view is employed to show texture randomness in both a roll and sheet surface. Fig. 7 of the drawings shows the texture of a sheet of 5182 aluminum (magnified 200 times) that has been rolled with a work roll having its surface machined by electric discharge machining (EDM). Such a technique produces overlapping pits or craters in the roll surface. When an aluminum sheet is rolled with such a pitted surface, the sheet surface acquires debris (the dark areas in Fig. 7) in the form of aluminum oxide which significantly degrades sheet surface quality. The surface debris is generated by the random roughness of the roll which produces a sand paper effect, i.e., a fine particle debris occurs that is similar to that produced when one sands a wood surface with sand paper. Hence, the surfaces of the rolled product of Figs. 4, 5, 6 and 7 are dull, as incident light 28 striking the surfaces is diffused from the surfaces. The diffused light is indicated by numeral 50 in Fig. 6. The diffused light in Fig. 6 is in contrast to the highly directional specularly reflected light 30 in Fig. 9. The diagrammatic presentation of Fig. 9 represents the surface of sheet 20, as depicted by the micrograph of Fig. 8, said surface being substantially free of debris and fissures. Referring again to Figs. 1, 2, and 10, continuous grooves 14 or 40 in roll 10 are separated by substantially smooth, relatively broad areas 52 that extend about the roll surface, with the grooves, the width of the broad areas being on the order of five to 300 microns. The width of these areas, in any given case, is chosen in accordance with such rolling parameters as the material (alloy) being reduced in thickness, the composition of the lubricant employed and speed of the rolling process. Areas 52 provide broad smooth bearing surfaces that bear against strip 20 (Fig. 8) during the rolling process to form the broad, smooth and bright planar surfaces 26 on the surface of the strip. Areas 52 reduce the thickness of strip 20 under boundary lubrication conditions, i.e., any lubricant existing or entering between roll surfaces 52 and strip surfaces 26 is forced from the broad areas of 52 into grooves 14 or 40 provided in the roll such that virtually no thick film of lubricant is maintained between surfaces 52 and 26 during the rolling process. When the lubricant reaches the grooves it is freely channelled therealong as the rolls rotate against the strip. The lubricant is thus not confined in the manner described above in connection with the discontinuous depressions of ground rolls. Since the lubricant is not confined, the pressure of the lubricant does not grow and increase to cause cracking of the strip surface. In the broad areas of 52 and 26, no lubricant is available to open up the strip surface so that the strip exiting the mill is substantially free of transverse fissures. Neither do surfaces 26 contain random size valleys and crests, as the surface of roll 10 does not contain random valleys and crests. The surface of strip 20 is now comprised of a combination of broad, substantially smooth areas 26 of precisely chosen widths separated by ridges 22 of precise height, width, and configuration. Further, in the process of reducing the thickness of strip 20, the bearing areas 52 of roll 10 smear the surface of the strip engaging such bearing areas. Smearing is a process in which the force of the rolls bearing against the strip being rolled smooths out any remaining uneven profiles on the strip surface so that its specularly reflective capability is further enhanced. A further enhancement of reflectivity is effected by highly polishing the surface of roll 10 before it is machined by laser 12 or tool 35. This provides highly polished bearing areas 52 which transfer their polished characteristic to the rolled product in the thickness reduction process, and enhance the smearing or smoothing process. Roll 10 of the invention is thus provided with an engineered, predictable, non-random surface finish and texture made possible by pulsed laser beam 16 or cutting insert 36. Such an engineered roll surface provides an anisotropic, predictable, engineered strip having the desired uniformly bright surface. The texture of the roll is anisotropic, as it is provided with discrete grooves 14 or 40 spaced apart by bearing areas 52, with a pitch to groove ratio of 2.0 or greater.
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A method of reducing the thickness of metal material including the steps of passing the material to be reduced through work rolls of a rolling mill, rotating said rolls and maintaining a compressive force on the material by said rolls, characterized in that at least one of said rolls (10) has a polished finish and a rolling surface of smooth-bearing areas (52) spaced by at least one continuous minute groove (14) extending around the roll (10) by several revolutions in the general direction of rolling, said polished surface and the banks of said groove (10) being free of any material deposits, in that said polished finish and groove (10) have a coat of hard, dense material, and in that a lubricant is introduced against the rolling surfaces of said work rolls and forced into the minute groove (14) by said compressive force maintained against the material (20) between the rotating rolls whereby the thickness of the material between the rolls is substantially reduced under boundary lubrication conditions such that fissures are not created or enlarged in the surface of the material, and imparting the polish finish of said at least one roll (10) to the surface of the metal material contacting the polished finish of said roll. A method according to claim 1, characterized in that the groove (14) is formed in the roll surface by using a laser beam (16) to vaporize the material of the roll surface, in that a gaseous stream is directed adjacent the region of contact between the beam and surface to move the vapor ahead of the beam as the roll (10) and beam (16) are relatively moved, thereby preheating the roll surface in in area thereof ahead of the beam, said moving vapor minimizing deposition of roll material on the banks of the groove and on optics employed to focus the laser beam (16). A method according to claim 1, characterized in that the groove (40) is provided by a tool (35) having a predetermined profile and micron size cutting edge (38) in cross section. A method according to any of claims 1 to 3, characterized in that the width of the bearing areas (52) is in the range of five to 300 microns. A method according to any of claims 1 to 4, characterized in that the width of the groove (14, 40) is at least 2.5 and not more than twenty-five microns and the depth of said groove is in the range of 0.25 to five microns. A method according to claim 2, characterized in that the laser beam (16) is focused to inscribe a wedge shaped groove (14) in the roll surface. A method according to any of claims 1 to 6, characterized in that a plurality of discrete radial grooves extend around the roll (10) at spaced locations along the length thereof. A method according to any of claims 1 to 6, characterized in that a single groove extends helically around the roll (10). A roll (10) for a rolling mill suitable for carrying out the method according to claim 1, characterized in that said roll has a polished finish, in that at least one continuous groove (14) extends around the roll (10) by several revolutions in the general direction of rolling, in that both the polished surface and the banks of the groove (14) are free of material deposits and in that a coat of hard dense material covers said polished finish and groove. A roll according to claim 9, characterized in that a plurality of discrete radial grooves extend around the roll (10) at spaced locations along the length thereof. A roll according to claim 9, characterized in that a single groove extends helically around the roll (10).
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ALUMINUM CO OF AMERICA; ALUMINUM COMPANY OF AMERICA
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HECTOR LOUIS G; SHEU SIMON; HECTOR, LOUIS G.; SHEU, SIMON
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EP-0489968-B1
| 489,968 |
EP
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B1
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EN
| 19,961,106 | 1,992 | 20,100,220 |
new
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C07K14
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A61K39, G01N33
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G01N33, A61K39, C07K14, C07K16, C07K7
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K61K39:00, M07K203:00, C07K 14/18F4
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Synthetic antigens for the detection of antibodies to hepatitis C virus
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Peptide sequences having the amino acid sequences given in the Sequence Listing (Sequence ID No. 1 to 20) are provided which are capable of mimicking proteins encoded by HCV for use as reagents for screening of blood and blood products for prior exposure to HCV. The peptides are at least 5 amino acids long and can be used in various specific assays for the detection of antibodies to HCV, for the detection of HCV antigens, or as immunogens.
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The implementation of systematic testing for hepatitis B virus (HBV) has been instrumental in eliminating this virus from the blood supply. Nevertheless, a significant number of post-transfusion hepatitis (PTH) cases still occur. These cases are generally attributable to non-A, non-B hepatitis (NANBH) virus(es), the diagnosis of which is usually made by exclusion of other viral markers. The etiological agent responsible for a large proportion of these cases has recently been cloned (Choo, Q-L et al. Science (1988) 244:359-362) and a first-generation antibody test developed (Kuo, G. et al. Science (1989) 244:362-364). The agent has been identified as a positive-stranded RNA virus, and the sequence of its genome has been partially determined. Studies suggest that this virus, referred to subsequently as hepatitis C virus (HCV), may be related to flaviviruses and pestiviruses. A portion of the genome of an HCV isolated from a chimpanzee (HCVCDC/CHI) is disclosed in EPO 88310922.5. The coding sequences disclosed in this document do not include sequences originating from the 5'-end of the viral genome which code for putative structural proteins. Recently however, sequences derived from this region of the HCV genome have been published (Okamoto, H. et al., JapanJ.Exp.Med. 60:167-177, 1990.). The amino acid sequences encoded by the Japanese clone HC-J1 were combined with the HCVCDC/CHI sequences in a region where the two sequences overlap to generate the composite sequence depicted in Figure 1. Specifically, the two sequences were joined at glycine451. It should be emphasized that the numbering system used for the HCV amino acid sequence is not intended to be absolute since the existence of variant HCV strains harboring deletions or insertions is highly probable. Sequences corresponding to the 5' end of the HCV genome have also recently been disclosed in EPO 90302866.0. In order to detect potential carriers of HCV, it is necessary to have access to large amounts of viral proteins. In the case of HCV, there is currently no known method for culturing the virus, which precludes the use of virus-infected cultures as a source of viral antigens. The current first-generation antibody test makes use of a fusion protein containing a sequence of 363 amino acids encoded by the HCV genome. It was found that antibodies to this protein could be detected in 75 to 85% of chronic NANBH patients. In contrast, only approximately 15% of those patients who were in the acute phase of the disease, had antibodies which recognized this fusion protein (Kuo, G. et al. Science (1989) 244:362-364). The absence of suitable confirmatory tests, however, makes it difficult to verify these statistics. The seeming similarity between the HCV genome and that of flaviviruses makes it possible to predict the location of epitopes which are likely to be of diagnostic value. An analysis of the HCV genome reveals the presence of a continuous long open reading frame. Viral RNA is presumably translated into a long polyprotein which is subsequently cleaved by cellular and/or viral proteases. By analogy with, for example, Dengue virus, the viral structural proteins are presumed to be derived from the amino-terminal third of the viral polyprotein. At the present time, the precise sites at which the polyprotein is cleaved can only be surmised. Nevertheless, the structural proteins are likely to contain epitopes which would be useful for diagnostic purposes, both for the detection of antibodies as well as for raising antibodies which could subsequently be used for the detection of viral antigens. Similarly, domains of nonstructural proteins are also expected to contain epitopes of diagnostic value, even though these proteins are not found as structural components of virus particles. Brief Description of the DrawingsFigure 1shows the amino acid sequence of the composite HCVHC-J1/CDC/CHIFigure 2shows the antibody binding to individual peptides and various mixtures in an ELISA assay Description of the Specific EmbodimentsIt is known that RNA viruses frequently exhibit a high rate of spontaneous mutation and, as such, it is to be expected that no two HCV isolates will be completely identical, even when derived from the same individual. For the purpose of this disclosure, a virus is considered to be the same or equivalent to HCV if it exhibits a global homology of 60 percent or more with the HCVHC-J1/CDC/CHI composite sequence at the nucleic acid level and 70 percent at the amino acid level. Peptides are described which immunologically mimic proteins encoded by HCV. In order to accommodate strain-to-strain variations in sequence, conservative as well as non-conservative amino acid substitutions may be made. These will generally account for less than 35 percent of a specific sequence. It may be desirable in cases where a peptide corresponds to a region in the HCV polypeptide which is highly polymorphic, to vary one or more of the amino acids so as to better mimic the different epitopes of different viral strains. A peptide composition according to the present invention comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived. For BE, CH, LI, NL, AT, ES, GR, SE, these peptides have to be different from: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-IIe-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg. For LU, these peptides have to be different from: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln,wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-IIe-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln. For DE, FR, GB, IT, these peptides have to be different from: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg, (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly, (5) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, a peptide containing the peptide represented by the sequence and a peptide consisting of a part of the peptide represented by the sequence, (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-lle (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-IIe-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg. The present invention further relates to a peptide composition as defined above further characterized in that it also comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749, 2263-2282, 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above, and said fragments maintaining substantially all of the sensitivity of peptide sequences from which they are derived. The peptides of interest will include at least six, sometimes eight, sometimes twelve amino acids included within the sequence encoded by the HCV genome. In each instance, the peptide will preferably be as small as possible while still maintaining substantially all of the sensitivity of the larger peptide. It may also be desirable in certain instances to join two or more peptides together in one peptide structure. Substitutions which are considered conservative are those in which the chemical nature of the substitute is similar to that of the original amino acid. Combinations of amino acids which could be considered conservative are Gly, Ala; Asp, Glu; Asn, Gln; Val, Ile, Leu; Ser, Thr; Lys, Arg; and Phe, Tyr. The nature of the attachment of the peptide to a solid phase or carrier need not be covalent. Natural amino acids such as cysteine, lysine, tyrosine, glutamic acid, or aspartic acid may be added to either the amino- or carboxyl terminus to provide functional groups for coupling to a solid phase or a carrier. However, other chemical groups such as, for example, biotin and thioglycolic acid, may be added to the termini which will endow the peptides with desired chemical or physical properties. The termini of the peptides may also be modified, for example, by N-terminal acetylation or terminal carboxy-amidation. Of particular interest is the use of the mercapto-group of cysteines or thioglycolic acids used for acylating terminal amino groups for cyclizing the peptides or coupling two peptides together. The cyclization or coupling may occur via a single bond or may be accomplished using thiol-specific reagents to form a molecular bridge. The peptides may be coupled to a soluble carrier for the purpose of either raising antibodies or facilitating the adsorption of the peptides to a solid phase. The nature of the carrier should be such that it has a molecular weight greater than 5000 and should not be recognized by antibodies in human serum. Generally, the carrier will be a protein. Proteins which are frequently used as carriers are keyhole limpet hemocyanin, bovine gamma globulin, bovine serum albumin, and poly-L-lysine. There are many well described techniques for coupling peptides to carriers. The linkage may occur at the N-terminus, C-terminus or at an internal site in the peptide. The peptide may also be derivatized for coupling. Detailed descriptions of a wide variety of coupling procedures are given, for example, in Van Regenmortel, M.H.V., Briand, J.P., Muller, S., and Plaué, S., Laboratory Techniques in Biochemistry and Molecular Biology, Vol. 19, Synthetic Polypeptides as Antigens, Elsevier Press, Amsterdam, New York, Oxford, 1988. The peptides may also be synthesized directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides. The number of lysines comprising the core is preferably 3 or 7. Additionally, a cysteine may be included near or at the C-terminus of the complex to facilitate the formation of homo- or heterodimers. The use of this technique has been amply illustrated for hepatitis B antigens (Tam, J.P., and Lu, Y-A., Proc. Natl. Acad. Sci. USA (1989) 86:9084-9088) as well as for a variety of other antigens (see Tam, J.P., Multiple Antigen Peptide System: A Novel Design for Synthetic Peptide Vaccine and Immunoassay, in Synthetic Peptides, Approaches to Biological Problems, Tam, J.P., and Kaiser, E.T., ed. Alan R. Liss Inc., New York, 1989). Depending on their intended use, the peptides may be either labeled or unlabeled. Labels which may be employed may be of any type, such as enzymatic, chemical, fluorescent, luminescent, or radioactive. In addition, the peptides may be modified for binding to surfaces or solid phases, such as, for example, microtiter plates, nylon membranes, glass or plastic beads, and chromatographic supports such as cellulose, silica, or agarose. The methods by which peptides can be attached or bound to solid support or surface are well known to those versed in the art. Of particular interest is the use of mixtures of peptides for the detection of antibodies specific for hepatitis C virus. Mixtures of peptides which are considered particularly advantageous are: A. II (SEQ ID NO 2), III (SEQ ID NO 4), V (SEQ ID NO 6), IX (SEQ ID NO 10), and XVIII (SEQ ID NO 19), B. I (SEQ ID NO 1), II (SEQ ID NO 2), V (SEQ ID NO 6), IX (SEQ ID NO 10), XI (SEQ ID NO 12), XVI (SEQ ID NO 17), and XVIII (SEQ ID NO 19), C. II (SEQ ID NO 2), III (SEQ ID NO 4), IV (SEQ ID NO 5), V (SEQ ID NO 6), VIII (SEQ ID NO 9), XI (SEQ ID NO 12), XVI (SEQ ID NO 17), and XVIII (SEQ ID NO 19), D. II (SEQ ID NO 2), IX (SEQ ID NO 10), and XVIII (SEQ ID NO 19), E. II (SEQ ID NO 2), III ( SEQ ID NO 4), IV (SEQ ID NO 5), and V (SEQ ID NO 6). Antibodies which recognize the peptides can be detected in a variety of ways. A preferred method of detection is the enzyme-linked immunosorbant assay (ELISA) in which a peptide or mixture of peptides is bound to a solid support. In most cases, this will be a microtiter plate but may in principle be any sort of insoluble solid phase. A suitable dilution or dilutions of serum or other body fluid to be tested is brought into contact with the solid phase to which the peptide is bound. The incubation is carried out for a time necessary to allow the binding reaction to occur. Subsequently, unbound components are removed by washing the solid phase. The detection of immune complexes is achieved using antibodies which specifically bind to human immunoglobulins, and which have been labeled with an enzyme, preferably but not limited to either horseradish peroxidase, alkaline phosphatase, or beta-galactosidase, which is capable of converting a colorless or nearly colorless substrate or co-substrate into a highly colored product or a product capable of forming a colored complex with a chromogen. Alternatively, the detection system may employ an enzyme which, in the presence of the proper substrate(s), emits light. The amount of product formed is detected either visually, spectrophotometrically, electrochemically, or luminometrically, and is compared to a similarly treated control. The detection system may also employ radioactively labeled antibodies, in which case the amount of immune complex is quantified by scintillation counting or gamma counting. Other detection systems which may be used include those based on the use of protein A derived from Staphylococcusaureus Cowan strain I, protein G from group C Staphylococcus sp. (strain 26RP66), or systems which make use of the high affinity biotin-avidin or streptavidin binding reaction. Antibodies raised to carrier-bound peptides can also be used in conjunction with labeled peptides for the detection of antibodies present in serum or other body fluids by competition assay. In this case, antibodies raised to carrier-bound peptides are attached to a solid support which may be, for example, a plastic bead or a plastic tube. Labeled peptide is then mixed with suitable dilutions of the fluid to be tested and this mixture is subsequently brought into contact with the antibody bound to the solid support. After a suitable incubation period, the solid support is washed and the amount of labeled peptide is quantified. A reduction in the amount of label bound to the solid support is indicative of the presence of antibodies in the original sample. By the same token, the peptide may also be bound to the solid support. Labeled antibody may then be allowed to compete with antibody present in the sample under conditions in which the amount of peptide is limiting. As in the previous example, a reduction in the measured signal is indicative of the presence of antibodies in the sample tested. Another preferred method of antibody detection is the homogeneous immunoassay. There are many possible variations in the design of such assays. By way of example, numerous possible configurations for homogeneous enzyme immunoassays and methods by which they may be performed are given in Tijssen, P., Practice and Theory of Enzyme Immunoassays, Elsevier Press, Amersham, Oxford, New York, 1985. Detection systems which may be employed include those based on enzyme channeling, bioluminescence, allosteric activation and allosteric inhibition. Methods employing liposome-entrapped enzymes or coenzymes may also be used (see Pinnaduwage, P. and Huang, L., Clin. Chem. (1988) 34/2: 268-272, and Ullman, E.F. et al., Clin. Chem. (1987) 33/9: 1579-1584 for examples). The synthesis of the peptides can be achieved in solution or on a solid support. Synthesis protocols generally employ the use t-butyloxycarbonyl- or 9-fluorenylmethoxycarbonyl-protected activated amino acids. The procedures for carrying out the syntheses, the types of side-chain protection, and the cleavage methods are amply described in, for example, Stewart and Young, Solid Phase Peptide Synthesis, 2nd Edition, Pierce Chemical Company, 1984; and Atherton and Sheppard, Solid Phase Peptide Synthesis, IRL Press, 1989. The invention also relates to a kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising at least the following components: a peptide composition according to the invention, a means for detecting an immunological complex formed between said peptides and said antibodies. ExperimentalI. Peptide SynthesisAll of the peptides described were synthesized on Pepsyn K polyamide-Kieselguhr resin (Milligen, Novato, California) which had been functionalized with ethylenediamine and onto which the acid-labile linker 4-(alpha-Fmoc-amino-2',4'-dimethoxybenzyl) phenoxyacetic acid had been coupled (Rink, Tetrahedron Lett. (1987) 28:3787). t-Butyl-based side-chain protection and Fmoc alpha-amino-protection was used. The guanidino-group of arginine was protected by the 2,2,5,7,8-pentamethylchroman-6-sulfonyl moiety. The imidazole group of histidine was protected by either t-Boc or trityl and the sulfhydryl group of cysteine was protected by a trityl group. Couplings were carried out using performed O-pentafluorophenyl esters except in the case of arginine where diisopropylcarbodiimidemediated hydroxybenzotriazole ester formation was employed. Except for peptide I, all peptides were N-acetylated using acetic anhydride. All syntheses were carried out on a Milligen 9050 PepSynthesizer (Novato, California) using continuous flow procedures. Following cleavage with trifluoroacetic acid in the presence of scavengers and extraction with diethylether, all peptides were analyzed by C18 -reverse phase chromatography. II. Detection of Antibodies to Hepatitis C VirusA. Use of peptides bound to a nylon membrane.Peptides were dissolved in a suitable buffer to make a concentrated stock solution which was then further diluted in phosphate-buffered saline (PBS) or sodium carbonate buffer, pH 9.6 to make working solutions. The peptides were applied as lines on a nylon membrane (Pall, Portsmouth, United Kingdom), after which the membrane was treated with casein to block unoccupied binding sites. The membrane was subsequently cut into strips perpendicular to the direction of the peptide lines. Each strip was then incubated with a serum sample diluted 1 to 100, obtained from an HCV-infected individual. Antibody binding was detected by incubating the strips with goat anti-human immunoglobulin antibodies conjugated to the enzyme alkaline phosphatase. After removing unbound conjugate by washing, a substrate solution containing 5-bromo-4-chloro-3-indolylphosphate and nitro blue tetrazolium was added. Positive reactions are visible as colored lines corresponding to the positions of the peptides which are specifically recognized. The reaction patterns of thirty-six different sera are tabulated in Table 1. The results shown in Table 1 are further summarized in Table 2. B. Use of peptides in an enzyme-linked immunosorbent assay (ELISA).Peptide stock solutions were diluted in sodium carbonate buffer, pH 9.6 and used to coat microtiter plates at a peptide concentration of 2 micrograms per milliliter. A mixture consisting of peptides II, III, V, IX, and XVIII was also used to coat plates. Following coating, the plates were blocked with casein. Fifteen HCV-antibody-positive sera and control sera from seven uninfected blood donors were diluted 1 to 20 and incubated in wells of the peptide-coated plates. Antibody binding was detected by incubating the plates with goat anti-human immunoglobulin antibodies conjugated to the enzyme horseradish peroxidase. Following removal of unbound conjugate by washing, a solution containing H2O2 and 3,3',5,5'-tetramethylbenzidine was added. Reactions were stopped after a suitable interval by addition of sulfuric acid. Positive reactions gave rise to a yellow color which was quantified using a conventional microtiter plate reader. The results of these determinations are tabulated in Table 3. To correct for any aspecific binding which could be attributable to the physical or chemical properties of the peptides themselves, a cut-off value was determined for each peptide individually. This cut-off absorbance value was calculated as the average optical density of the negative samples plus 0.200. Samples giving absorbance values higher than the cut-off values are considered positive. The results for the fifteen positive serum samples are further summarized in Table 4. While it is evident that some of the peptides are recognized by a large percentage of sera from HCV-infected individuals, it is also clear that no single peptide is recognized by all sera. In contrast, the peptide mixture was recognized by all fifteen sera and, for six of the fifteen sera, the optical densities obtained were equal to or higher than those obtained for any of the peptides individually. These results serve to illustrate the advantages of using mixtures of peptides for the detection of anti-HCV antibodies. C. Binding of antibodies in sera from HCV-infected patients to various individual peptides and peptide mixtures in an ELISA.Five peptides were used individually and in seven different combinations to coat microtiter plates. The plates were subsequently incubated with dilutions of fifteen HCV antibody-positive sera in order to evaluate the relative merits of using mixtures as compared to individual peptides for antibody detection. The mixtures used and the results obtained are shown in Figure 2. In general, the mixtures functioned better than individual peptides. This was particularly evident for mixture 12 (peptides I, III, V, IX, and XVIII) which was recognized by all twelve of the sera tested. These results underscore the advantages of using mixtures of peptides in diagnostic tests for the detection of antibodies to HCV. D. Use of a mixture of peptides in an ELISA assay for the detection of anti-HCV antibodies.A mixture of peptides II, III, V, IX, and XVIII was prepared and used to coat microtiter plates according to the same procedure used to test the individual peptides. A total of forty-nine sera were tested from patients with clinically diagnosed but undifferentiated chronic non A non B hepatitis as well as forty-nine sera from healthy blood donors. Detection of antibody binding was accomplished using goat anti-human immunoglobulin antibodies conjugated to horseradish peroxidase. The resulting optical density values are given in Table 5. These results indicate that the mixture of peptides is not recognized by antibodies in sera from healthy donors (0/49 reactives) but is recognized by a large proportion (41/49, or 84%) of the sera from patients with chronic NANBH. These results demonstrate that the peptides described can be used effectively as mixtures for the diagnosis of HCV infection. E. Detection of anti-HCV antibodies in sera from patients with acute NANB infection using individual peptides bound to nylon membranes and a mixture of peptides in an ELISA assay, and comparison with a commercially available kit.Peptides were applied to nylon membranes or mixed and used to coat microtiter plates as previously described. The peptide mixture consisted of peptides II, III, V, IX, and XVIII. Sera obtained from twenty-nine patients with acute non-A, non-B hepatitis were then tested for the presence of antibodies to hepatitis C virus. These same sera were also evaluated using a commercially available kit (Ortho, Emeryville, CA, USA). The results of this comparative study are given in Table 6. In order to be able to compare the peptide-based ELISA with the commercially available kit, the results for both tests are also expressed as signal to noise ratios (S/N) which were calculated by dividing the measured optical density obtained for each sample by the cut-off value. A signal-to-noise ratio greater or equal to 1.0 is taken to represent a positive reaction. For the commercially available kit, the cut-off value was calculated according to the manufacturer's instructions. The cut-off value for the peptide-based ELISA was calculated as the average optical density of five negative samples plus 0.200. The scale used to evaluate antibody recognition of nylon-bound peptides was the same as that given in Table 1. Of the twenty-nine samples tested, twenty-five (86%) were positive in the peptide-based ELISA and recognized one or more nylon-bound peptides. In contrast, only fourteen of the twenty-nine sera scored positive in the commercially available ELISA. These results serve to illustrate the advantages of using peptide mixtures for the detection of anti-HIV antibodies as well as the need to include in the mixtures peptides which contain amino acid sequences derived from different regions of the HCV polyprotein. Summary of antibody binding to nylon-bound HCV peptides by sera from infected patients. Peptide No. reactive sera % reactive sera I13/3537 II22/3563 III27/3577 IV24/3569 V14/3540 VI11/3531 VII11/3531 VIII19/3653 IX9/3625 X17/3647 XI15/3642 XII1/363 XIII13/3636 XIV7/3619 XV9/3625 XVI20/3656 XVII14/3639 XVIII14/3639 XIX8/3622 Summary of antibody-binding to individual peptides in an ELISA assay. Peptide No. reactive sera % reactive sera I1387 II1387 III1493 IV1067 V1067 VI747 VII853 VIII1387 IX1280 X1387 XI1387 XII17 XIII747 XIV853 XV213 XVI533 XVII427 XVIII1067 XIX640 Use of a peptide mixture for the detection of antibodies to HCV in sera from chronic NANBH patients and comparison to sera from healthy blood donors. Chronic NANB Sera Control Sera Serum nr. Optical Density Serum nr. Optical Density 1010.04110.049 1021.38720.047 1031.57830.049 1041.80440.046 1051.39350.049 1071.60460.045 1081.14870.043 1091.71480.053 1101.69290.049 1120.919100.047 1131.454110.060 1140.936120.044 1150.041130.049 1161.636140.051 1181.242150.056 1191.568160.050 1201.290170.049 1211.541180.055 1221.422190.054 1231.493200.058 1241.666210.050 1251.644220.044 1261.409230.043 1271.625240.045 1281.061250.046 1291.553260.049 1301.709270.050 1310.041280.047 1320.044290.050 1331.648300.053 1340.043310.051 1351.268320.053 1361.480330.055 1380.628340.064 1390.042350.063 1400.040360.057 1410.039380.048 1421.659390.045 1431.457400.046 1440.722410.046 1451.256420.051 1460.373430.057 1471.732440.050 1481.089450.050 1491.606460.045 1501.725470.041 1511.449480.064 1541.639490.040 1551.775500.036
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Claims for the following Contracting States : BE, CH, LI, NL, AT, SE, DKA peptide composition comprising at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived, and provided that said peptides are different from the following list of peptides: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-Ile-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg A peptide composition according to claim 1, further characterized in that it also comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749, 2263-2282, 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above, and said fragments maintaining substantially all of the sensitivity of peptide sequences from which they are derived. A peptide composition according to any of claim 1 or 2, further characterized in that it contains at least one of the following mixtures of peptides as defined in any of claims 1 or 2: (a) peptides II, III, V, IX, and XVIII, (b) peptides I, II, V, IX, XI, XVI, and XVIII, (c) peptides II, III, IV, V, VIII, XI, XVI, and XVIII, (d) peptides II, IX, and XVIII, (e) peptides II, III, IV, and V. A peptide composition according to any of claims 1 to 3, further characterized in that said peptides are coupled N-terminally, C-terminally or internally to a carrier molecule for the purpose of raising antibodies or facilitating the adsorption of said peptides to a solid phase. A peptide composition according to any of claims 1 to 4, further characterized in that said peptides contain a detectable label. Use of a peptide composition according to any of claims 1 to 5, for the incorporation into an immunoassay for detecting the presence of antibodies to Hepatitis C virus present in a body fluid. A method for the in vitro detection of antibodies to hepatitis C virus present in a body fluid such as serum or plasma, comprising at least the steps of: (a) contacting body fluid of a person to be diagnosed with a peptide composition according to any of claims 1 to 5, and, (b) detecting the immunological complex formed between said antibodies and the peptide(s) used. A kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising at least the following components: a peptide composition according to any of claims 1 to 5, a means for detecting an immunological complex formed between said peptides and said antibodies. A method according to claim 7, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to claim 8, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to any of claims 8 or 10, further characterized in that said peptides, seperately or in combination, are used to coat the wells of microtiter plates. Use of a peptide composition according to any of claims 1 to 5, for incorporation into a vaccine composition against HCV. Peptide composition according to any one of claims 1 to 5, for raising antibodies against HCV. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by cyclizing any of the peptides of claims 1 to 2, or by coupling together two peptides of claims 1 to 2. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by synthetizing the peptides of claims 1 or 2 directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides. Claims for the following Contracting States : DE, FR, GB, ITA peptide composition comprising at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions; or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived, and provided that said peptides are different from the following list of peptides: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg, (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly, (5) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, a peptide containing the peptide represented by the sequence and a peptide consisting of a part of the peptide represented by the sequence, (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-IIe-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg A peptide composition according to claim 1, further characterized in that it also comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups and provided that when Y or Z-X are amino acid(s), they are different from any naturally occurring HCV flanking regions; or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749, 2263-2282, 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived. A peptide composition according to any of claims 1 or 2, further characterized in that it contains at least one of the following mixtures of peptides as defined in any of claims 1 or 2: (a) peptides II, III, V, IX, and XVIII, (b) peptides I, II, V, IX, XI, XVI, and XVIII, (c) peptides II, III, IV, V, VIII, XI, XVI, and XVIII, (d) peptides II, IX, and XVIII, (e) peptides II, III, IV, and V. A peptide composition according to any of claims 1 to 3, further characterized in that said peptides are coupled N-terminally, C-terminally or internally to a carrier molecule for the purpose of raising antibodies or facilitating the adsorption of said peptides to a solid phase. A peptide composition according to any of claims 1 to 4, further characterized in that said peptides contain a detectable label. Use of a peptide composition according to any of claims 1 to 5, for the incorporation into an immunoassay for detecting the presence of antibodies to Hepatitis C virus present in a body fluid. A method for the in vitro detection of antibodies to hepatitis C virus present in a body fluid such as serum or plasma, comprising at least the steps of: (a) contacting body fluid of a person to be diagnosed with a peptide composition according to any of claims 1 to 5, and, (b) detecting the immunological complex formed between said antibodies and the peptide(s) used. A kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising at least the following components: a peptide composition according to any of claims 1 to 5, a means for detecting an immunological complex formed between said peptides and said antibodies. A method according to claim 7, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to claim 8, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to any of claims 8 or 10, further characterized in that said peptides, seperately or in combination, are used to coat the wells of microtiter plates. Use of a peptide composition according to any of claims 1 to 5, including peptide (5) such as defined in claim 1, for incorporation into a vaccine composition against HCV. Peptide composition according to any one of claims 1 to 5, for raising antibodies against HCV. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by cyclizing any of the peptides of claims 1 to 2, or by coupling together two peptides of claims 1 to 2. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by synthetizing the peptides of claims 1 or 2 directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides. Claims for the following Contracting States : ES, GRA peptide composition comprising at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived, and provided that said peptides are different from the following list of peptides: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-Ile-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg A peptide composition according to claim 1, further characterized in that it also comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749, 2263-2282, 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above, and said fragments maintaining substantially all of the sensitivity of peptide sequences from which they are derived. A peptide composition according to any of claim 1 or 2, further characterized in that it contains at least one of the following mixtures of peptides as defined in any of claims 1 or 2: (a) peptides II, III, V, IX, and XVIII, (b) peptides I, II, V, IX, XI, XVI, and XVIII, (c) peptides II, III, IV, V, VIII, XI, XVI, and XVIII, (d) peptides II, IX, and XVIII, (e) peptides II, III, IV, and V. A peptide composition according to any of claims 1 to 3, further characterized in that said peptides are coupled N-terminally, C-terminally or internally to a carrier molecule for the purpose of raising antibodies or facilitating the adsorption of said peptides to a solid phase. A peptide composition according to any of claims 1 to 4, further characterized in that said peptides contain a detectable label. Use of a peptide composition according to any of claims 1 to 5, for the incorporation into an immunoassay for detecting the presence of antibodies to Hepatitis C virus present in a body fluid. A method for the in vitro detection of antibodies to hepatitis C virus present in a body fluid such as serum or plasma, comprising at least the steps of: (a) contacting body fluid of a person to be diagnosed with a peptide composition according to any of claims 1 to 5, and, (b) detecting the immunological complex formed between said antibodies and the peptide(s) used. A kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising at least the following components: a peptide composition according to any of claims 1 to 5, a means for detecting an immunological complex formed between said peptides and said antibodies. A method according to claim 7, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to claim 8, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to any of claims 8 or 10, further characterized in that said peptides, seperately or in combination, are used to coat the wells of microtiter plates. Use of a peptide composition according to any of claims 1 to 5, for incorporation into a vaccine composition against HCV. Peptide composition according to any one of claims 1 to 5, for raising antibodies against HCV. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by cyclizing any of the peptides of claims 1 to 2, or by coupling together two peptides of claims 1 to 2. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by synthetizing the peptides of claims 1 or 2 directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides. Process for preparing a peptide composition comprising at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived, and provided that said peptides are different from the following list of peptides: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-IIe-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln (12) Gln-Arg-Lys-Thr-Lys-Arg with said peptides being synthesized in solution or on a solid support employing t-butyloxycarbonyl- or 9-fluorenylmethoxy-carbonyl-protected activated amino acids as described in, for example, Stewart and Young, Solid Phase Peptide Synthesis, 2nd Edition, Pierce Chemical Company, 1984; and Atherton and Sheppard, Solid Phase Peptide Synthesis, IRL Press, 1989, and with said peptides being mixed in case different peptides are comprised in said composition. Process according to claim 16, for preparing a peptide composition comprising at least one peptide according to claim 16 and at least one peptide selected from : (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749, 2263-2282, 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above, and said fragments maintaining substantially all of the sensitivity of peptide sequences from which they are derived. Process according to any one of claims 16 or 17 for preparing at least one of the following mixtures of peptides as defined in claim 16 or 17 : (a) peptides II, III, V, IX, and XVIII, (b) peptides I, II, V, IX, XI, XVI, and XVIII, (c) peptides II, III, IV, V, VIII, XI, XVI, and XVIII, (d) peptides II, IX, and XVIII, (e) peptides II, III, IV, and V. Process according to any one of claims 16 to 18, further characterized in that said peptides are coupled N-terminally, C-terminally or internally to a carrier molecule for the purpose of raising antibodies or facilitating the adsorption of said peptides to a solid phase and with said coupling step being carried out as described in, for example, Van Regenmortel et al., 1988, Laboratory techniques in biochemistry and molecular biology, vol. 19, Synthetic Polypeptides as Antigens, Elsevier Press, Amsterdam, New York, Oxford. Process according to any of claims 16 to 19, characterized in that said peptides contain a detectable label added to said peptide. Process for the preparation of a kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising gathering at least the following components: a peptide composition according to any of claims 1 to 5, a means for detecting an immunological complex formed between said peptides and said antibodies. Process for the preparation of a kit according to claim 21, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. Process for the preparation of a kit according to claim 21 or 22, further characterized in that said peptides, seperately or in combination, are used to coat the wells of microtiter plates. Process for the preparation of a peptide composition according to any one of claims 16 to 20, for incorporation into a vaccine composition against HCV. Process for the preparation of a peptide composition according to any one of claims 16 to 20, for raising antibodies against HCV. Process for the preparation of a peptide composition according to any one of claims 16 to 20, wherein said peptides are such as obtained by cyclizing any of the peptides of claims 1 to 2, or by coupling together two peptides of claims 1 to 2. Process for the preparation of a peptide composition according to any one of claims 16 to 20, wherein said peptides are such as obtained by synthetizing the peptides of claims 1 or 2 directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides. Claims for the following Contracting State : LUA peptide composition comprising at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (I) to (VII), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (I) to (VII) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (I) to (VII) having at least 6 amino acids of any of the peptide sequences 1-20, 7-26, 8-18, 13-32, 37-56, 49-68, 61-80 and 73-92 as defined above; and said fragments maintaining substantially all of the sensitivity of said peptide sequences from which they are derived, and provided that said peptides are different from the following list of peptides: (1) Met-Ser-Thr-Asn-Pro-Lys-Pro-Gln-X1-Lys, wherein X1 represents Arg (2) Pro-Lys-Pro-Gln-X1-Lys-X2-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln, wherein X1 represents Arg, and X2 represents Thr, (3) Gln-Asp-Val-Lys-Phe-Pro, (4) Gly-Tyr-Pro-Trp-Pro-Leu-Tyr-Gly-Asn-Glu-Gly. (6) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg (7) Arg-Arg-Gly-Pro-Arg-Leu-Gly-Val-Arg-Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (8) Ala-Thr-Arg-Lys-Thr-Ser-Glu-Arg-Ser (9) Gln-Pro-Arg-Gly-Arg-Arg-Gln-Pro-Ile (10) Pro-Lys-Val-Arg-Arg-Pro-Glu-Gly-Arg (11) Met-Ser-Thr-Ile-Pro-Lys-Pro-Gln-Arg-Lys-Thr-Lys-Arg-Asn-Thr-Asn-Arg-Arg-Pro-Gln A peptide composition according to claim 1, further characterized in that it also comprises at least one peptide selected from: (a) the group of amino acid sequences consisting of: wherein Y is H or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid, Y can be modified by for instance N-terminal acetylation; Z is a bond or a linker arm by which the peptide can be attached to a carrier or solid phase comprising at least one amino acid and as many as 60 amino acids, most frequently 1 to 10 amino acids, such as cysteine, lysine, tyrosine, glutamic acid or aspartic acid, or chemical groups such as biotin or thioglycolic acid; and X is NH2, OH or a linkage involving either of these two groups; and provided that when Y or Z-X are (an) amino acid(s), they are different from any naturally occurring HCV flanking regions, or, (b) the variants of each of the above peptides (VIII) to (XIX), with said variants presenting conservative as well as non-conservative amino acid substitutions accommodating for less than 35 % strain-to-strain variation in HCV sequences with respect to each of the amino acid sequences (VIII) to (XIX) provided that said variant peptides are capable of providing for immunological competition with at least one strain of HCV; or, (c) fragments of peptides (VIII) to (XIX) having at least 6 amino acids of any of the peptide sequences 1688-1707, 1694-1713, 1706-1725, 1712-1731, 1718-1737, 1724-1743, 1730-1749. 2263-2282. 2275-2294, 2287-2306, 2299-2318 and 2311-2330, as defined above, and said fragments maintaining substantially all of the sensitivity of peptide sequences from which they are derived. A peptide composition according to any of claim 1 or 2, further characterized in that it contains at least one of the following mixtures of peptides as defined in any of claims 1 or 2: (a) peptides II, III, V, IX, and XVIII, (b) peptides I, II, V, IX, XI, XVI, and XVIII, (c) peptides II, III, IV, V, VIII, XI, XVI, and XVIII, (d) peptides II, IX, and XVIII, (e) peptides II, III, IV, and V. A peptide composition according to any of claims 1 to 3, further characterized in that said peptides are coupled N-terminally, C-terminally or internally to a carrier molecule for the purpose of raising antibodies or facilitating the adsorption of said peptides to a solid phase. A peptide composition according to any of claims 1 to 4, further characterized in that said peptides contain a detectable label. Use of a peptide composition according to any of claims 1 to 5, for the incorporation into an immunoassay for detecting the presence of antibodies to Hepatitis C virus present in a body fluid. A method for the in vitro detection of antibodies to hepatitis C virus present in a body fluid such as serum or plasma, comprising at least the steps of: (a) contacting body fluid of a person to be diagnosed with a peptide composition according to any of claims 1 to 5, and, (b) detecting the immunological complex formed between said antibodies and the peptide(s) used. A kit for the detection of anti-hepatitis C virus antibodies in a body fluid, comprising at least the following components: a peptide composition according to any of claims 1 to 5, a means for detecting an immunological complex formed between said peptides and said antibodies. A method according to claim 7, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to claim 8, further characterized in that said peptides are applied as lines on a nylon membrane, and with said nylon membrane being preferably cut into strips perpendicular to the direction of the peptide lines, thus allowing each strip to be incubated with an appropriately diluted serum sample from an individual. A kit according to any of claims 8 or 10, further characterized in that said peptides, seperately or in combination, are used to coat the wells of microtiter plates. Use of a peptide composition according to any of claims 1 to 5, for incorporation into a vaccine composition against HCV. Peptide composition according to any one of claims 1 to 5, for raising antibodies against HCV. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by cyclizing any of the peptides of claims 1 to 2, or by coupling together two peptides of claims 1 to 2. Peptide composition according to any one of claims 1 to 5, wherein said peptides are such as obtained by synthetizing the peptides of claims 1 or 2 directly on an oligo-lysine core in which both the alpha as well as the epsilon-amino groups of lysines are used as growth points for the peptides.
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INNOGENETICS NV; INNOGENETICS N.V.
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DELEYS ROBERT J; MAERTENS GEERT; POLLET DIRK; VAN HEUVERSWYN HUGO; DELEYS, ROBERT J.; MAERTENS, GEERT; POLLET, DIRK; VAN HEUVERSWYN, HUGO
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EP-0489974-B1
| 489,974 |
EP
|
B1
|
EN
| 19,950,517 | 1,992 | 20,100,220 |
new
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C10G25
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C10G29
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C10G29, C10G25
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C10G 25/00B, C10G 29/16
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Process for reducing the amount of metal contaminants in a hydrocarbon oil
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Process for reducing the amount of metal(s)-containing solid contaminants present in a hydrocarbon oil containing such contaminants, which process comprises contacting the hydrocarbon oil with porous solid material having a pore volume of at least 0.05 ml/g in pores having a diameter of at least 15 microns, which process is carried out without adding hydrogen.
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The present invention relates to a process for reducing the amount of metal(s)-containing solid contaminants present in a hydrocarbon oil containing such contaminants. It is well known that various metallic elements are found in hydrocarbon oils. These metals, particularly iron, nickel and vanadium, are harmful when included in feedstocks used for further refining operations in that they limit the life of catalyst used in such further refining operations. Such metals tend to deposit on the outer surface of the catalyst and in this way cause plugging of the catalyst bed. In particular the interstitial voids become blocked. This limits catalyst life since unacceptable pressure drops develop. Additionally, the deposits deactivate (poison) the catalyst requiring premature shutdown of the reactor and replacement of the catalyst. For the removal of metals like nickel and vanadium, hydrogen may be present, preferably together with a catalytically active metal. Surprisingly, it has now been found that the metal content of some other metals, such as certain metals from Group 1a, 2a, 3a, 4a, 6b and/or 8 of the Periodic Table of the Elements such as given in the CRC Handbook of Chemistry and Physics, 63rd edition, e.g. sodium, calcium, iron and/or molybdenum, can be brought down to an acceptable level by removing solids containing such contaminating metals. Such process can be carried out without adding hydrogen to the process and at ambient temperature and atmospheric pressure. Solid contaminants having a relatively large diameter can be removed in a conventional desalting step. However, contaminants having a smaller diameter must be removed in another way. It has now been found that such metal(s)-containing solid contaminants can be removed without adding hydrogen by the use of certain porous solid material having a substantial pore volume in pores having a diameter which is larger than the diameter of solid contaminants generally present in hydrocarbon oils. It is thought that thus metal containing solid contaminants are taken up inside the porous material by a combination of convection and diffusion such that the contaminants are removed from the hydrocarbon oil while the interstitial voids remain substantially open. Documents EP-A-0 175 799 and US-A-4 414 098 describe the upgrading of hydrocarbon oil feed by reduction of all heavy metals by contacting the feed under sorbing conditions with a high surface area, high pore volume sorbent material. Therefore, the present invention relates to a process for reducing the amount of metal(s)-containing solid contaminants present in a hydrocarbon oil containing such contaminants, which process comprises contacting the hydrocarbon oil with porous solid material having a pore volume of at least 0.05 ml/g in pores having a diameter of at least 15 microns, which process is carried out without adding hydrogen. The pore diameter in which a substantial amount of pore volume is preferred to be present depends on the diameter of the solid contaminants which are to be removed. Generally a pore volume of at least 0.05 ml/g in pores having a diameter of at least 15 microns is suitable. Preferably, a substantial pore volume, e.g. 0.03 ml/g, is present in pores having a diameter of at least 100 microns. Very suitable porous material to be used has a pore volume of at least 0.02 ml/g in pores having a diameter of at least 200 micons. The pore size distribution and pore volume of the material employed can be readily measured by the mercury intrusion method. The shape of the material is not critical and may take the form of spheres, hollow tubes, wheels, trilobes, quadrulobes, etc. Preferably, the diameter of the porous solid material particles is between 0.50 and 60 mm, more preferably between 1 and 40 mm. The surface area of the porous solid material is not critical. However, due to the requirements on the pore diameter and pore volume, the porous material to be employed in the process according to the present invention will generally have a surface area of less than 2 m²/gram. Porous solid material to be used comprises e.g. silica, alumina and silica/alumina. Preferred materials comprise pumice stone and some commercially available catalyst carriers, e.g. as used in the preparation of ethylene oxyde catalysts. Suitable materials are mentioned in European patent specification 399.592, in which a hydrotreating process for the removal of suspended and dissolved (organo)metallic compounds has been described. The process can be carried out at ambient temperature and atmospheric pressure. If desired, the process can be carried out at a temperature up to 500 °C and a pressure up to 20,000 kPa (200 bar). The operating conditions which are preferred depend on the hydrocarbon oil which is subjected to the process. If for example a short residue, i.e. a residual hydrocarbon oil boiling above 520 °C, is to be subjected to the process of the present invention, the temperature and optionally pressure will be elevated due to the viscosity of such residue; suitable process conditions would comprise a temperature of between 200 and 350 °C and a pressure up to 8000 kPa (80 bar). A long residue, containing hydrocarbons boiling above 270 °C, is preferably processed at a temperature of between 150 and 350 °C and a pressure up to 8000 kPa (80 bar). The amount of metal(s)-containing solid contaminants which is to be removed from the hydrocarbon oil by the present process can vary. Suitably, a substantial amount of the metal(s)-containing solid contaminants is removed.
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Process for reducing the amount of solid contaminants containing metal(s) from Group 1a, 2a, 3a, 4a, 6b and/or 8 of the Periodic Table of the Elements present in a hydrocarbon oil, which process comprises contacting the hydrocarbon oil with porous solid material having a pore volume of at least 0.05 ml/g in pores having a diameter of at least 15 microns, which process is carried out without adding hydrogen. Process according to claim 1, in which process the solid contaminants comprise sodium, calcium, iron and/or molybdenum. Process according to claim 1 or 2, in which process the porous solid material has a pore volume of at least 0.03 ml/g in pores having a diameter of at least 100 microns. Process according to any one of claims 1 to 3, in which process the porous solid material has a pore volume of at least 002 ml/g in pores having a diameter of at least 200 microns. Process according to any one of claims 1-4, in which process the porous solid material has a diameter of between 0.5 and 60 mm. Process according to any one of claims 1-5, which process is carried out at a temperature up to 500 °C and a pressure up to 200 bar. Process according to any one of claims 1-6, in which process use is made of porous solid material comprising pumice stone.
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SHELL INT RESEARCH; SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
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BOON ANDRIES QUIRIN MARIA; DEN OUDEN CONSTANTINUS JOHANNE; ROEBSCHLAEGER KARL-HEINZ WILHE; VAN DEN BERG FRANCISCUS GONDUL; BOON,ANDRIES QUIRIN MARIA; DEN OUDEN,CONSTANTINUS JOHANNES JACOBUS; ROEBSCHLAEGER,KARL-HEINZ WILHELM; VAN DEN BERG,FRANCISCUS GONDULFUS ANTONIUS; Röbschläger,Karl-Heinz Wilhelm
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EP-0489975-B1
| 489,975 |
EP
|
B1
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EN
| 19,940,824 | 1,992 | 20,100,220 |
new
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F01P11
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B01D46
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B01D46, F01P11
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B01D 46/26, F01P 11/12
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Filter element cleaning arrangement
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An air filtering arrangement comprises a generally cylindrical, rotary, perforate filter element (29), a fan (18) operable to draw air therethrough, drive means (36/.) operable rotatably to drive the filter element (29) and blanking off means (38) mounted within the filter element (29) for blanking off the perforations thereof over a predetermined region. The filtering arrangement further also comprises rotatable brush means (48) provided in cleaning engagement with a section of the filter element (29) for releasing foreign matter restrained thereby. The brush means (48) are positioned adjacent the blanking off means (38) at the inner side of the filter element (29) and are operable to pierce through the perforations thereof in a direction from the inside of the filter element (29) towards the outside thereof.
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This invention relates to an air filtering arrangement which can generally be applied to many different devices which have to operate in an atmosphere which besides dry foreign matter, such as dust, chaff, short straw particles, etc., also contains damp and gluey particles and in which air from this athmosphere has to pass through relatively small openings in an element of the filtering arrangement to hold back this foreign matter on the one hand, but whereby there is a danger of the openings becoming blocked if no special precautions are taken on the other hand. Such an air filtering arrangement can, for example, be used with cooling devices for combustion engines or hydraulic equipment. One particular application of the present invention is that of harvesting machines, such as combine harvesters, since these machines, when harvesting e.g. wheat or barley, normally work in a very dusty atmosphere as they can only harvest efficiently when the whole crop is ripe and dry, whereby, during operation, a considerable amount of dust, chaff and short straw particles are displaced in the vicinity of the machine. Harvesting other crops however, especially corn, requires only the ears of corn to be ripe and dry, while the cornstalks still may stand green and succulent as they usually are not processed through the harvesting machine but instead are comminuted thereby and left in the field. In chopping the cornstalks, sap thereof is beaten out generating clouds of damp, sticky particles. Occasionally, in addition, the ears of corn are infested e.g. by fungous diseases, resulting in a gluey powder to be spread into the air when stripping said ears from the cornstalks. Whilst the use of a filter element prevents all this foreign matter in the atmosphere around the harvesting machine from reaching the device being cooled, for example the radiator through which the coolant for a combustion engine flows, it is necessary to prevent that same foreign matter blocking the filter element itself and thereby interrupting the flow of air to the cooling device and causing overheating. It is known from EP-A-0.269.765 to remove foreign matter from a rotary filter element by relying partially on gravity and centrifugal forces. In the arrangement disclosed, the filter element is rotatably mounted and on the side thereof opposite to that through which air enters the filter element, there is provided a stationary means such as a plate, which serves to blank off a given area of the filter element as the latter rotates. Thus, any foreign matter collected on the area blanked off by the plate at any given instant is no longer held by the flow of air through the filter element and can thus fall free of the latter under gravity and centrigugal forces. In order to discharge the dislodged foreign matter at a location remote from the filter element, a duct is provided exteriorly thereof which is open in the region of the blanking off plate. The fan, operable to draw air through the filter element, generates a flow of pressurized air in said duct by virtue of the latter having its inlet opening at the pressure side of the fan. Any foreign matter falling free from the filter element in the predetermined region is captured by the pressurized air flow and is discharged at a remote location from the filter element. Whilst a rotary air filter of the type above has been found satisfactory in conditions where foreign matter adheres exclusively to the outer surface of the filter element, it also has been experienced that said arrangement is unable to clean the internal space of the filter perforations expecially when they are clogged with sticky particles. Indeed, neither gravity nor centrigual forces are strong enough to expel foreign matter which firmly clings to the filter element. Also, since the flow of presurized cleaning air is directed parallel to the filter screen, the inside of the perforations neither can be reached thereby. Another air filter, disclosed in DE-B-453.597 which forms the basis for the preamble of claim 1, is similar to that of EP-A-0.269.765 to the extent that blanking off plates are employed for removing foreign matter from the filter element. In this arrangement however, brush elements in addition are operable to wipe off the outer surface of the filter screen, without intending or succeeding to clean the perforations provided therein. In fact, foreign particles nevertheless released from the perforations by the action of the brush elements, are carried along with the cooling air into the inside of the cooling arrangement and are likely to collect e.g. on the radiator which ultimately will perform inefficiently as a result thereof. It is also known from an embodiment shown in DE-B-2.841.052 to clean a filter element by forcing air through it in the opposite direction to the flow of air to be filtered. For this purpose, air under pressure is collected on the pressure side of the cooling fan, said air being transmitted through a duct to a nozzle, which further directs the air through the filter element in a generally radial direction. In this manner, dust particles which have managed to reach the inner surface of the filter screen are forced back through the filter perforations and are removed from the filter element. Yet, the generated flow of air is unsuccessful to eject damp and gluey particles from clogged perforations, as this would require the use of high-pressure air, such as generated by high-pressure cleaning equipment for example. It is therefore the objective of the present invention to provide a filter element cleaning arrangement which overcomes the aforedescribed shortcomings and drawbacks and which ensures a thorough cleaning of the filter element by means of a simple and carefree construction. According to the present invention, there is provided an air filtering arrangement comprising : a perforate filter element; a fan operable to urge air, which is contaminated with foreign matter, in a given direction through the filter element from an upstream side to a downstream side thereof; said filter element being operable to restrain said foreign matter as said air passes through the perforations thereof; filter element cleaning means comprising rotatable brush means provided in cleaning engagement with a section of the filter element for releasing foreign matter restrained thereby; and drive means for, in use, varying the relative position of the filter element with respect to the brush means such that other sections of the filter element successively are exposed to the brush means; and which is characterized in that : the brush means are positioned at the downstream side of the filter element and are operable to pierce through said perforations thereof in a direction opposite to said given direction whereby foreign matter, collected in said perforations, is expelled towards the upstream side of the filter element. Preferably, the fan is positioned at the downstream side of the filter element and therefore is operable to draw in air through the perforations provided therein. Blanking off means may be provided closely adjacent this side of the filter element for blanking off the perforations thereof over a predetermined region so as to obstruct the passage therethrough of air to be filtered whereby foreign matter collected on the opposite surface of the perforate filter falls free therefrom. In combination with the blanking off means, duct means may be provided in the vicinity of the filter element at this opposite side thereof and which are open in the region of said blanking off means for exposing the filter element to a cleaning air blast captured at the pressure side of the fan. In this combination, the brush means preferably are arranged immediately in front of the blanking off means when seen in the direction of movement of the filter element; said brush means being urged against the facing surface of the perforate filter in order to force the bristles of the brush means through the perforations for expelling any foreign matter collected therein. An air filtering arrangement in accordance with the present invention will now be described, by way of example, with reference to the accompanying drawings, in which : Figure 1 is a schematic side view of a combine harvester having an air filtering arrangement in accordance with the present invention, Figure 2 is a sectional view of the cooling system of the combine harvester of Figure 1, and Figure 3 is a front view, partially in section, of Figure 2, i.e. in the direction of arrow III of Figure 2. Referring first to Figure 1, the combine harvester on which the air filtering arrangement of the present invention is applied, is of generally known form and comprises a main chassis or frame 1 supported on a front pair of drive wheels 2 and a rear pair of steerable wheels 3. Supported on the main chassis 2 are an operator's platform 4, a grain tank 5, a threshing and separating mechanism indicated generally at 6, a grain cleaning mechanism indicated generally at 7, and an engine (not shown). A corn header 8 and elevator housing 9 extend forwardly of the main chassis 1 and the header is pivotably secured to the chassis for generally vertical movement which is controlled by extensible hydraulic cylinders 11. As the combine harvester is propelled forwardly over a field with standing row crop, such as corn, the corn header 8 separates the ears of corn from the corn stalks and the former are conveyed to the elevator housing 9 which supplies them to the threshing and separating mechanism 6 for further processing. The corn stalks, stripped from their ears, are comminuted by a cutter device 12 provided underneath the corn header 8 and are left on the field. The combine harvester further comprises a rotary air filter or screen indicated generally at 14 and illustrated in greater detail in Figures 2 and 3 of the drawings. Referring now to Figures 2 and 3, the rotary air filter 14 forms part of a cooling system for the internal combustion engine of the combine harvester of which only the engine block 16 is illustrated schematically in Figure 2. The cooling system comprises a radiator 17 which is disposed with the engine block 16 at one side thereof and with a cooling fan 18 at the opposite side thereof. The cooling fan 18 is mounted on one end of a collar 19 with the other end of the collar 19 being provided with a pulley 22 which is driven by a belt 23 from a further pulley 24 in order to impart rotational drive to the cooling fan 18. To this end the collar 19 is mounted for rotation, via bearings 21, on a stationary shaft 25 which itself is supported via a support frame 26 provided in a radiator housing 27. The rotary air screen of filter 14 is mounted for rotation on said shaft 25 via bearings 20 and 28 and comprises a filter element 29 in the form of a cylinder which is open at one end facing the radiator 17 and which is closed at the opposite end. The fan 18 is mounted within the cylindrical filter element 29 adjacent its open end. The filter element 29 is imperforate at its closed end but perforate around its periphery for at least a portion of its axial length. Spokes 30, connected to flanges 32 of a hub 34, are operable to rotatably support the filter element 29 on the stationary shaft 25. Rotational drive of the filter element 29 is obtained by a belt 36 engaging the cylindrical surface thereof, thereby rotating the filter 29 at a rotational speed in the range of 200 RPM for example. A stationary blanking off plate 38 is provided within the filter element 29 on the aforementioned shaft 25 in a manner so as to be closely adjacent a region of the perforate periphery of the filter element 29. It will be seen from Figure 3 that, in a preferred embodiment, this plate 38 extends over an arc of approximatley 30°, thus preventing cooling air from flowing through the filter element 29 over that arc at the perforate periphery thereof. Accordingly, any dust, short particles of leaves or other foreign matter collected on the outer surface of the air filter 29 at that blanked off portion in use of the air filtering arrangement tend to fall loose of the filter element due to gravity forces and eventually also centrifugal forces whereafter this foreign matter can readily be removed. To this end, a pneumatic foreign matter evacuation system or blow-off system is provided. This system comprises duct means 40 which is curved so that the open end 42 thereof is directed towards, and positioned adjacent, the pressure side of the cooling fan 18, whereby the latter provides a source of pressurized air which flows through the duct 40. A portion 44 of the duct means 40 extends closely beneath the filter element 29 and is open at its top in the region of the blanking off plate 38. In use, foreign matter that has accumulated on the perforate surface of the filter element 29 and that tends to fall loose beneath the blanking off plate 38 in a manner as already described, is picked up by the localized pressurized air flow and is discharged thereby at a remote location from the rotary air screen. For more details on this blow-off system, reference is made to EP-A-0.269.765, already mentioned. It has been experienced however that under certain adverse operating conditions of the combine harvester, foreign matter not only tends to accumulate on the outer periphery of the perforate surface of the air screen 29, but moreover also tends to creep into the perforations provided therein, as such forming bridges therein and ultimately closing off the perforations completely. As a result, the air screen 29 starts to choke up whereby the cooling efficiency of the combine harvester engine is greatly reduced. The adverse operating conditions referred to hereabove are likely to occur when harvesting corn of which the ears are infested e.g. by fungous disease, which leaves a black, sticky powder on the husk. During harvesting operation, when the ears are stripped from the corn stalks, a large amount of this powder becomes airborne, forming clouds of particles enveloping the combine harvester. It will be appreciated that, since the fan 18 of the engine cooling system draws in air from the immediate surroundings of the harvester, this cooling air inevitably is contaminated with said sticky particles. As the latter are smaller in size than the perforations provided in the filter element 29, lots of these particles are not retained by the outer surface of the filter 29 but are instead carried along with the cooling air into the perforations. Due to their gluey characteristics, and as a result of collisions against the side walls of the perforations, those particles tend to adhere thereto, whereby the free passage of air through the perforations is reduced. In a further stage, particles start to stick to each other, after a while, fill up the perforations completely to the extent that air is prevented from flowing therethrough. The above depicted phenomenon also happens to occur when corn is harvested of which the ears are ripe and dry while the corn stalks are still unripe and green. In chopping those cornstalks with the cutter device 12 underneath the corn header 8, sap of the stalks is smashed thereout by the vigorous action of the cutter knives thereon, forming a haze of liquid particles through which the combine harvester is driving. Said particles, by their nature, equally are rather gluey and as such also effect a rapid clogging of the air filter 29 when air thereby polluted is drawn through the perforations of said filter 29. It is evident that a clogged air filter is highly ineffective and undesirable in that it can cause overheating of the combine harvester engine. Precautions thereagainst, such as the already described blanking off plate 38 or the blow-off system 40, have proven to provide minimal effect when the obstruction of the air filter 29 is concentrated inside the perforations and not on the outer surface of the filter. Indeed, the advantageous effect of the blanking off plate 38 is mainly based on the gravity forces succeeding to loosen foreign matter collected on the outer surface of the air filter 29. However, gravity forces alone are not sufficiently strong to extract the sticky particles from the perforations. Also the blow-off system 40 is unable to clear the filter element 29, as the flow of pressurized air generated in the duct 40 is oriented parallel to the outer surface of the filter 29, thus having no effect whatsoever on the hidden obstructions inside the perforations. A solution to this problem is provided by a filter element cleaning means 46 comprising a brush 48, rotatably mounted parallel to the perforate portion of the filter element 29 and at the inner side thereof, when seen in the direction of normal air flow therethrough. A pair of lever arms 50, hingeably connected at 52 to the retaining members 54 of the blanking off plate 38, is operable to support the brush 48 either in an inoperative position as shown in full lines in Figure 3 or in an operative position shown in dashed lines in the same Figure. A solenoid 56 is attached to a mounting member 58, in turn fixedly secured to the stationary shaft 25. The plunger side of the solenoid 56 is provided with a threaded rod 60 which adjustably receives a bifurcated connector 62, the open end of which hingeably holds a hook-shaped member 64. A further threaded rod 66 is adjustably connected at one side to the hook-shaped member 64, while the other side is attached, via a ball-and-socket joint 68, to a cross member 70 which links the arms 50 to each other. At the brush supporting end of the arms 50, two upright brackets 72 are welded thereto, holding inbetween a rod 74 which extends parallel to the brush 48. A tension spring 76 is provided between an anchor point on the mounting member 58 and the rod 74, at a portion halfway thereof. When the solenoid 56 is not energized, the spring 76 is able to swivel the brush 48 on its supporting arms 50 around their pivots 52 to its inoperative position clear from the perforate portion of the filter element 29. Any further movement away from the filter 29 is prevented by an angled member 78, firmly connected to the rod 60 of the solenoid 56 and which abuts against an extending flange 80 of the mounting member 58. Upon energizing the solenoid 56 by means to be described furtheron, the threated rod 60 is retracted to some degree into the solenoid body in a straight line. Hence also the bifurcated connector 62 is subjected to this linear movement, resulting in all intermediate members 64, 66 and 68 to swivel the levers 50 in a clockwise direction as seen in Figure 3, whereby the brush 48 is urged into its operative position against the filter element 29. It readily will be appreciated that the hook-shaped member 64 and the threaded rod 66 are not moved in a linear path since the levers 50 are pivoted around their fulcrum 52. To intercept this discrepancy in movements, the member 64 is hingeably attached at the bifurcated connector 62 by a hinge 82 which extends parallel to the hinge axis 52 of the levers 50. In order to ensure that the connecting members between the solenoid 56 and the levers 50 are always assembled in a correct manner i.e. with the bifurcated connector 62 always facing in a same direction having its hinge 82 parallel to the hinge axis 52, an elongated recess is provided in the extending flange 80 of the mounting members 58. As such, the hook-shaped member 64 can only enter the recess with its smallest side up front, as seen in Figure 2, and thus consequently the bifurcated connector 62 must be positioned correctly to be able to make the connection. As the filter element 29 is constantly rotating during operation of the combine harvester, rotational power is transmitted to the brush 48 in contact therewith, which starts spinning at an elevated RPM, considering the ratio of the diameters of the filter screen 29 on the one hand and the brush 48 on the other hand. The bristles of the brush 48 are of a size able to pierce through the perforations in de filter element 29 without running the risk of getting stuck therein. In piercing through, the foreign particles accumulated in the perforations are repelled in the direction opposite to the direction in which they entered. As the blanking off plate 38 is positioned immediately behind the brush 48 when seen in the direction of rotation of the screen 29, the repelled particles are not given a chance to be sucked in again by the fan 18, but instead are received in the blow-off duct 44 and evacuated from the vicinity of the screen 29 and, provided the brush 48 is constructed according to some specific requirements, only a few revolutions of the screen 29 are imperative to clean the same. What the construction of the brush 48 is concerned, lightweight synthetic materials are applied to keep the weight as low as possible for reasons to avoid slip of the screen 29 on the brush 48 which would lead to excessive wear of the brush bristles. In the same connection, low friction bearings aligned with respect to each other are used to freely rotatably support the brush 48 on the lever arms 50. The bristles of the brush 48 should meet two almost contradicting requirements : on the one hand being wear-resistant and strong, but on the other hand being very flexible. In a preferred embodiment the bristles are formed by nylon fibres which are attached to a hollow plastic core. To improve the cleaning efficiency, the amount of bristles must be chosen in relation to the amount of perforations instantaneously presented to the brush 48. Indeed, if the outer surface of the brush 48 is too dense, then the brush will act as a near rigid structure and the bristles, which have to enter the perforations, will experience great difficulty to do so. In the opposite case however, if too few bristles are provided, the brush 48 will be too flexible and all the bristles will bend, without entering the perforations. As already mentioned, the brush 48 need not to be in constant engagement with the filter element 29 for satisfactorily cleaning the same. Therefore, in order to prolong the lifetime of the brush 48 and to reduce power consumption of the rotary air filter drive, provisions are made for only periodically energizing the solenoid 56 and thus subjecting the filter 29 to an intermittent cleaning action. To this end, the solenoid 56 is connected to a low voltage electric source (not shown) by means of wires 84, which are suitably guided through a central bore in the shaft 25 for not impeding the operation of rotating elements thereon. Control means (not shown) are included in the electric circuit comprising the electric source and the solenoid 56; the control means being operable to intermittently energize and deenergize the solenoid 56 for moving the brush 48 respectively in and out of engagement with the filter element 29. In a very simple embodiment, the control means may take the form of an electric switch, mounted within reach of the operator on the platform 4. Although such a system undeniably has the advantage of being cheap, it nevertheless suffers from the disadvantage that the operator is likely to forget to manually switch the filter element cleaning means 46 on or off at timely intervals. In the former case he will be driving on for longer periods without noticing that the filter element 29 gradually becomes clogged, resulting in the engine starting to overheat. In the latter case however, the brush 48 will wear faster, reducing the lifetime thereof. To avoid the foregoing from happening, a preferred embodiment is employed wherein the control means are automatically actuated at regular intervals, without any determined action from the part of the operator being required. Said control means comprises an electric switch (not shown), provided underneath the operator's platform 4, which is operatively coupled to the engagement lever (equally not shown) of the graintank unloading tube. A timer mechanism (not shown) is also integrated in the electric circuit of the solenoid 56. In operation, the graintank 5 is gradually filling while the combine harvester is driven over the field. To unload the graintank 5 through the unloading tube into a grain trailer or truck, the operator manipulates the lever to engage the unloading tube drive. By the same action, the electric switch underneath the platform 4 is actuated, whereby electric current is provided to the solenoid 56 and consequently the brush 48 is brought into engagement with the filter 29 for starting its cleaning operation. The timer mechanism ensures that, following the energizing of the solenoid 56, the current supply to this solenoid 56 is interrupted after a predetermined period of time and irrespective of the position of the lever for engaging the unloading tube drive. As during normal operation, the graintank regularly has to be emptied (i.e. in the order of each half hour for example), not enough time is provided to the flow of polluted cooling air to clog the filter screen 29 beyond an acceptable level between two successive cleaning operations. As such, an optimal effect of the cooling system is guaranteed. The timer mechanism referred to hereabove preferably takes the form of an electronic circuit of which the operating time can be adjusted according to the needs. In this respect, it has been experienced that, in most conditions, the timer mechanism may cut the current to the solenoid 56, thereby disengaging the brush 48 from the screen 29, already after a few seconds, since, as mentioned before, only a few revolutions of the screen 29 with the brush 48 in engagement are needed to remove the foreign particles from the perforations therein. All this implies that, during a full harvesting day, the brush 48 becomes operational for a reduced period of time only which nevertheless is sufficient to safeguard the free flow of cooling air through the perforated screen 29. By the same token, the lifetime of the brush 48 is increased considerably. It will be appreciated by a person skilled in the art that the control means for initiating the operation of the brush 48 operatively may be coupled to another control mechanism besides the graintank unloading device, provided said control mechanism is actuated at regular intervals during the harvesting operation. One further example of such a control mechanism is found in the header height adjustment lever (not shown) as indeed said lever is manipulated frequently for raising the header when the combine harvester starts driving on the headlands. It also will be appreciated that besides the measures already taken, still further steps may be taken to prolong the lifetime of the brush 48. One such step consists of ensuring that the inner surface of the perforate screen 29 against which the brush 48 is rubbing, is made as smooth as possible. This is accomplished by taking account of the punch direction during manufacture of the perforations in the screen 29. More specifically, the screen 29 should be assembled such that said punch direction is oriented from the inside of the screen 29 to the outside thereof, so that any serrated bulges, resulting from the punch operation, are located at the outer surface of the screen 29. In an alternative embodiment, the blow-off duct 40 may be omitted without seriously decreasing the cleaning efficiency of the brush 48. In this event, evacuation of the expelled particles from the filter 29 solely depends on gravity forces experienced underneath the blanking off plate 38. Also the latter may be left out from the filter arrangement, although this would demand much longer engagement periods of the brush 48 to keep the filter 29 clean, as particles expelled from the perforations are more likely to be sucked in again immediately behind the brush 48, as seen in the direction of rotation of the filter 29. In case the friction between the brush 48 and the surface of the filter 29 is kept sufficiently low during the cleaning operation, then the spokes 30, which support the filter 29, advantageously may be substituted by a set of turbine blades; these blades being acted upon by the flow of cooling air drawn through the filter by the cooling fan 18, thus rotating the filter at a relatively low rotational speed.
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An air filtering arrangement comprising : a perforate filter element (29); a fan (18) operable to urge air, which is contaminated with foreign matter, in a given direction through the filter element (29) from an upstream side to a downstream side thereof; said filter element (29) being operable to restrain said foreign matter as said air passes through the perforations thereof; filter element cleaning means (46) comprising rotatable brush means (48) provided in cleaning engagement with a section of the filter element (29) for releasing foreign matter restrained thereby; and drive means (36/.) for, in use, varying the relative position of the filter element (29) with respect to the brush means (48) such that other sections of the filter element successively are exposed to the brush means (48); and characterized in that : the brush means (48) are positioned at the downstream side of the filter element (29) and are operable to pierce through said perforations thereof in a direction opposite to said given direction whereby foreign matter, collected in said perforations, is expelled towards the upstream side of the filter element (29). An air filtering arrangement according to claim 1 characterized in that the fan (18) and the brush means (48) are positioned at the same side of the filter element (29); the fan (18) being operable to draw air therethrough. An air filtering arrangement according to claim 2 characterized in that : blanking off means (38) are provided closely adjacent the filter element (29) at the side thereof facing in the direction of the fan (18) for blanking off the perforations in this filter element (29) over a predetermined region so as to obstruct the passage therethrough of air to be filtered, and the brush means (48) are positioned closely adjacent the blanking off means (38). An air filtering arrangement according to claim 3 characterized in that : the filter element (29) is rotatably driven by the drive means (36/.); the blanking off means (38) are stationary and, in use, blank off successive sections of the filter element (29); and the brush means (48), in use, are stationarily positioned upstream of the blanking off means (38) when seen in the direction of rotation of the filter element (29). An air filtering arrangement according to claim 3 or 4 characterized in that : the filter element (29) is generally cylindrical in shape and is perforate around its periphery for at least a portion of its axial length; the fan (18) is operable to draw air to be filtered from outside the filter element (29) through said filter element (29) to the inside thereof ; the blanking off means (38) are provided stationarily within the filter element and extend over an arc of, and closely adjacent the perforate periphery of the filter element (29); and the brush means (48) are generally shaped as a cylinder, the diameter of which is smaller than the diameter of the filter element (29) and which extends generally parallel to the axis of said filter element (29) over the perforate portion thereof. An air filtering arrangement according to claim 5 characterized in that the brush means (48) comprise a hollow core provided with exteriorly extending bristles, dimensioned such that, during cleaning engagement, these bristles are operable to penetrate into the perforations of the filter section exposed to the brush means (48) thereby expelling foreign matter from said perforations in a direction opposite to the direction of entrance of said foreign matter. An air filtering arrangement according to claim 5 or 6 characterized in that the brush means (48) are freely rotatably mounted and are rotatably driven by engagement thereof with the filter element (29). An air filtering arrangement according to any of the claims 3 to 7 characterized in that a filter element cleaning air blast is oriented generally parallel to and closely adjacent a section of the filter element (29) at the side thereof facing away from and in the region of the blanking off means (38); the cleaning air blast being operable to remove foreign matter from said section in said parallel direction and to discharge the removed foreign matter remote from the filter element (29). An air filtering arrangement according to claim 8 characterized in that duct means (44) are provided in the vicinity of the filter element (29) and which are open towards said filter element (29) in the region of the blanking off means (38); the duct means being operable to channel the cleaning air blast in said generally parallel direction relative to and closely adjacent said section of the filter element (29) and the arrangement being such that foreign matter, expelled from the filter perforations by the cleaning action of the brush means (48), is blanked off by the blanking off means (38) from the air drawn into the filter element (29) by the fan (18) and is captured by the cleaning air blast in the duct means (44) through the open portion thereof for being discharged at a location remote from the filter element. An air filtering arrangement according to any of the claims 5 to 9 characterized in that the drive means for the filter element (29) comprises either a belt (36) in driving engagement with the cylindrical surface of the filter element (29) or turbine blades coupled to said filter element (29) whereby, in use, the filter element (29) is driven by the flow of air therethrough as drawn by the fan (18). A harvesting machine characterized in that it comprises an air filtering arrangement (14) in accordance with any of the claims 1 to 10.
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FORD NEW HOLLAND NV; NEW HOLLAND BELGIUM N.V.
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VERGOTE GEERT R J; WITDOEK DANIEL C; VERGOTE, GEERT R.J.; WITDOEK, DANIEL C.
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EP-0489976-B1
| 489,976 |
EP
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B1
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EN
| 19,940,817 | 1,992 | 20,100,220 |
new
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F01P11
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B01D46
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B01D46, F01P11
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F01P 11/12, B01D 46/26
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Control means for use in an air filtering arrangement
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An air filtering arrangement comprises a generally cylindrical, rotary, perforate filter element (29), a fan (18) operable to draw air therethrough, drive means (36/.) operable rotatably to drive the filter element (29) and blanking off means (38) mounted within the filter element (29) for blanking off the perforations thereof over a predetermined region. The filtering arrangement further also comprises rotatable brush means (48) provided in cleaning engagement with a section of the filter element (29) for releasing foreign matter restrained thereby. The brush means (48) are positioned adjacent the blanking off means (38) at the inner side of the filter element (29) and are movable from an inoperative position out of engagement with the filter element (29) to an operative position engaging said filter element (29). Control means (56, 84) are provided for intermittently moving the brush means (48) in and out of engagement with the filter element (29).
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This invention relates to an air filtering arrangement which can generally be applied to many different devices which have to operate in an atmosphere which besides dry foreign matter, such as dust, chaff, short straw particles, etc., also contains damp and gluey particles and in which air from this athmosphere has to pass through relatively small openings in an element of the filtering arrangement to hold back this foreign matter on the one hand, but whereby there is a danger of the openings becoming blocked if no special precautions are taken on the other hand. Such an air filtering arrangement can, for example, be used with cooling devices for combustion engines or hydraulic equipment. One particular application of the present invention is that of harvesting machines, such as combine harvesters, since these machines, when harvesting e.g. wheat or barley, normally work in a very dusty atmosphere as they can only harvest efficiently when the whole crop is ripe and dry, whereby, during operation, a considerable amount of dust, chaff and short straw particles are displaced in the vicinity of the machine. Harvesting other crops however, especially corn, requires only the ears of corn to be ripe and dry, while the cornstalks still may stand green and succulent as they usually are not processed through the harvesting machine but instead are comminuted thereby and left in the field. In chopping the cornstalks, sap thereof is beaten out generating clouds of damp, sticky particles. Occasionally, in addition, the ears of corn are infested e.g. by fungous diseases, resulting in a gluey powder to be spread into the air when stripping said ears from the cornstalks. Whilst the use of a filter element prevents all this foreign matter in the atmosphere around the harvesting machine from reaching the device being cooled, for example the radiator through which the coolant for a combustion engine flows, it is necessary to prevent that same foreign matter blocking the filter element itself and thereby interrupting the flow of air to the cooling device and causing overheating. It is known from EP-A-0.269.765 to remove foreign matter from a rotary filter element by relying partially on gravity and centrifugal forces. In the arrangement disclosed, the filter element is rotatably mounted and on the side thereof opposite to that through which air enters the filter element, there is provided a stationary means such as a plate, which serves to blank off a given area of the filter element as the latter rotates. Thus, any foreign matter collected on the area blanked off by the plate at any given instant is no longer held by the flow of air through the filter element and can thus fall free of the latter under gravity and centrigugal forces. In order to discharge the dislodged foreign matter at a location remote from the filter element, a duct is provided exteriorly thereof which is open in the region of the blanking off plate. The fan, operable to draw air through the filter element, generates a flow of pressurized air in said duct by virtue of the latter having its inlet opening at the pressure side of the fan. Any foreign matter falling free from the filter element in the predetermined region is captured by the pressurized air flow and is discharged at a remote location from the filter element. Whilst a rotary air filter of the type described above has been found satisfactory in conditions where only dry foreign matter is retained on the filter surface exclusively by the flow of air passing through the filter element, it also has been experienced that this arrangement is unable to remove damp and gluey particles which firmly stick to the filter element. This problem partially has been overcome by another air filter, disclosed in DE-B-453.597, which is similar to that of EP-A-0.269.765 to the extent that blanking off plates are employed for allowing dry foreign matter to fall free from the outer surface of the filter element. However, in this arrangement additional brush elements are operable to wipe off said outer surface for removing any particles which might stick too firmly thereto. Yet, a serious drawback inherent to DE-B-453.597 results from the fact that the brush elements are in constant engagement with and are constantly moved over the outer surface of the filter element during operation of the filter arrangement, causing the softest parts, in casu the brush elements, to wear rapidly whereby the lifetime thereof is below the acceptable. Moreover, besides the noise already produced by the fan of the filter arrangement, the rotating brush elements are a source of additional noise pollution. This is particularly true because the brush elements are mounted exteriorly of the filter element, i.e. in the free atmosphere. In the same respect, the brush elements are continuously exposed to all sorts of foreign matter, contained in the surrounding air, thereby running the risk of accumulating dirt onto their surface. Finally, driving the brush elements at all times is power consuming. In SU-A-729.098 a more durable brush means is provided in as much as on the one hand the brush is intermittently rotated over the filter surface and on the other hand the filter itself is a stationary element. However, due to the fact that the brush means are urged in constant engagement with the filter surface, the bristles of the brush in time become deformed whereby the cleaning characteristics of the brush are diminished. It is therefore the objective of the present invention to overcome the aforedescribed drawbacks by providing a filter element cleaning means which is durable in construction, carefree of maintenance and still effective in use. According to the present invention, there is provided an air filtering arrangement comprising : a perforate filter element; a fan operable to urge air, which is contaminated with foreign matter, through the filter element; the arrangement being such that the filter element is operable to restrain said foreign matter as said air passes through the perforations thereof; and filter element cleaning means comprising rotatable brush means for releasing foreign matter from the filter element; and which is characterized in that : the brush means are movable from an inoperative position out of engagement with the filter element to an operative position engaging the filter element; and control means are provided for intermittently moving the brush means in and out of engagement with the filter element. In a preferred embodiment, the fan is operable to draw air through the perforate filter element which is generally cylindrical in shape and is rotatably mounted. Blanking off means are provided within the filter element for blanking off the perforations thereof over a predetermined region so as to obstruct the passage therethrough of air to be filtered whereby foreign matter collected on the outer surface of the perforate filter element falls free therefrom. The brush means are positioned adjacent the blanking off means equally at the inner side of the filter element. The brush means are mounted on a pivotable structure of which the position is controlled by a low voltage solenoid. Upon energizing the solenoid, the brush means are urged against the perforate filter element for cleaning the perforations thereof. In a very simple embodiment, the operation of the solenoid is manually controlled. Preferably however, the solenoid is energized automatically by means of an operative connection to a control mechanism not related to the air filtering arrangement but which is actuated at regular intervals, thereby also initializing the operation of the brush means at regular intervals. In order to retract the brush means from their operative position, a timer mechanism is operable to de-energize the solenoid after a predetermined lapse of time following the actuation thereof. An air filtering arrangement in accordance with the present invention will now be described, by way of example, with reference to the accompanying drawings, in which : Figure 1 is a schematic side view of a combine harvester having an air filtering arrangement in accordance with the present invention, Figure 2 is a sectional view of the cooling system of the combine harvester of Figure 1, and Figure 3 is a front view, partially in section, of Figure 2, i.e. in the direction of arrow III of Figure 2. Referring first to Figure 1, the combine harvester on which the air filtering arrangement of the present invention is applied, is of generally known form and comprises a main chassis or frame 1 supported on a front pair of drive wheels 2 and a rear pair of steerable wheels 3. Supported on the main chassis 2 are an operator's platform 4, a grain tank 5, a threshing and separating mechanism indicated generally at 6, a grain cleaning mechanism indicated generally at 7, and an engine (not shown). A corn header 8 and elevator housing 9 extend forwardly of the main chassis 1 and the header is pivotably secured to the chassis for generally vertical movement which is controlled by extensible hydraulic cylinders 11. As the combine harvester is propelled forwardly over a field with standing row crop, such as corn, the corn header 8 separates the ears of corn from the corn stalks and the former are conveyed to the elevator housing 9 which supplies them to the threshing and separating mechanism 6 for further processing. The corn stalks, stripped from their ears, are comminuted by a cutter device 12 provided underneath the corn header 8 and are left on the field. The combine harvester further comprises a rotary air filter or screen indicated generally at 14 and illustrated in greater detail in Figures 2 and 3 of the drawings. Referring now to Figures 2 and 3, the rotary air filter 14 forms part of a cooling system for the internal combustion engine of the combine harvester of which only the engine block 16 is illustrated schematically in Figure 2. The cooling system comprises a radiator 17 which is disposed with the engine block 16 at one side thereof and with a cooling fan 18 at the opposite side thereof. The cooling fan 18 is mounted on one end of a collar 19 with the other end of the collar 19 being provided with a pulley 22 which is driven by a belt 23 from a further pulley 24 in order to impart rotational drive to the cooling fan 18. To this end the collar 19 is mounted for rotation, via bearings 21, on a stationary shaft 25 which itself is supported via a support frame 26 provided in a radiator housing 27. The rotary air screen of filter 14 is mounted for rotation on said shaft 25 via bearings 20 and 28 and comprises a filter element 29 in the form of a cylinder which is open at one end facing the radiator 17 and which is closed at the opposite end. The fan 18 is mounted within the cylindrical filter element 29 adjacent its open end. The filter element 29 is imperforate at its closed end but perforate around its periphery for at least a portion of its axial length. Spokes 30, connected to flanges 32 of a hub 34, are operable to rotatably support the filter element 29 on the stationary shaft 25. Rotational drive of the filter element 29 is obtained by a belt 36 engaging the cylindrical surface thereof, thereby rotating the filter 29 at a rotational speed in the range of 200 RPM for example. A stationary blanking off plate 38 is provided within the filter element 29 on the aforementioned shaft 25 in a manner so as to be closely adjacent a region of the perforate periphery of the filter element 29. It will be seen from Figure 3 that, in a preferred embodiment, this plate 38 extends over an arc of approximatley 30°, thus preventing cooling air from flowing through the filter element 29 over that arc at the perforate periphery thereof. Accordingly, any dust, short particles of leaves or other foreign matter collected on the outer surface of the air filter 29 at that blanked off portion in use of the air filtering arrangement tend to fall loose of the filter element due to gravity forces and eventually also centrifugal forces whereafter this foreign matter can readily be removed. To this end, a pneumatic foreign matter evacuation system or blow-off system is provided. This system comprises duct means 40 which is curved so that the open end 42 thereof is directed towards, and positioned adjacent, the pressure side of the cooling fan 18, whereby the latter provides a source of pressurized air which flows through the duct 40. A portion 44 of the duct means 40 extends closely beneath the filter element 29 and is open at its top in the region of the blanking off plate 38. In use, foreign matter that has accumulated on the perforate surface of the filter element 29 and that tends to fall loose beneath the blanking off plate 38 in a manner as already described, is picked up by the localized pressurized air flow and is discharged thereby at a remote location from the rotary air screen. For more details on this blow-off system, reference is made to EP-A-0.269.765, already mentioned. It has been experienced however that under certain adverse operating conditions of the combine harvester, foreign matter not only tends to accumulate on the outer periphery of the perforate surface of the air screen 29, but moreover also tends to creep into the perforations provided therein, as such forming bridges therein and ultimately closing off the perforations completely. As a result, the air screen 29 starts to choke up whereby the cooling efficiency of the combine harvester engine is greatly reduced. The adverse operating conditions referred to hereabove are likely to occur when harvesting corn of which the ears are infested e.g. by fungous disease, which leaves a black, sticky powder on the husk. During harvesting operation, when the ears are stripped from the corn stalks, a large amount of this powder becomes airborne, forming clouds of particles enveloping the combine harvester. It will be appreciated that, since the fan 18 of the engine cooling system draws in air from the immediate surroundings of the harvester, this cooling air inevitably is contaminated with said sticky particles. As the latter are smaller in size than the perforations provided in the filter element 29, lots of these particles are not retained by the outer surface of the filter 29 but are instead carried along with the cooling air into the perforations. Due to their gluey characteristics, and as a result of collisions against the side walls of the perforations, those particles tend to adhere thereto, whereby the free passage of air through the perforations is reduced. In a further stage, particles start to stick to each other, after a while, fill up the perforations completely to the extent that air is prevented from flowing therethrough. The above depicted phenomenon also happens to occur when corn is harvested of which the ears are ripe and dry while the corn stalks are still unripe and green. In chopping those cornstalks with the cutter device 12 underneath the corn header 8, sap of the stalks is smashed thereout by the vigorous action of the cutter knives thereon, forming a haze of liquid particles through which the combine harvester is driving. Said particles, by their nature, equally are rather gluey and as such also effect a rapid clogging of the air filter 29 when air thereby polluted is drawn through the perforations of said filter 29. It is evident that a clogged air filter is highly ineffective and undesirable in that it can cause overheating of the combine harvester engine. Precautions thereagainst, such as the already described blanking off plate 38 or the blow-off system 40, have proven to provide minimal effect when the obstruction of the air filter 29 is concentrated inside the perforations and not on the outer surface of the filter. Indeed, the advantageous effect of the blanking off plate 38 is mainly based on the gravity forces succeeding to loosen foreign matter collected on the outer surface of the air filter 29. However, gravity forces alone are not sufficiently strong to extract the sticky particles from the perforations. Also the blow-off system 40 is unable to clear the filter element 29, as the flow of pressurized air generated in the duct 40 is oriented parallel to the outer surface of the filter 29, thus having no effect whatsoever on the hidden obstructions inside the perforations. A solution to this problem is provided by a filter element cleaning means 46 comprising a brush 48, rotatably mounted parallel to the perforate portion of the filter element 29 and at the inner side thereof, when seen in the direction of normal air flow therethrough. A pair of lever arms 50, hingeably connected at 52 to the retaining members 54 of the blanking off plate 38, is operable to support the brush 48 either in an inoperative position as shown in full lines in Figure 3 or in an operative position shown in dashed lines in the same Figure. A solenoid 56 is attached to a mounting member 58, in turn fixedly secured to the stationary shaft 25. The plunger side of the solenoid 56 is provided with a threaded rod 60 which adjustably receives a bifurcated connector 62, the open end of which hingeably holds a hook-shaped member 64. A further threaded rod 66 is adjustably connected at one side to the hook-shaped member 64, while the other side is attached, via a ball-and-socket joint 68, to a cross member 70 which links the arms 50 to each other. At the brush supporting end of the arms 50, two upright brackets 72 are welded thereto, holding inbetween a rod 74 which extends parallel to the brush 48. A tension spring 76 is provided between an anchor point on the mounting member 58 and the rod 74, at a portion halfway thereof. When the solenoid 56 is not energized, the spring 76 is able to swivel the brush 48 on its supporting arms 50 around their pivots 52 to its inoperative position clear from the perforate portion of the filter element 29. Any further movement away from the filter 29 is prevented by an angled member 78, firmly connected to the rod 60 of the solenoid 56 and which abuts against an extending flange 80 of the mounting member 58. Upon energizing the solenoid 56 by means to be described furtheron, the threated rod 60 is retracted to some degree into the solenoid body in a straight line. Hence also the bifurcated connector 62 is subjected to this linear movement, resulting in all intermediate members 64, 66 and 68 to swivel the levers 50 in a clockwise direction as seen in Figure 3, whereby the brush 48 is urged into its operative position against the filter element 29. It readily will be appreciated that the hook-shaped member 64 and the threaded rod 66 are not moved in a linear path since the levers 50 are pivoted around their fulcrum 52. To intercept this discrepancy in movements, the member 64 is hingeably attached at the bifurcated connector 62 by a hinge 82 which extends parallel to the hinge axis 52 of the levers 50. In order to ensure that the connecting members between the solenoid 56 and the levers 50 are always assembled in a correct manner i.e. with the bifurcated connector 62 always facing in a same direction having its hinge 82 parallel to the hinge axis 52, an elongated recess is provided in the extending flange 80 of the mounting members 58. As such, the hook-shaped member 64 can only enter the recess with its smallest side up front, as seen in Figure 2, and thus consequently the bifurcated connector 62 must be positioned correctly to be able to make the connection. As the filter element 29 is constantly rotating during operation of the combine harvester, rotational power is transmitted to the brush 48 in contact therewith, which starts spinning at an elevated RPM, considering the ratio of the diameters of the filter screen 29 on the one hand and the brush 48 on the other hand. The bristles of the brush 48 are of a size able to pierce through the perforations in de filter element 29 without running the risk of getting stuck therein. In piercing through, the foreign particles accumulated in the perforations are repelled in the direction opposite to the direction in which they entered. As the blanking off plate 38 is positioned immediately behind the brush 48 when seen in the direction of rotation of the screen 29, the repelled particles are not given a chance to be sucked in again by the fan 18, but instead are received in the blow-off duct 44 and evacuated from the vicinity of the screen 29 and, provided the brush 48 is constructed according to some specific requirements, only a few revolutions of the screen 29 are imperative to clean the same. What the construction of the brush 48 is concerned, lightweight synthetic materials are applied to keep the weight as low as possible for reasons to avoid slip of the screen 29 on the brush 48 which would lead to excessive wear of the brush bristles. In the same connection, low friction bearings aligned with respect to each other are used to freely rotatably support the brush 48 on the lever arms 50. The bristles of the brush 48 should meet two almost contradicting requirements : on the one hand being wear-resistant and strong, but on the other hand being very flexible. In a preferred embodiment the bristles are formed by nylon fibres which are attached to a hollow plastic core. To improve the cleaning efficiency, the amount of bristles must be chosen in relation to the amount of perforations instantaneously presented to the brush 48. Indeed, if the outer surface of the brush 48 is too dense, then the brush will act as a near rigid structure and the bristles, which have to enter the perforations, will experience great difficulty to do so. In the opposite case however, if too few bristles are provided, the brush 48 will be too flexible and all the bristles will bend, without entering the perforations. As already mentioned, the brush 48 need not to be in constant engagement with the filter element 29 for satisfactorily cleaning the same. Therefore, in order to prolong the lifetime of the brush 48 and to reduce power consumption of the rotary air filter drive, provisions are made for only periodically energizing the solenoid 56 and thus subjecting the filter 29 to an intermittent cleaning action. To this end, the solenoid 56 is connected to a low voltage electric source (not shown) by means of wires 84, which are suitably guided through a central bore in the shaft 25 for not impeding the operation of rotating elements thereon. Control means (not shown) are included in the electric circuit comprising the electric source and the solenoid 56; the control means being operable to intermittently energize and deenergize the solenoid 56 for moving the brush 48 respectively in and out of engagement with the filter element 29. In a very simple embodiment, the control means may take the form of an electric switch, mounted within reach of the operator on the platform 4. Although such a system undeniably has the advantage of being cheap, it nevertheless suffers from the disadvantage that the operator is likely to forget to manually switch the filter element cleaning means 46 on or off at timely intervals. In the former case he will be driving on for longer periods without noticing that the filter element 29 gradually becomes clogged, resulting in the engine starting to overheat. In the latter case however, the brush 48 will wear faster, reducing the lifetime thereof. To avoid the foregoing from happening, a preferred embodiment is employed wherein the control means are automatically actuated at regular intervals, without any determined action from the part of the operator being required. Said control means comprises an electric switch (not shown), provided underneath the operator's platform 4, which is operatively coupled to the engagement lever (equally not shown) of the graintank unloading tube. A timer mechanism (not shown) is also integrated in the electric circuit of the solenoid 56. In operation, the graintank 5 is gradually filling while the combine harvester is driven over the field. To unload the graintank 5 through the unloading tube into a grain trailer or truck, the operator manipulates the lever to engage the unloading tube drive. By the same action, the electric switch underneath the platform 4 is actuated, whereby electric current is provided to the solenoid 56 and consequently the brush 48 is brought into engagement with the filter 29 for starting its cleaning operation. The timer mechanism ensures that, following the energizing of the solenoid 56, the current supply to this solenoid 56 is interrupted after a predetermined period of time and irrespective of the position of the lever for engaging the unloading tube drive. As during normal operation, the graintank regularly has to be emptied (i.e. in the order of each half hour for example), not enough time is provided to the flow of polluted cooling air to clog the filter screen 29 beyond an acceptable level between two successive cleaning operations. As such, an optimal effect of the cooling system is guaranteed. The timer mechanism referred to hereabove preferably takes the form of an electronic circuit of which the operating time can be adjusted according to the needs. In this respect, it has been experienced that, in most conditions, the timer mechanism may cut the current to the solenoid 56, thereby disengaging the brush 48 from the screen 29, already after a few seconds, since, as mentioned before, only a few revolutions of the screen 29 with the brush 48 in engagement are needed to remove the foreign particles from the perforations therein. All this implies that, during a full harvesting day, the brush 48 becomes operational for a reduced period of time only which nevertheless is sufficient to safeguard the free flow of cooling air through the perforated screen 29. By the same token, the lifetime of the brush 48 is increased considerably. It will be appreciated by a person skilled in the art that the control means for initiating the operation of the brush 48 operatively may be coupled to another control mechanism besides the graintank unloading device, provided said control mechanism is actuated at regular intervals during the harvesting operation. One further example of such a control mechanism is found in the header height adjustment lever (not shown) as indeed said lever is manipulated frequently for raising the header when the combine harvester starts driving on the headlands. It also will be appreciated that besides the measures already taken, still further steps may be taken to prolong the lifetime of the brush 48. One such step consists of ensuring that the inner surface of the perforate screen 29 against which the brush 48 is rubbing, is made as smooth as possible. This is accomplished by taking account of the punch direction during manufacture of the perforations in the screen 29. More specifically, the screen 29 should be assembled such that said punch direction is oriented from the inside of the screen 29 to the outside thereof, so that any serrated bulges, resulting from the punch operation, are located at the outer surface of the screen 29. In an alternative embodiment, the blow-off duct 40 may be omitted without seriously decreasing the cleaning efficiency of the brush 48. In this event, evacuation of the expelled particles from the filter 29 solely depends on gravity forces experienced underneath the blanking off plate 38. Also the latter may be left out from the filter arrangement, although this would demand much longer engagement periods of the brush 48 to keep the filter 29 clean, as particles expelled from the perforations are more likely to be sucked in again immediately behind the brush 48, as seen in the direction of rotation of the filter 29. In case the friction between the brush 48 and the surface of the filter 29 is kept sufficiently low during the cleaning operation, then the spokes 30, which support the filter 29, advantageously may be substituted by a set of turbine blades; these blades being acted upon by the flow of cooling air drawn through the filter by the cooling fan 18, thus rotating the filter at a relatively low rotational speed.
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An air filtering arrangement comprising : a perforate filter element (29); a fan (18) operable to urge air, which is contaminated with foreign matter, through the filter element (29); the arrangement being such that the filter element (29) is operable to restrain said foreign matter as said air passes through the perforations thereof; and filter element cleaning means (46) comprising rotatable brush means (48) for releasing foreign matter from the filter element; and characterized in that : the brush means (48) are movable from an inoperative position out of engagement with the filter element (29) to an operative position engaging the filter element (29); and control means (56, 84) are provided for intermittently moving the brush means (48) in and out of engagement with the filter element (29). An air filtering arrangement according to claim 1 characterized in that the control means include : an electric circuit (84) comprising an electric power source; a solenoid (56) operatively coupled to the brush means (48) and integrated in said electric circuit (84); and switch means equally integrated in said electric circuit (84) and operable to control the operation of the solenoid (56). An air filtering arrangement according to claim 2 characterized in that said switch means either are manually operable or are automatically operated by means of an operative connection to a further control means not related to the air filtering arrangement; said further control means being actuated at regular intervals thereby also controlling the operation of the brush means (48) as a result of said operative connection therebetween. An air filtering arrangement according to claim 3 characterized in that the control means (56, 84) further also include timer means operable to de-energize the solenoid (56) after a predertermined lapse of time following the actuation thereof and during which the brush means (48) are in engagement with the filter element (29) to thereby move said brush means (48) to their inoperative position. An air filtering arrangement according to any of the claims 2 to 4 characterized in that the brush means (48) are rotatably mounted on a pivotable structure (50, 70) operatively connected to the plunger side of the solenoid (56) by means of intermediate linkage means (60, 62, 65, 66 and 68); pivotal movement of said pivotable structure (50, 70) together with the brush means (48) thereon towards the operative position being effected by energizing the solenoid (56) whereas spring means (70) are operable to retract the brush means (48) towards the inoperative position upon deactivation of the solenoid. An air filtering arrangement according to any of the preceding claims wherein said arrangement further comprises drive means (36/.) for, in use, varying the relative position of the filter element (29) with respect to the brush means (48) such that other sections of the filter element successively are exposed to the brush means (48); and characterized in that : the fan is operable to urge air through the filter element (29) in a given direction; and the brush means (48) are positioned at the side of the filter element (29) which faces in said given direction and are operable to pierce through said perforations thereof in the opposite direction. An air filtering arrangement according to any of the preceding claims characterized in that the fan (18) and the brush means (48) are positioned at the same side of the filter element (29); the fan (18) being operable to draw air therethrough. An air filtering arrangement according to claim 7 characterized in that : blanking off means (38) are provided closely adjacent the filter element (29) at the side thereof facing in the direction of the fan (18) for blanking off the perforations of the filter element (29) over a predetermined region so as to obstruct the passage therethrough of air to be filtered, and the brush means (48) are positioned closely adjacent the blanking off means (38). An air filtering arrangement according to claim 8 characterized in that : the filter element (29) is rotatably driven by the drive means (36/.); the blanking off means (38) are stationary and, in use, blank off successive sections of the filter element (29); and the brush means (48), when in the operative position, are stationary at a position upstream of the blanking off means (38) when seen in the direction of rotation of the filter element (29). An air filtering arrangement according to claim 8 or 9 characterized in that : the filter element (29) is generally cylindrical in shape and is perforate around its periphery for at least a portion of its axial length; the fan (18) is operable to draw air to be filtered from outside the filter element (29) through said filter element (29) to the inside thereof ; the blanking off means (38) are provided stationarily within the filter element and extend over an arc of, and closely adjacent the perforate periphery of the filter element (29); and the brush means (48) are generally shaped as a cylinder, the diameter of which is smaller than the diameter of the filter element (29) and which extends generally parallel to the axis of said filter element (29) over the perforate portion thereof. An air filtering arrangement according to claim 10 characterized in that the brush means (48) comprise a hollow core provided with exteriorly extending bristles, dimensioned such that, during cleaning engagement, the bristles are operable to penetrate into the perforations of the filter section exposed to the brush means (48) thereby expelling foreign matter from said perforations in a direction opposite to the direction of entrance of said foreign matter. An air filtering arrangement according to claim 10 or 11 when appended either directly or indirectly to claim 5 characterized in that the brush means (48) are freely rotatably mounted on the pivotable structure (50, 70) and are rotatably driven by the filter element (29) when in engagement therewith. An air filtering arrangement according to any of the claims 8 to 12 characterized in that a filter element cleaning air blast is oriented generally parallel to and closely adjacent a section of the filter element (29) at the side thereof facing away from and in the region of the blanking off means (38); the cleaning air blast being operable to remove foreign matter from said section in said parallel direction and to discharge the removed foreign matter remote from the filter element (29). An air filtering arrangement according to claim 13 characterized in that duct means (44) are provided in the vicinity of the filter element (29) and which are open towards said filter element (29) in the region of the blanking off means (38); the duct means being operable to channel the cleaning air blast in said generally parallel direction relative to and closely adjacent said section of the filter element (29) and the arrangement being such that foreign matter, expelled from the filter perforations by the cleaning action of the brush means (48), is blanked off by the blanking off means (38) from the air drawn into the filter element (29) by the fan (18) and is captured by the cleaning air blast in the duct means (44) through the open portion thereof for being discharged at a location remote from the filter element. An air filtering arrangement according to any of the claims 10 to 14 characterized in that the drive means for the filter element (29) comprises either a belt (36) in driving engagement with the cylindrical surface of the filter element (29) or turbine blades coupled to said filter element (29) whereby, in use, the filter element (29) is driven by the flow of air therethrough as drawn by the fan (18). An air filtering arrangement according to any of the preceding claims characterized in that the filtering arrangement (14) is provided in a harvesting machine. An air filtering arrangement according to claim 16 when appended either directly or indirectly to claim 3, characterized in that : the harvesting machine comprises a grain tank and grain tank unloading means; and said further control means is operable to control the operation of the grain tank unloading means for unloading the grain tank at regular intervals.
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FORD NEW HOLLAND NV; NEW HOLLAND BELGIUM N.V.
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VERGOTE GEERT R J; WITDOEK DANIEL C; VERGOTE, GEERT R.J.; WITDOEK, DANIEL C.
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EP-0489978-B1
| 489,978 |
EP
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B1
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EN
| 19,960,320 | 1,992 | 20,100,220 |
new
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G03C1
| null |
B05C5, G03C1
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G03C 1/74
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Curtain coater
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A curtain coater for coating a layer of liquid coating composition on a web in the manufacture of a photographic element, which comprises an air shield (26) that is curved about an angular portion of a backing roller (18). This air shield has arrangements at least near the inlet (22) and outlet (23) of the shield determining zones wherein the resistance to air flow is larger than that in a zone that is located between such arrangements, and means (11) for reducing the air pressure in the zone which is located between the zones of larger air resistance. The operation of this air shield is to remove the boundary layer of air from the web to an extent that is sufficient to allow higher coating speeds than before.
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BACKGROUND OF THE INVENTIONField of the invention The present invention relates to a curtain coater for coating a layer of liquid coating composition on a continuous web in the manufacture of a photographic element. Description of the prior artIn the manufacture of a photographic coating element the coating compositions typically consist of aqueous solutions or dispersions containing hydrophilic colloids with or without other materials dissolved or dispersed therein. They are liquid compositions of relatively low viscosity, for example, of less than about 150 cP (centipoise), most in the range from about 5 to about 100 cP. After having been coated onto the surface of a support they are subjected to controlled temperatures to effect setting and drying. In the photographic art coating compositions are used which differ very much in chemical composition and, to a more limited extent, in physical characteristics. Various materials are used as the support. Thus, for example, the support is made of paper, film base, glass, cloth and the like, and it may be coated in the form of discrete sheets or, as is more usual, in the form of a continuous web. The manufacture of photographic elements is an tremendously difficult art requiring extremely accurate control. Unlike coating operations in other arts, where complete coverage of the article being coated and attractive appearance are usually the only essentials for any particular coating method, in the photographic art the coating method must provide for precise control. A photographic element requires coating of individual layers which are extremely thin, i.e. a maximum wet thickness of about 150 micrometer, and generally far below this value e.g. as low as about 10 micrometer. After coating the layers have to be set and/or dried before the product can be handled and their surfaces generally cannot be subjected to any physical treatment to increase their smoothness and/or their thickness uniformity. For this reason, the coating composition must be applied to the support in such a precise manner that after the layer is set and/or dried it will be within permissible tolerances with respect to both thickness and uniformity. Since an individual layer must be extremely thin, as is indicated above, and since the maximum variation in thickness uniformity is mostly plus or minus some percents, it is obvious that the coating operation in the manufacture of photographic elements is an unusually complex and demanding procedure. Moreover, the difficulties involved in meeting the requirements of utmost thinness and extreme uniformity further grow by the fact that in order to be commercially practical, the coating operation must be capable of handling continuous webs with a width up to one meter or more and must enable the web to be coated at high speeds, for example, speeds as high as several meters per second. A particularly interesting coater for realizing the objects set forth hereinbefore is a curtain coater. If such apparatus is arranged to provide exact control of the means by which the free-falling curtain is generated, and of certain critical relationships between the operating variables, high quality photographic elements may be produced with this type of coater. Basic patents on the use of a curtain coater for the production of photographic elements are US-A 3,632,374 and US-A 3,508,147 relating to a single-layer and to a multiple-layer curtain coater respectively. A phenomenon observed at coating speeds higher than approximately 150 m.min⁻¹ is the displacement of the curtain in the direction of the web movement by the air entrained by the web. A small layer of air that sticks to the moving web hits the contact line between curtain and web. Moreover the displacement of this contact line is not uniform since the curtain assumes a wavelike or undulating deformation, considered in the transverse direction of the curtain. As a consequence of the curtain deformation, the coated layer gets longitudinal bandlike thickness deviations. These bandlike deformations are of the order of magnitude of some percents only, and are mostly not disturbing in the case of opaque photographic materials that are viewed or used in reflection. In the case, however, of photographic materials that are viewed in transmission, the density variations caused by bandlike thickness variations of one or more og its light-absorbing layers, whether these layers are light-sensitive or not, are unacceptable. In order to avoid this problem, one has to evacuate the boundary layer of air from the surface of the web. It has been proposed to obviate the mentioned problem by means of different techniques. First, it is known to provide the coater with shield means that extend parallel with the curtain and terminate in close proximity of the web surface, with an end portion deflected in countercurrent direction. The shield means may occasionally be provided with a vacuum manifold operatively connected thereto for evacuating air from the surface of the web. The described improvement is disclosed in US-A 3,867,901. We have noticed that at speeds over 150 to 200 m.min ⁻¹, depending on the thickness of the applied layer, the mentioned shield means do not prevent the formation of bands in the coated layer. Another arrangement for removing the boundary layer of air from a web in a curtain coater is disclosed in FR-A 1,463,674. In this patent specification, not mentioned for the manufacture of photographical elements, a coater is described in which a web (such as cardboard or cellulose derivatives) is transported through a coating curtain by means of a conveyor roller before and after the curtain, and in which the web is deflected slightly downwards by contact with a knife edge that forms an air-tight joint between the knife and the web, a certain distance upstream of the curtain. According to an alternative embodiment of the arrangement, the knife is hollow and has an open edge at its underside, whereby the entrained air may be sucked off. Although the knife effectively removes the boundary layer of air from the web and also stabilizes the curtain as well as the web, its use is excluded in the manufacture of photographic elements since the frictional contact with the support inevitably damages the surface of the support. Damaging of a delicate web also occurs by particles of dust and the like that become collected at the front side of the knife and that causes scratching of the web surface. Positioning this knife above the web as in fig 9 of US 3,362,374 without making any contact, requires the use of large flowrates of sucked-off air in order to remove the boundary layer sufficiently. However, it is practically impossible to get an uniform evacuation, transversal to the direction of the curtain, of the boundary layer when flowrates of this order of magnitude are used. Any non-uniformity causes bandlike disturbances in the coated layer. A still further arrangement for removing a boundary layer of air from a web comprises an arcuate shield that is curved concentrically about the axis of the web-supporting roller and has arrangements at least near its inlet and outlet determining zones wherein the resistance to air flow is larger than in a zone located between such arrangements. The narrow gap that is formed between such arcuate shield and the web on the roller forms an important resistance to air entrained with the web, and thereby allows the use of higher coating speeds. The mentioned arrangement is disclosed in Research Disclosure No. 18916 of January 1980, but also with this arrangement a practical upper limit of the coating speed is approximately 200 m.min⁻¹ for a shield spacing of 1 mm. Due to constructive limitations smaller shield spacings can be used only for smaller curtain widths, such as curtain widths smaller than about 40 cm. Finally, in DE-B-1,269,546 is disclosed a curtain coater in which objects to be coated are transported through a coating zone by means of two endless belts. Disturbing influences of air displacements in the coating room and of air entrained by the objects are reduced by brushes that bear on the end of the straight advancing stretch of the first belt. The effect of the described measure is also limited and in fact is advantageous only for the types of coating that are disclosed in the cited document, namely paints and adhesives. It is clear that brushes with bristles or hairs that are stiff and/or sharp-ended are not suited for use in manufacturing of photographic material. It is even possible that the brush catches and gathers dust particles, and finally that large agglomerates of such particles loose adherence to the bristles and slip under the brush. Suchlike agglomerates become then wound between successive convolutions of the roll of web and cause a permanent defect in the web surface. Positioning the brush above the web without making contact is an embodiment whereby the problem of gathering the dust particles is avoided but whereby the removal of the boundary layer is unsatisfactory. SUMMARY OF THE INVENTIONObjects of the inventionIt is an object of the present invention to provide an improved curtain coater that allows the application of thin layers at elevated speeds by means of curtain coating in the manufacturing of photographic elements. It is a further object to provide such curtain coater that is simple of construction and easily to adjust and to maintain. Other objects will become apparent from the description hereinafter. Statement of the inventionAccording to the present invention, a curtain coater for coating a layer of liquid photographic coating composition on a continuous web in the manufacture of a photographic element, comprising a coating hopper for producing a free-falling curtain of coating composition, a backing roller for moving said web along a circularly curved path underneath said hopper and an air shield that is curved about an angular portion of the backing roller, said air shield having arrangements at least near its inlet and outlet ends that determine zones wherein the resistance to air flow is larger than in a zone located between such arrangements, is characterized in that said air shield includes means for reducing the air pressure in said zone which is located between said zones of larger air resistance. The operation of this air shield is to remove the boundary layer of air from the web to an extent satisfactory to allow higher coating speeds than before. In order to suck off the entrained air uniformly, a stable, i.e. in time and place, reduced pressure is required. To obtain a reduced pressure with these qualities a high resistance must be built up between the area which is reduced to a lower pressure and the ambient air. For this reason the arrangements that form an air barrier are to be placed close to the support, at a distance d smaller than 2 mm. It is obvious that for constructive reasons there is a limit in reducing this distance d. For coaters which can handle widths up to one meter or more this limit is about 0.5 mm. The term web as used in the statement of invention includes uncoated supports made of paper, film base, and the like, but also supports that have received already one or more coatings, such as a subbing layer, a first light-sensitive layer, etc. The term layer stands for a single layer as well as for a multiple layer of coating composition. A multiple layer may comprise two, three or more distinct layers that have been formed through separate slots, but that are brought into contact with each other before they leave the coating hopper. The air shield can be constructed as a solid member curved about an angular portion of the backing roller, this solid air shield having at least one recessed area forming a chamber. The chamber is the area in which a reduced pressure is maintained. The unrecessed portions of the air shield constitute the arrangements wherein the resistance to air flow is larger than the resistance in the chamber. The arrangements that form a zone of increased air resistance can also be constructed in other ways. They can be protruding parts, strips or even one or more laminae connected to that shield and directed towards the web. These laminae can extend over the total width of the air shield, or a group of smaller randomly placed laminae can construct a labyrinth. The only function of these obstacles is to form an increased air resistance, as compared with the resistance to air flow in the region of the shield located between such arrangements. The presence of a high resistance is necessary to maintain the required reduced pressure with a low flow rate of evacuated air. Higher flowrates are not desirable since they can cause non-uniformities inside the air shield. Any non-uniformity may cause bandlike disturbances in the coated material. The pressure difference between the ambient air and the inside of the air shield has to be high enough in order to evacuate the boundary layer of air adhering to the web, but is also limited. When this pressure difference becomes too high, a strong air flow in a direction from the coating curtain towards the airshield might be created. This may cause the entire liquid curtain or at least a part of it to become sucked up into the airshield. This phenomenon destroys the coating procedure and therefore is to be avoided. The reauired pressure difference depends on the geometry of the arrangement, the distance between the web and the arrangement, the distance between the outlet end of the air shield and the coating curtain and the velocity of the web, and practically is comprised between 10 and 500 Pa. In order to maintain this reduced pressure it is desirable to provide a means for restricting the inflow of air at the sides of the lateral ends of the shield. Therefore, at the sides too, arrangements are provided that determine zones wherein the resistance to air flow is larger than in a zone located between such arrangements. These lateral end arrangements can be constructed in the same way as those forming the inflow end and outflow end of the air shield. According to a prefered embodiment of the invention, the outlet end of the air shield is placed at a distance between 5 and 30 mm upstream of the line of coating, i.e. the line where the coating curtain first contacts the moving web. Smaller distances involve the risk for a swinging curtain to touch and to soil the air shield, whereas larger distances strongly reduce the effect of the air removal. Without the use of reduced pressure zones the rebuilding of a new boundary layer of entrained air takes place at the outlet end of the air shield towards the line of coating. Due to this reduced pressure a small air movement from above the air shield towards the zones of reduced pressure underneath the shield prevents the establishment of a new boundary layer of air on the web. The new boundary layer not rebuilds itself immediately after the outlet end of the air shield but starts to form at a point closer to the line of coating. In this way the effect of the air shield is extended to a point which may be up to some mm downstream of the outlet end of that shield. BRIEF DESCRIPTION OF THE DRAWINGSThe invention is described hereinafter by way of an example with reference to the accompanying drawings, wherein : fig. 1is a diagrammatic illustration of a curtain coater, fig. 2is a cross-sectional view of one embodiment of an air shield configuration, fig. 3is a top view of fig 2, fig. 4ais a diagrammatic illustration of an experimental set-up with no air shield, fig. 4bis a diagrammatic illustration of an experimental set-up with an air shield without a reduced pressure area, fig. 4cis a diagrammatic illustration of an experimental set-up with an air shield with a reduced pressure area, and fig. 5is a diagram illustrating the results of the arrangements 4a to 4c. Detailed description of the inventionReferring to figure 1, a curtain coater is illustrated comprising a coating head 10 of the slide-hopper type that is arranged for applying a layer of liquid coating composition to a moving support by curtain coating. The hopper is supplied with coating composition through a manifold 12 and has an elongate discharge slot 13 from which the coating composition flows over a slide surface 14 unto a lip 15 from which it falls freely downwardly in the form of a curtain 16. The hopper extends transversely of the path of travel of a web 17 to be coated, the path of which is determined by a backing roller 18 to which the web is advanced over a guide roller 19. Means is provided, not illustrated, for controlling the correct web speed, the lateral web position, and the web tension. Edge guides, not illustated, as known in the art are provided near both lateral ends of lip 15 that are in adherent contact with the edges of the free-falling curtain and thereby keep the curtain stretched in the transverse direction until it contacts the web on a transverse line, illustrated in the figure by point 20. The coating hopper preferably is mounted for vertical displacement so that the height of the curtain may be adjusted and in consequence the speed of impingement of the curtain on the web be set. Further, the coating hopper 10 or roller 18 may be arranged for horizontal displacement so that at the start of a new coating procedure, the coating may be made to fall from the lip directly into a pan (not illustrated) until a bubble-free liquid flow and a satisfactory transverse thickness profile of the curtain have been established. Then the hopper or the roller 18 may be reset to obtain the operative position as shown in the figure. Alternatively, displaceable shield means may be provided between lip 15 and roller 18 in order to temporarily intercept the curtain from contacting web 17, until a stable curtain has been established. The coater comprises an air shield 26 that is concavely curved concentrically about the axis of roller 18. Figure 2 is a cross-sectional view of a preferred embodiment of an air shield configuration. Figure 3 is a top view of this embodiment, the manifold being removed. The air shield 26, the inlet and outlet arrangements (22,23), and the lateral end arrangements 24 and 31 are constructed as one solid member. The recessed area between these zones of relatively large air resistance forms zone 25 in which a reduced pressure is maintained. This configuration, made for instance of stainless steel, has the major benefit to be mechanically strong and easy to construct. The zone of reduced pressure 25 is connected through elliptic slots 30 with an air manifold 29 which extends over the full width of the air shield 26. A reduced pressure, stationary in time and place, can easily be maintained by any means 11 such as a suction pump. The following data illustrate the configuration described in figures 2 and 3. Backing roller 18 has a diameter of 230 mm, and a length of 240 mm. The air shield 25 covers 110 degrees of the backing roller 18. The inflow arrangement of higher air resistance 22 extends over 65 degrees, the recessed area 25 wherein the reduced pressure can be maintained extends over 20 degrees, while the outflow arrangement covers 25 degrees of the backing roller. The width of the lateral end arrangements 24 and 31 is 20 mm. The distance d between the inflow and outflow arrangements 22,23 and backing roller 18 is 1 mm. The fact that both in- and outlet arrangements are at the same distance from the backing roller is not a limitation but allows its mechanically easy construction. The outlet end of the air shield is placed at a distance e of 10 mm from the contact line 20. The air shield has heating means 28 to avoid condensation of the air between web 17 and air shield 26. Condensation may soil the web or unstabilise the reduced pressure. Anyway, condensation endangers the coating procedure. The heating means 28 are electrical in this example, but other means such as water- or steam circuits may be used. The air velocities at different levels above backing roller 18 characterize the boundary layer of air sticked to the web that would disturb the coating curtain. In order to get information about these velocities the following experimental set-up was used : backing roller 18 was driven at a peripheral velocity of 266 m/min. The air velocities at different distances from the peripheral surface of the driven roller have been measured by means of a laser doppler anemometer. The term measuring point as will be used hereinafter, is the point of intersection of the two laser beams of the laser anemometer. The air velocities as a function of the distance from a measuring point 27 (see fig. 4) from the roller surface along an axis A are illustrated in figure 5, the curves a, b and c corresponding with the respective arrangements in figs 4a, b and c. The abcissa represents the measured air velocity in m/min, whereas the ordinate represents the distance between measuring point 27 and roller 18. In fig. 4a the measurements were carried out with no air shield. It may be seen that for a distance f = 0, i.e. the measuring point 27 being situated right on the surface of roller 18, the measured velocity perfectly corresponds with the actual roller speed, which may be calculated from the diameter of the roller and its number or revolutions per minute. The surface area of the diagram included between a curve and the axes of the diagram is important, since it represents the rate of air flow that impinges on the curtain of coating composition, because actually the curtain is a shield that is in the way of the air entrained with the moving roller surface (i.e. in practice the web surface). It can be seen that the velocity of the boundary layer of air increases beyond proportion at distances f less than 1 mm, as compared with f larger than 1 mm. Obviously, this rapid acceleration of air entrained closely to the roller surface gives rise to an undesirable disturbance of the vulnerable curtain at the position where the effect is greatest, viz. at the position of impingement on the web. The measured air velocities remain absolutely constant if the measuring point is displaced in a direction parallel to the roller axis. Thus it could be concluded that the impingement of a uniformly structured air volume on a coating curtain that itself is likewise extremely uniform, only could result in the uniform deflection of the curtain in the direction of the advancing web. However, practice shows that the curtain deflection is not uniform and that instead the curtain is deformed in an undulating way as described already in the introduction of this specification. These wavelike deformations of the curtain cause corresponding thickness variations of a coated layer as has been established experimentally. In figure 4b the use of an air shield reduces the surface area of the diagram included between curve b and the axes, even when there is no pressure difference. Figure 4c illustrates that a pressure difference (50 Pa in the present example) reduces this area even more. The improvement according to the invention reduces the amount of entrained air by approximately 50 %, whereas the velocity of the entrained air at less than 1 mm near contact line 20 is diminished by a factor larger than 2. The invention is not limited to the embodiment described hereinbefore. The arrangements that determine the zones of the shield where the resistance to air flow is larger than at the other central zone(s), may take other forms than the one illustrated hereinbefore. They may be protruding parts having a straight, cylindrical, elliptical or other form of which the surface faces the backing roller . They may be strips, brushes or even one or more laminae connected to the shield and directed towards the web. These laminae may extend over the total width of the air shield, or a group of smaller laminae randomly placed can construct a labyrinth. More than one zone of reduced pressure can be used. These different zones may be connected with one common air manifold. However, each such zone may also have its own means for reducing the air pressure.
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Curtain coater for coating a layer of a liquid coating composition on a continuous web (17) in the manufacture of a photographic element, which comprises : a coating hopper (10) for producing a free-falling curtain (16) of coating composition, a backing roller (18) for moving said web (17) along a circularly curved path underneath said hopper (10) to have said composition deposited onto said web (17) from said curtain (16) and an air shield (26) that is curved about an angular portion of the backing roller (18), said air shield (26) having arrangements (22, 23) at least near its inlet and outlet ends that determine zones wherein the resistance to air flow is larger than in a zone (25) located between such arrangements, characterized in that said air shield (26) includes means (11) for reducing the air pressure in said zone (25) which is located between said zones of larger air resistance (22, 23). Curtain coater according to claim 1, wherein said air shield (26) is constructed as a solid member curved about an angular portion of said backing roller (18), said solid member having at least one recessed chamber, said recessed chamber constituting the zone of reduced air pressure (25) and said unrecessed portions of said member constituting said arrangements (22, 23) where the resistance to air flow is longer than in zone (25). Curtain coater according to claim 1, wherein said arrangements (22, 23) are strips connected to said air shield (26). Curtain coater according to any of claims 1 to 3, wherein the distance d between said arrangements (22, 23) and said backing roller (18) is comprised between 0.5 and 2 mm. Curtain coater according to any of claims 1 to 3, wherein also the lateral ends (24, 31) of said air shield (26) have arrangements that determine zones wherein the resistance to air flow is larger than in a zone located between such arrangements (25). Curtain coater acoording to any claims of 1 to 5, wherein said reduced pressure is comprised between 10 and 500 Pa. Curtain coater according to any of claims 1 to 6, wherein said air shield is provided with heating means (28). Curtain coater according to any of claims 1 to 7, wherein the distance e between the outlet end of said air shield (26) and said curtain (20) is comprised between 5 and 30 mm.
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AGFA GEVAERT NV; AGFA-GEVAERT NAAMLOZE VENNOOTSCHAP
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GEERTS HENDRIK JOSEF; GHYS JAN JOSEF; MUES WILLEM; GEERTS, HENDRIK JOSEF; GHYS, JAN JOSEF; MUES, WILLEM
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EP-0489980-B1
| 489,980 |
EP
|
B1
|
EN
| 19,980,318 | 1,992 | 20,100,220 |
new
|
D05B57
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D05B57
|
D05B57
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D05B 57/20, D05B 57/14
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Bobbin holding structure
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In accordance with the invention, the bobbin holding member (20, 40, 60, 80) which magnetically adheres is installed in the bobbin case holder (24) which houses the bobbin (25). With this constitution, the bobbin (25) can be securely retained in the bobbin case holder (24) without allowing the bobbin (25) to come off the bobbin case holder (24), during sewing operation. Also because the bobbin holding member (20, 40, 60, 80) is installed in the bobbin case holder (24) freely detachably, the bobbin (25) can be replaced easily resulting improvement of the efficiency of sewing work.
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The invention relates to a bobbin holding structure for detachably mounting a bobbin in a bobbin case holder rotatably mounted but axially locked in a rotating hook of a looptaker said bobbin case holder including a bottom of ferromagnetic material and having an open end. Looptakers of the above type have been produced and delivered in great numbers, are widely known from practice and are shown in Figs. 1-5, in which Fig. 1 is a perspective view of a typical prior art structure, Fig. 2 is a perspective view of a bobbin 5 and Fig. 3 is a perspective view of a bobbin case 6 where the bobbin case 6 is shown partially cut away. A horizontal axis full rotary looptaker 1 provided in a lock stitch sewing machine includes a rotating hook 3 driven by a rotary shaft 2 to rotate around a horizontal axis and a bobbin case holder 4 housed in the rotating hook 3. Bobbin case 6 housing a bobbin 5 fits in the bobbin case holder 4. The bobbin case holder 4 is prevented from rotating by a rotation stopper member 7. When the rotary shaft 2 is rotated, the rotating hook 3 rotates around the rotary axis while the bobbin case holder 4 remains stationary. Fig. 4 is a perspective view of the horizontal axis full rotary looptaker 1 with the bobbin 5 and the bobbin case 6 removed therefrom. Fig. 5 is a partially enlarged perspective view of the bobbin case 6. With reference made also to Fig. 1 through Fig. 3, a stud 9 projects perpendicularly from a bottom 8 of the bobbin case holder 4 to an open end thereof. As shown in Fig. 3, a hollow shaft 10 of straight cylindrical shape is positioned within the bobbin case 6. The hollow shaft 10 is inserted through a central hole 11 of the bobbin 5, and the bobbin 5 is housed in the bobbin case 6. The bobbin case 6 which houses the bobbin 5 is housed in the bobbin case holder 4 with the stud 9 inserted through the hollow shaft 10.When the bobbin 5 is within the bobbin case holder 4, a locking piece 13 which is provided on the bobbin case 6 is locked in a locking groove 12 which is formed at a free end of the stud 9, thereby locking the bobbin case 6 in the bobbin case holder 4. Thus, the bobbin 5 is retained in the bobbin case holder 4 by the bobbin case 6. In order to remove bobbin 5 from the bobbin case holder 4, a pivotable flap 14 is operated to release the lock between the locking piece 13 and the stud 9 and the bobbin case 6 is removed from the bobbin case holder 4 and the bobbin 5 is removed from the bobbin case 6.In such a prior art structure as described above, it takes much time to replace the bobbin, resulting in poor productivity. Moreover, the mechanism for holding the bobbin is complicated.It is an object of the invention to provide a bobbin holding structure which makes it possible to easily attach and detach the bobbin in and from the bobbin case holder, and which is capable of securely holding the bobbin in the bobbin case holder by means of a simple structure and which further has a bobbin thread tensioning function.According to the invention there is provided a bobbin holding structure, which is characterized by a body member in the form of a bar to be mounted at the open end of the bobbin case holder and having opposite ends, at least one of said ends having therein a slot for receiving the open end of the bobbin case holder such that said body member when mounted will extend in a direction of a diameter of the bobbin case holder;a shaft extending perpendicularly from a center of the body member in an axial direction of the bobbin case holder when said body member is mounted thereon, said shaft having a tip end positioned adjacent the bottom of the bobbin case holder when said body member is mounted thereon;an attraction member located at the tip end of said shaft and formed of magnetic material;whereby when a bobbin is mounted in the bobbin case holder, said shaft is passed through a center opening of the bobbin, said body member is positioned at the open end of the bobbin case holder, and magnetic attraction between said attraction member and the bottom of the bobbin case holder retains said body member in position and the bobbin within the bobbin case holder;a bobbin thread tensioner spring having a base end mounted on said body member and a free end elastically abutting said body member, the free end having therein a thread guide slot through which passes a bobbin thread when a bobbin is mounted in the bobbin case holder; andan adjusting screw member extending through the tensioner spring for moving said tensioner spring relative to said body member and thereby adjusting the tension applied to a bobbin thread passing through said thread guide slot.When this bobbin holding member is installed in the bobbin case holder, the body member is disposed in the direction of the diameter of the bobbin case holder and the free end of the bobbin case holder fits in the slot, thereby preventing displacement in the direction of the diameter and ensuring the position of the body with respect to the bobbin case holder. The tip of the shaft extends to adjacent the bottom of the bobbin case holder, and the attraction member provided at the tip magnetically adheres to the bottom, thus retaining the bobbin in the bobbin case holder. This construction makes it possible to change the bobbin easily and quickly, thereby minimizing the time taken to change the bobbin and improving the efficiency of a sewing operation. Also, because the body is equipped with a bobbin thread tensioner spring, the bobbin thread lead extending from the bobbin, retained in the bobbin case holder can be properly tensioned, thereby enabling the formation of stitches of good quality without allowing slack in the thread.Moreover, the bobbin holding structure of the invention makes possible the replacement of only the bobbin case holder unlike the rotating hooks of the prior art, and therefore can be employed with a wide range of rotating hooks in existing sewing machines.It is observed that from CH-A-332,443 (Fig. 8) a looptaker is known, in which magnetic forces are used to keep different parts of the looptaker in their correct relative position. In this known structure the bobbin case holder is axially attracted by a permanent magnet, installed in the bottom of the rotating hook. The bobbin is positioned on the shaft of the bobbin case holder and mechanically locked in that position by a locking member. BRIEF DESCRIPTION OF THE DRAWINGSOther and further objects, features and advantages of the invention will be apparent from the following detailed description, taken with reference to the drawings wherein: Fig.1 is a perspective view of a typical prior art structureFig.2 is a perspective view of a bobbin;Fig.3 is a perspective view of a bobbin case;Fig.4 is a perspective view of a horizontal axis full rotary looptaker with the bobbin and the bobbin case removed therefrom;Fig.5 is a partially enlarged cross sectional view of the bobbin case;Fig.6 is a perspective view of a bobbin case having a magnetic attraction member;Fig.7 is a perspective view of a horizontal axis full rotary looptaker to be equipped with the bobbin case of fig 6,Fig.8 is a perspective view of a bobbin holding member illustrative of a first embodiment of the invention;Fig.9 is an enlarged perspective view of such bobbin holding member;Fig.10 is a partially enlarged perspective view of a bobbin thread tensioner spring;Fig.11 is a perspective view of a bobbin holding member illustrative of a second embodiment of the invention; andFig.12 is a perspective view of a bobbin holding member illustrative of a third embodiment of the invention.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSNow referring to the drawings, preferred embodiments of the invention are described below.Fig.6 is a perspective view of a bobbin case or bobbin holding member 20 illustrative of an embodiment of the invention, and Fig.7 is a perspective view of a horizontal axis full rotary looptaker 21 which may be equipped with the bobbin holding member 20. In Fig.6, the bobbin holding member 20 is shown partially cut away. The horizontal axis full rotary looptaker 21 to be installed in a lock stitch sewing machine is provided with a rotating hook 23 fixed to a rotary shaft 22 which is driven to rotate about a horizontal rotary axis. A bobbin case holder 24 made of a ferromagnetic material such as iron is housed in the rotating hook 23, and the bobbin holding member 20 with a bobbin 25 housed therein is installed in the bobbin case holder 24.A rotation stopper 26 prevents the bobbin case holder 24 from rotating, when the rotating hook 23 is rotated about the rotary axis thereof. In this embodiment, the bottom 27 of the bobbin case holder 24 is flat because it is not necessary to provide a stud 9 as required in the above described prior art structure.The bobbin holding member 20 has a cylindrically shaped shaft 28 which extends along a center center axis 11 thereof. Formed at the tip of the shaft 28 is a recess 29 having fixed therein an attraction member 30 made of a magnetic material e.g. a permanent magnet. By housing the bobbin 25 in such a bobbin holding member 20 and installing it in the bobbin case holder 24, the bobbin 25 can be retained securely in the bobbin case holder 24 by the magnetic attraction of the attraction member 30 to the bottom 27. The bobbin 25 can be easily removed from the bobbin case holder 24 by picking up the bobbin holding member 20 and removing it from the bobbin case holder 24.In another embodiment, installation of a cylindrical attraction member in a hollow shaft 10 of the conventional bobbin case 6 makes it possible to use the conventional bobbin case holder 4. As such, the invention may widely be employed with existing rotating hooks.Fig.8 is a perspective view of the bobbin holding member 40 installed in the horizontal axis full rotary looptaker 21 according to a first embodiment of the invention. Fig.9 is an enlarged perspective view of the bobbin holding member 40. Fig.10 is a partially enlarged perspective view of a bobbin thread tensioner spring 43. Parts which correspond to those of the embodiment mentioned above are designated by like reference numerals. The bobbin holding member 40 includes a body 41 in the form of an elongated bar which is installed at the end face 24a of the bobbin case holder 24 at an axially open end and extends in the direction of the diameter thereof, and a shaft 28 extending perpendicularly from the center of the body 41 in axial direction of the bobbin case holder 24.The body 41 has at opposite ends thereof fitting slots 42a, 42b to accommodate the end face 24a of the bobbin case holder 24. Thus, it is possible to install the bobbin holding member 40 in the bobbin case holder 24 so that the axis of the shaft 28 is coaxial with the center axis of the bobbin case holder. Bobbin thread tensioner 43 has a curved plate shape and has a base end section thereof fixed to body 41 by a screw 44.An adjustment screw 45 freely passes axially through the center of the bobbin thread tensioner spring 43 and is threaded into a screw hole formed in the body 41. Formed at the free end of the bobbin thread tensioner spring 43 is a pressurizing portion 47 which makes elastic contact with one side 41a of the body 41 and pressurizes a bobbin thread 46. A bobbin thread guiding slot 48 is formed in portion 47, as shown in Fig.10. The bobbin thread 46 is passed through the bobbin thread guiding slot 48, and is elastically pressed against the side face 41a by the pressurizing portion 47.By turning the adjustment screw 45 in opposite directions, the force acting on the bobbin thread can be adjusted. Therefore, it is possible to apply a proper tension, by the rotary action of the rotating hook 23, to the bobbin thread 46 removed from the bobbin 25, thereby ensuring a sewing operation conducted with a desired thread tension.Fig.11 is a perspective view of a bobbin holding member 60 illustrative of a second embodiment of the invention. A body 61 of the bobbin holding member 60 has integrally formed therewith a bobbin thread guiding member 62. The bobbin thread guiding member 62 has formed therein a notch 63 through which fits the bobbin thread 46. The bobbin thread 46 removed from the bobbin 25 passes through the bobbin thread guiding slot 48, is elastically pressed by the pressurizing portion 47 against a side face 61a of the body 61, and is passed through the notch 63.This constitution makes it possible to retain the bobbin 25 in the bobbin case holder 24 and, by applying a desired tension to the bobbin thread 46, to remove the bobbin with the desired thread tension. Because the fitting slot 42b (Fig.9) described in relation to the previous embodiment is not formed in this embodiment, the bobbin holding member 60 may be magnetically attracted to the end face 24a of the bobbin case holder 24 by magnetizing the body 61 adjacent a portion or end 64 thereof. By such arrangement, the bobbin holding member 60 can be installed securely without lateral displacement thereof relative to the end face 24a of the bobbin case holder 24 during a sewing operation.Fig.12 is a perspective view of a bobbin holding member 80 illustrative of a third embodiment of the invention. A bobbin thread tensioner spring 82 is installed on the base end section of the body 81 of the bobbin holding member 80 by a set screw 83. The body 81 is made of a magnetic material so that the bobbin thread tensioner spring 82 is magnetically attracted and thereby presses the bobbin thread 46 against a side face 81a.Formed at a free end of the bobbin thread tensioner spring 82 is a pressurizing portion 84 having formed therein a bobbin thread guiding slot 85. Formed between the base end section and the free end section of the bobbin thread tensioner spring 82 is a mounting section 87 through which is threaded an adjustment screw 86. A tip end of the screw 86 is in contact with a top face 81b of the body 81. By turning screw 86 in opposite directions it is possible to displace bobbin thread tensioner spring 82 angularly about the set screw 83 thus changing the contact length of the bobbin thread 46 interposed between the pressurizing portion 84 and the side face 81a of the body 81.When such contact length is increased, a friction force applied to the bobbin thread is increased, and when such length is decreased the friction force is decreased. This makes it possible to apply a proper tension to the bobbin thread 46 to perform a sewing operation at the desired thread tension.As described above, by means of the bobbin holding members 40, 60 and 80 in accordance with the invention, it is possible to apply a proper tension to the bobbin thread removed from the bobbin 25 and perform a sewing operation at the desired thread tension.
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A bobbin holding structure for detachably mounting a bobbin (25) in a bobbin case holder (24) rotatably mounted but axially locked in a rotating hook (23) of a looptaker (1) said bobbin case holder (24) including a bottom (27) of ferromagnetic material and having an open end (24a), characterized by a body member (41, 61, 81) in the form of a bar to be mounted at the open end (24a) of the bobbin case holder (24) and having opposite ends, at least one of said ends (42a, 42b) having therein a slot for receiving the open end (24a) of the bobbin case holder (24) such that said body member when mounted will extend in a direction of a diameter of the bobbin case holder (24);a shaft (28) extending perpendicularly from a center of the body member (41, 61, 81) in an axial direction of the bobbin case holder (24) when said body member (41, 61, 81) is mounted thereon, said shaft (28) having a tip end positioned adjacent the bottom (27) of the bobbin case holder (24) when said body member (41, 61, 81) is mounted thereon;an attraction member (30) located at the tip end of said shaft (28) and formed of magnetic material;whereby when a bobbin (25) is mounted in the bobbin case holder (24), said shaft (28) is passed through a center opening (11) of the bobbin (25), said body member (41, 61, 81) is positioned at the open end (24a) of the bobbin case holder (24), and magnetic attraction between said attraction member (30) and the bottom (27) of the bobbin case holder (24) retains said body member (41, 61, 81) in position and the bobbin (25) within the bobbin case holder (24);a bobbin thread tensioner spring (43, 82) having a base end mounted on said body member (41, 61, 81) and a free end elastically abutting said body member (41, 61, 81), the free end having therein a thread guide slot (48, 85) through which passes a bobbin thread (46) when a bobbin (25) is mounted in the bobbin case holder (24); andan adjusting screw member (45, 86) extending through the tensioner spring (43, 82) for moving said tensioner spring (43, 82) relative to said body member (41, 61, 81) and thereby adjusting the tension applied to a bobbin thread (46) passing through said thread guide slot (48, 85).
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HIROSE MFG CO LTD; HIROSE MANUFACTURING COMPANY LIMITED
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HIROSE TOKUZO; HIROSE, TOKUZO
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EP-0489984-B1
| 489,984 |
EP
|
B1
|
EN
| 19,950,927 | 1,992 | 20,100,220 |
new
|
A22C21
| null |
A22C21
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A22C 21/00G, A22C 21/00
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Method for controlling the processing of poultry, and device for carrying out this method
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Method for controlling the processing of poultry in different production lines (13, 14, 15) operating in parallel, wherein the control of the processing of a specific bird (30) or a part thereof takes place on the basis of data derived from one or more observed contours of the bird (30) or a part thereof. For purposes of the control the data may be supplemented by the weight of the bird (30) or part thereof. In a device for carrying out the method the observation takes place with the aid of one or more radiation sources (36) which transmit radiation rays (34) to one or more radiation detectors (40), which radiation rays (34) can be interrupted or weakened by the birds (30) or parts thereof.
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The invention relates to a method for controlling the processing of poultry or a part thereof, having at least a breast or a back, in a slaughterhouse in one or more production lines operating in parallel, comprising the steps of: conveying a bird or part thereof along a predetermined path; directing radiation across the path; and detecting radiation from the path when conveying the bird or part thereof along the path. The invention also relates to a device for carrying out this method. Such a method is known from US-A-4 627 007, which discloses a system in which the beginning and the end for the path of an injection needle in a poultry carcass is established using two photodetectors each measuring a single isolated point of the outer contour of the carcass. The measurement data are used for controlling the setting of the processing system. Generally speaking, the processing of poultry in a slaughterhouse intended for the purpose takes place using different machines, each of which carries out a specific operation on a bird or part of a bird. These machines, which, for example, cut off heads, cut off necks, eviscerate the birds and joint the carcass, are arranged in a logical sequence along conveyor lines, and thus form production lines along which the birds are conveyed, hanging by the two legs from a hook, in order to undergo the successive processing operations. The poultry supplied to the slaughterhouse is not uniform in body build and/or weight, even if it comes from the same flock (a collection of birds belonging together), which means, for example, that variations of up to 20% in the size of body parts may occur between individual birds coming from the same flock or reared under comparable conditions. On the other hand, a great variety of products is desired by the customers of the slaughterhouse. In order to make it possible to meet current customer demands in the optimum manner, bifurcations are fitted at certain points on the conveyor lines, which bifurcations are in general formed by automatic overhang machines which are known per se, and where according to the state of the art it is decided on the basis of the weight of each bird and/or on the basis of a visual inspection which conveyance route must be followed from the bifurcuration. It is important here that the most suitable processing should be carried out on the birds on the machine most suitable for that purpose, resulting in the maximum production output. In the prior art, it is only possible to a very partial extent to guide each bird or part of a bird to the most suitable processing machine, i.e. at a bifurcation in a conveyor line to determine the most suitable path to control an automatic overhang machine, because the means for determining the characteristics of the birds (shape, size of the breast and/or the legs, injuries etc.) on the basis of which a decision has to be made are non-existent or, in the case of a visual inspection, are inadequate, in particular at high speeds at which the birds are conveyed along the conveyor line. The object of the method and device according to the invention is to eliminate the above-mentioned disadvantages. The method according to the invention, in which radiation is directed across a conveyance path of a bird or part thereof, and radiation is detected from the path, is to that end characterized in that the bird or part thereof is conveyed with its breast or its back essentially facing the radiation detectors, and that the detection results are evaluated to derive therefrom the shape of the contour of at least a portion of the bird or part thereof, whereafter the processing of the bird or part thereof is controlled in response to the shape of the contour. Determining the shape of a contour of a bird or part thereof, possibly combined with the determination of its weight, produces important advantages. Important data for controlling the processing of poultry can be derived from the contour, which is an image of a boundary of a bird or a part thereof, at right angles to the direction of observation. If a choice has to be made between which of two or more identical machines operating in parallel and set for different bird sizes a bird or a part thereof must be fed to for optimum processing, it is possible on the basis of the data obtained to select a machine which is best suited to the specific size of the bird or a part thereof. The data can, of course, also be used directly for controlling the setting of a processing machine adapted to it. For a bird, such data preferably comprises the position of the neck/head transition, the shoulder/neck transition, the hip joints and the rump. The neck/head transition gives the correct position for cutting off the head, the shoulder/neck transition gives the correct position for cutting off the neck, the hip joints form a reference for cutting off legs and jointing, and the position of the rump, together with the position of the shoulder/neck transition, is particularly important as a reference point for evisceration. If the observation takes place while the birds or parts thereof are in motion, the production need not be interrupted for it. A device by which the above-mentioned observation can be carried out effectively comprises a conveyor for conveying a bird or part thereof along a predetermined path; one or more radiation sources for transmitting radiation across the path; and one or more radiation detectors for detecting radiation from the path, each detector producing an output signal corresponding to the detected radiation, and is characterized by a conveyor which is adapted for conveying a bird or part thereof with its breast or its back essentially facing the radiation detectors; evaluating means which are adapted for deriving from the detector output signals the shape of the contour of at least a portion of the bird or part thereof; and processing control means which are adapted for controlling the processing of the bird or part thereof in response to the output of the evaluating means. A bird moving past can interrupt or weaken the radiation and thus modulate the output signal of one or more radiation detectors. The evaluation of the detector output signals produces the shape of the contour of the bird or a part thereof, at right angles to the radiation rays. Using image analysis techniques, it is possible to establish from the observed contour not only the positions of body parts of the birds, but also any damage (for example, a broken wing) or other irregularities. The most contour data are obtained if the conveyor is adapted for conveying a bird or part thereof with its breast or its back essentially facing the radiation detectors, since in that case the fewest number of body parts will be situated at the shadow side of the bird or part thereof, where they cannot be detected. The radiation used for the observation may comprise visible or non-visible radiation or a combination of different kinds of radiation, depending on the part of the bird to be observed. For the observation of contours of internal parts of the body, e.g. bones or organs, Röntgen radiation may be used. For the observation of contours of body outer parts the radiation preferably consists of visible light or infrared radiation. In a preferred embodiment the observation takes place with the aid of a row of radiation detectors, the radiation sources being adapted for transmitting parallel radiation rays to the radiation detectors With this embodiment, a combination of the various detector output signals can be interpreted to produce the contour of at least a portion of the bird or a part thereof. The position in which birds are fed through the radiation rays will generally be upside down, hanging by both legs from a hook which is movable in a conveyor line. Then, advantageously, the row of radiation sources as well as the row of radiation detectors are set up vertically. Other positions of the bird or part thereof are, of course, also possible for certain operations, for example on the back for filleting the breast, where the method according to the invention can be used to advantage. Of course, it is possible to determine various contours of a bird or a part thereof, e.g. a leg, from different observation directions, so that the surface of the piece of poultry can be reconstructed in more than two dimensions with the aid of suitable calculating devices. This could be, for example, observation of the birds at the breast side and at a hip side, to determine the breast dimensions. The invention is explained with reference to the drawing, in which: Fig. 1 shows a schematic general view of a possible arrangement of processing machines, c.q. processing stations, in a slaughterhouse; Fig. 2 shows a front view of a preferred embodiment of the device according to the invention; Fig. 3 shows a side view of a part of a similar device to that of Fig. 2; and Figs. 4A to 4L show time charts of signals from the detectors of Fig. 3. The same reference numbers relate to the same parts in the figures. Fig. 1 schematically shows an arrangement of processing machines, indicated by rectangular boxes, places on conveyor lines 1, 2, 3, 4, 5, 6 and 7, along which birds or parts thereof are carried in the direction indicated by arrows. In processing machine 10 the still live birds fed in are stunned and stuck, following which the birds are left to bleed dry. The birds are then plucked in processing machine 11. At bifurcation 12 between the conveyor lines it must then be determined to which oven-ready line 13, 14 or 15 the birds are to be conveyed. The oven-ready lines 13, 14 and 15 are each set for a specific size of bird; oven-ready line 13 is, for example, set for relatively small birds, oven-ready line 14 for medium-sized birds, and oven-ready line 15 for relatively large birds. Before the bifurcation 12 the contour and weight of a bird are determined, following which an overhang machine in bifurcation 12 is controlled in such a way that each bird is conveyed on conveyor lines 2, 3 or 4 to the respective oven-ready line 13, 14 or 15 of which the setting is most suitable for the processing of that bird. The bifurcation, like other bifurcations, contains buffers which prevent one of the following conveyor lines from being supplied with too many birds which cannot be processed. Bifurcations 16, 17 and 18 respectively are placed at the end of the conveyor lines 2, 3 and 4 passing through the oven-ready line, in order to make it possible to take birds, for example, along conveyor line 5 to a processing station 19 for damaged birds, along conveyor line 6 to a processing station 20 for undamaged birds of a certain weight, with the object of smoking or deepfrying them there, or along conveyor line 7 to processing station 21 for removal of certain parts of the body, for example the breast or the legs. The bifurcations 16, 17 and 18 are preceded by determination of the contour and the weight of each bird or part thereof conveyed there, and on the basis of these data an overhang machine in the bifurcations 16, 17 and 18 is controlled, so that each bird is conveyed to the processing station 19, 20 or 21 for which the bird is most suitable. Fig. 2 shows a bird 30, hanging by the legs from a hook 32, which bird is guided through a plurality of parallel radiation rays 34 in a direction at right angles to the plane of the drawing. The radiation rays 34 come from radiation sources 36 which are fitted on a bar 38, and are directed at the same number of radiation detectors 40 fitted on a bar 42. If the bird is guided through the plurality of radiation rays 34, the radiation from the radiation sources 36 on the radiation detectors 40 will be interrupted or weakened in a certain pattern. This is discussed in greater detail with reference to Figs. 3 and 4. Fig. 3 shows the bird 30 hanging from the hook 32 being moved along a conveyor rail 50 at a certain speed in the direction of the arrow, by drive means which are not shown in any further detail. The hook 32 is for this purpose provided with a roller 52 which is rotatable about a shaft 54. The bird 30 is moved past in front of a bar 38 disposed on a fixed base 56, on which bar 38 twelve light sources 36 which emit light rays are fitted at right angles to the direction of conveyance. The bird 30 thus temporarily interrupts the light rays coming from the light sources 36. The output signal thus produced by the twelve light detectors (not shown) belonging to the light sources is shown in Figs. 4A to 4L, in which Fig. 4A represents the output signal from the light detector belonging to the uppermost light source 36, Fig. 4B the output signal from the light detector belonging to the light source 36 below it, and so on. Figs. 4A to 4L also indicate by L ( light ) the signal level going with the receipt of light from the light source 36, while the signal level going with the absence of light is indicated by D ( dark ). The time t is plotted on the horizontal axis. It can be seen from Figs. 3 and 4 that a horizontal dimension of the bird at the level of a light source can be determined by multiplying the dark period of time in the appropriate light detector by the average horizontal speed of the bird during the period. The accuracy of the measurement is limited by the dimensions of the components in the optical circuit. Since the light sources are discrete, also in the vertical direction a limited resolution is achieved. For example, it can be deduced from the combination of the signals according to Figs. 4B and 4C, through halving of the light interruption frequency, that the rump of the bird 30 is lying at a level somewhere between the level of the corresponding light detectors. The uncertainty in the level determination thus amounts to the centre-to-centre distance between the light sources/light detectors plus the dimensions of the components in the optical circuit, and can be reduced by selecting a greater density of light sources and light detectors in the vertical direction and/or using smaller components. The contour of each bird can be determined in this way. The position of the hip joint within the contour can also be determined approximately from the shortening and the lengthening of the duration of the dark period when the signals according to Figs. 4C, 4D and 4E are compared. The position of the neck/head transition on the contour follows from the shortening and lengthening of the dark period when the signals according to Figs. 4J, 4I and 4H are compared. The position of the neck/shoulder transition on the contour follows from comparisons of the duration of the dark period in the signals according to Figs. 4G and 4H.
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Method for controlling the processing of poultry or a part thereof, having at least a breast or a back, in a slaughterhouse in one or more production lines (13, 14, 15) operating in parallel, comprising the steps of: conveying a bird (30) or part thereof along a predetermined path; directing radiation (34) across the path; and detecting radiation from the path when conveying the bird (30) or part thereof along the path, characterized in that the bird (30) or part thereof is conveyed with its breast or its back essentially facing the radiation detectors (40), and that the detection results are evaluated to derive therefrom the shape of the contour of at least a portion of the bird (30) or part thereof, whereafter the processing of the bird or part thereof is controlled in response to the shape of the contour. Method according to claim 1, characterized in that the radiation detection takes place while the bird (30) or part thereof is in motion. Method according to claim 1 or 2, characterized in that the position of an outer body part with respect to the rump is derived from the evaluated contour. Method according to claim 3, characterized in that the position of the neck/head transition, the position of the shoulder/neck transition, the position of the hip joints and the position of the rump are derived from the evaluated contours. Method according to any of claims 1-4, characterized in that the weight of the bird or part thereof is established, and additionally the processing of the bird or part thereof is controlled in response to said weight. Device for carrying out the method according to any of claims 1-5, comprising: a conveyor for conveying a bird (30) or part thereof along a predetermined path; one or more radiation sources (36) for transmitting radiation (34) across the path; and one or more radiation detectors (40) for detecting radiation from the path, each detector producing an output signal corresponding to the detected radiation, characterized by a conveyor which is adapted for conveying a bird (30) or part thereof with its breast or its back essentially facing the radiation detectors (40); evaluating means which are adapted for deriving from the detector output signals the shape of the contour of at least a portion of the bird or part thereof; and processing control means which are adapted for controlling the processing of the bird or part thereof in response to the output of the evaluating means. Device according to claim 6, characterized in that each radiation source is adapted for transmitting visible light or infrared radiation. Device according to claim 6 or 7, characterized by a row of radiation sources (36) which are set up opposite a row of radiation detectors (40), the radiation sources being adapted for transmitting parallel radiation rays (34) to the radiation detectors. Device according to claim 8 for controlling the processing of a bird (30) or a part thereof hanging free, characterized in that the row of radiation sources (36) as well as the row of radiation detectors (40) are set up vertically.
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STORK PMT; STORK PMT B.V.
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PERSOON NICOLAAS WILHELMUS COR; VAN DEN NIEUWELAAR ADRIANUS JO; PERSOON, NICOLAAS WILHELMUS CORNELIS; VAN DEN NIEUWELAAR, ADRIANUS JOSEPHES
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EP-0489987-B1
| 489,987 |
EP
|
B1
|
EN
| 19,950,125 | 1,992 | 20,100,220 |
new
|
H01F41
| null |
H01F41
|
H01F 41/12A
|
Insulating tape for winding coils
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An insulating tape for winding coils which includes a guide sheet (2) having a predetermined width and a plurality of narrow insulating strips (3) provided with adhesive on both surfaces thereof and removably connected to the guide sheet at predetermined spaces, facilitating accurate winding of insulating strips on a bobbin (10) or the like and further enabling the winding operation to be carried out automatically.
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INSULATING TAPE FOR WINDING COILSThis invention relates to an insulating tape used for producing winding coils which are usually used in electric apparatus such as home electric appliances or in electronic devices used in telecommunication systems or the like. In electric apparatus such as home electric appliances or in electronic devices used in telecommunication systems or the like, the winding coils used as the switching transformers or the like usually have the construction as shown in Fig. 3, with wirings 21 and insulated tape 22 alternately wound on a bobbin 10. The bobbin 10 has rim portions 12 and 13 provided on both ends of a body portion 11 thereof, as shown in Fig. 4. One of the rim portions, for example, the rim portion 12, has a plurality of terminal portions 14 projected from a side surface. These bobbins 10 usually are given a common configuration instead of preparing several kinds of bobbins with different configurations for each winding coil. An insulating layer is usually formed on the body portion 11 of the bobbin 10 by winding narrow, insulating strips on the two side edge portions or one of the side edge portions, depending on the amount of wiring to be wound on the bobbin or the width of the winding in each winding layer. The manufacturing steps for producing the winding coil explained above illustrated in Fig. 5-A to 5-F. In these figures, each bobbin 10 is shown schematically. One of the rim portions 12 thereof is omitted from each drawing to make them more understandable. First, narrow insulating strips 23 having a predetermined width are wound on both side edge portions of the body portion 11 to form ridged portions 23A and 23B, respectively (as shown in Fig. 5-A). When an end portion of the wiring material 21 is terminated with a predetermined terminal 14, not shown in Fig. 5-B, it is wound on the body portion 11 of the bobbin 10 starting at the edge portion of the ridged portion 23A (as shown in Fig. 5-B). After a certain amount of the wiring material 21 is wound on the body portion 11 along a longitudinal direction thereof and when the wiring martial 21 reaches a position on which of end portion of the other ridged portion 23B exists (as shown in Fig. 5-C), an adhesive is coated over of whole surface of the wiring material 21 just wound on the body portion 11, then a predetermined amount of an insulating tape 22 having the same width as that of the body portion 11 is wound on the adhesive layer. After that, the wiring material 21 is folded on the surface of the insulating tape 22 toward the terminal 14 (as shown in Fig. 5-D). When the wiring material 21 is entangled with the terminal 14, a predetermined amount of the insulating tape 22 is wound again on the body portion 11 to cover the wiring material 21 arranged on the previously wound insulating tape 22 (as shown in Fig. 5-E). After a first wiring layer is formed by the operation as explained above, two further narrow insulating strips 23 having a predetermined width are wound on the two end portions of the insulating tape 22 to form two further ridged portions 23A and 23B (as shown in Fig. 5-F). Then, the wire winding operation as explained above is again carried out to form a second wiring layer, etc. Finally, a wiring coil is produced provided with a plurality of wiring layers, as shown in Fig. 3. As explained above, the wiring coil thus produced includes the narrow insulating strips 23 which form the ridged portions 23A and 23B as insulated layers. However, the narrow insulating strips have extremely small stiffness and strength since they are 0.05 to 1.0mm in thickness and 2 to 10mm in width. Accordingly, when the narrow insulating strips 23 are wound on the bobbin 10 or on a surface of the wiring material 21, the insulating strips 23 are twisted even with a slight tension applied thereto. This makes it difficult for the insulating strips 23 to be wound precisely on a predetermined place. Also, when tension is applied to the insulating strips 23, they are deformed, for example, are reduced in the thickness or the width, or are broken, to make it difficult to form a predetermined insulating layer. Therefore insulating strips having relatively high stiffness and strength should be used. Further, the operator should wind the insulating strips on the bobbin with a great care so as not to apply unnecessary tension thereto. These problems cause extremely low operational efficiency for producing the wiring coils. The need to provide coil winding separated by insulation tape and including, on the bobbin, spaced apart narrow insulating strips also arises during the manufacture of transformers. Thus JP-A-1-71112 discloses the alternate application, around a bobbin of, firstly an insulation tape to which is permanently attached a pair of spaced apart narrow corrugated insulation strips which, on application, project radially outwardly of the bobbin, then an array winding of copper wire disposed on the insulation tape and between the corrugated insulation strips and then another insulation tape of the same construction as the first tape, and so on. The present invention seeks to provide an insulating tape for winding coils which facilitates accurate winding of insulated strips on a bobbin or the like in a wiring coil producing method and further enables the winding operation to be carried out automatically. According to one aspect the present invention provides a tape comprising a backing sheet having a predetermined width and, removably secured thereto, a strip of material provided on both surfaces of the material with adhesive, characterized in that the backing sheet has secured thereto a plurality of strips in a predetermined spaced relationship with one another, which strips are narrow strips of insulating material, two said strips being arranged at opposite longitudinal edges of the backing sheet, whereby the strips may be applied to a winding coil, the backing sheet being capable of serving as a guide sheet during the said application and thereafter being capable of removal from the strips. According to another aspect, the invention provides a method of applying narrow strips of insulating material to a bobbin during production of a winding coil, which method comprises rotating the bobbin and supplying thereto a tape comprising a guide sheet having a predetermined width and to which the strips are secured in a predetermined spaced relationship with one another, the strips facing the bobbin during the supply thereto of the tape so as to provide on the bobbin a channel between respective strips spaced longitudinally apart from one another on the bobbin, which channel is thereby arranged to accommodate a coil of wire wound around the bobbin, characterized in that the strips have adhesive on both surfaces thereof and are releasably secured to the guide sheet, the method additionally including the steps of pressing the tape into contact with the bobbin so that the strips adhere thereto and removing the guide sheet from the tapes. A preferred embodiment of the invention will now be described in more detail with reference to the accompanying drawings, wherein Figure 1 is a schematic perspective view of one embodiment of an insulating tape for winding coils of the present invention; Figure 2 is a schematic view of one embodiment of a winding operation of an insulating tape for winding coils of the present invention; Figure 3 is a schematic cross-sectional view of one embodiment of a wiring coil; Figure 4 is a schematic perspective view of one embodiment of a construction of a wiring coil used in the present invention; and Figures 5A to 5F are schematic views of steps in a wiring coil producing method. As explained above, the insulating tape 1 for winding coils of the present invention includes guide sheet 2 having a predetermined width and a plurality of narrow insulating strips 3 provided with adhesive on both surfaces thereof and removably connected to the guide sheet at predetermined spaces. The guide (release) sheet 2 is made of a nonadhesive sheet-like material, such as paper or plastic film. The insulating strips 3 are preferably made of an epoxy resin impregnated fabric tape. In the illustrated case they are provided along the edge margins of the sheet 2. The insulating tape for winding coils 1 of the present invention is wound on a reel 4 or the like made of paper or plastic. At one end, there is a portion on which the narrow insulating strips 3 are not provided, to form a portion 2a to be wound on a winding reel 5. When a wiring coil is produced utilizing the insulating tape 1, as shown in Fig. 2, the reel 4 on which the insulating tape is wound is mounted on a chuck (not shown) rotatably supported on a machine frame (not shown) or a movable arm (not shown) moving in both vertical and horizontal directions, then the end of the guide sheet 2 is withdrawn from the reel 4 and wound on a reel 5. After this preparatory operation is completed, the wiring winding operation and the insulated tape 22 winding operation are started. The narrow insulating strips 3 are wound on a bobbin 10 while moving a pressing means 30 or a movable arm to a surface of the bobbin 10 or a surface of wound insulated tape 22 to make the insulating strips 3 contact the surface while the bobbin is rotated. Therefore, the insulating strips 3 are adhered to the end surfaces of the bobbin in predetermined lengths by the rotation of the bobbin 10 to form the ridge portions 3A and 3B, respectively. After the predetermined lengths of the insulating strips 3 are wound on the bobbin 10, the rotation of the bobbin is stopped. The pressing means 30 is removed from a contact position X at which the insulating strips 3 contact the surface of the bobbin and is moved to a position Y at which the insulating strips 3 do not contact the surface of the bobbin. Simultaneously with this movement of the pressing means 30, the insulating strips 3 are cut with a suitable cutter (not shown). Then, the rotation of the winding bobbin 5 for winding the guide sheet 2 is stopped. After that, the bobbin 10 is started rotating to wind the wiring material 21 delivered from a reel 40 through a suitable guide member 41 onto the surface of the bobbin 10 and between the ridge portions 3A and 3B. After a predetermined amount of wiring material 21 is wound on the bobbin, insulating tape 22 delivered from a reel 30 through a suitable guide member 31 is wound on the bobbin 10 to cover the wiring material 21 and the ridge portions 3A and 3B. If required, a portion of the wiring material 21 is folded on the surface of the insulating tape 22 and covered with the tape 22 during the sheet winding operation as shown in Figs. 5-D and 5-E. Then, the pressing means 30 is again moved to the position X to bring the insulating strips 3 into contact with the surface of the insulating sheet previously wound thereto and covering a portion of the wiring material 21 to form stacked ridge portions. The same operation as explained above is repeated. In this operation, the guide sheet 2 provided with the insulating strips 3 is guided by the rim portions 12 and 13 of the bobbin. As explained above, since the insulating tape 1 of the present invention includes a guide sheet 2 having a wide width and a plurality of narrow insulating strips provided with adhesive on both surfaces thereof and since the guide sheet 2 has relatively high stiffness and high strength, there is no deformation or twisting due to tension or other external force applied thereto. Accordingly, the narrow insulating strips can be accurately wound on the surface portion of the bobbin alongside the rim portions 12 and 13. On the other hand, the guide sheet 2 is wound on the reel 5 after the narrow insulating strips 3 are removed therefrom and wound on the surface of the bobbin 10. Using the insulating tape for winding coils of the present invention, the narrow insulating strips can be precisely wound at predetermined defined positions of the bobbin just by arranging an end of the guide sheet at a predetermined winding position with respect to the bobbin. Also, an insulating layer having predetermined dimensions can be formed without deformation or twisting of the narrow insulating strips caused by tension or the like in the winding operation, since the narrow insulating strips are placed on the guide sheet. Moreover, the operation for winding the narrow insulating strips on the surface of the bobbin can be carried out utilizing an automatic apparatus, resulting in improved production efficiency in the wiring coil production.
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A tape comprising a backing sheet having a predetermined width and, removably secured thereto, a strip (3) of material provided on both surfaces of the material with adhesive, characterized in that the backing sheet has secured thereto a plurality of strips (3) in a predetermined spaced relationship with one another, which strips (3) are narrow strips of insulating material, two said strips being arranged at opposite longitudinal edges of the backing sheet whereby the strips (3) may be applied to a winding coil, the backing sheet being capable of serving as a guide sheet (2) during the said application and thereafter being capable of removal from the strips (3). A tape according to claim 1, wherein each strip (3) consists of an epoxy resin impregnated fabric. A method of applying narrow strips (3) of insulating material to a bobbin (10) during production of a winding coil, which method comprises rotating the bobbin (10) and supplying thereto a tape comprising a guide sheet (2) having a predetermined width and to which the strips (3) are secured in a predetermined spaced relationship with one another, the strips (3) facing the bobbin (10) during the supply thereto of the tape so as to provide on the bobbin (10) a channel between respective strips (3) spaced longitudinally apart from one another on the bobbin, which channel is thereby arranged to accommodate a coil of wire (21) wound around the bobbin, characterized in that the strips (3) have adhesive on both surfaces thereof and are releasably secured to the guide sheet (2), the method additionally including the steps of pressing the tape into contact with the bobbin (10) so that the strips (3) adhere thereto and removing the guide sheet (2) from the tapes. A method according to claim 3, wherein two said narrow strips (3) of insulating material are arranged at respective opposite longitudinal edges of the guide sheet (2). A method according to claim 3 or claim 4, wherein each strip (3) consists of an epoxy resin impregnated fabric.
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FUJI ELECTROCHEMICAL CO LTD; TORAY ENG CO LTD; FUJI ELECTROCHEMICAL CO.LTD.; TORAY ENGINEERING CO., LTD.
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KAMBARA KENJI; KAMBARA, KENJI
|
EP-0489988-B1
| 489,988 |
EP
|
B1
|
EN
| 19,970,305 | 1,992 | 20,100,220 |
new
|
E01C11
|
E04B1
|
F16B13, E01C11, E04B1
|
E04B 1/48, E01C 11/14, F16B 13/14C
|
Concrete dowel placement sleeves
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Slip and non-slip dowel placement sleeves (10,100) are disclosed. The slip dowel placement sleeve (10) generally comprises a tubular dowel receiving sheath (12) having a closed distal end (14) and an open proximal end (16). A connecting means of perpendicular flange (18) is formed around the proximal opening (16) of the sheath to facilitate attachment of the sheath to a concrete form (30). Smooth sections of dowel rod (42) may then be advanced through holes drilled in the concrete form (30) and into the interior compartment of the sheath (12). Concrete (36) is poured within the form (30) and the dowel rod (42) remains slidably disposed within the interior of the sheath (12). Variations of the basic slip dowel placement sleeve (10) of the invention includes a tapered extractable sleeve (100) and a Corrugated grout tube (200) for placement of non-slip dowel or rebar (400).
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The invention pertains generally to the art of concrete construction and more particularly to devices for facilitating placement of slip and/or non-slip dowel rods within adjacent concrete slabs. In the art of concrete construction, it is commonplace to form cold joints between two or more poured concrete slabs. Such cold joints frequently become uneven or buckled due to normal thermal expansion and contraction of the concrete and/or compaction of the underlying soil caused by inadequate substrate preparation prior to pouring of the concrete. As a means of preventing buckling or angular displacement of such cold joints, it is common practice to insert smooth steel dowel rods generally known as slip dowels within the edge portions of adjoining concrete slabs in such a manner that the concrete slabs may slide freely along one or more of the slip dowels, thereby permitting linear expansion and contraction of the slabs while at the same time maintaining the slabs in a common plane and thus preventing undesirable buckling or unevenness of the cold joint. In order to function effectively, slip dowels must be accurately positioned parallel within the adjoining concrete slabs. If the dowels are non-parallel positioned, such will prevent the desired slippage of the dowels and will defeat the purpose of the slip dowel application. Additionally, the individual dowels must be placed within one or both of the slabs in such a manner as to permit continual slippage or movement of the dowel within the cured concrete slab(s). In the prior art, two methods of installing smooth slip dowels have become popular. According to the first method, a first concrete pour is made within a pre-existing form. After the first pour has cured, an edge of the form (usually wooden stud) is stripped away. A series of holes are then drilled parallel into the first pour along the exposed edge from which the form has been removed. The depth and diameter of the individual holes varies depending on the application and the relative size of the concrete slabs to be supported. As a general rule, however, such holes are at least 0.305 m (12 ) deep and typically have a diameter of approximately 1.54cm (5/8 ). After the parallel aligned series of holes has been drilled into the first pour, smooth dowel rods are advanced into each such hole such that one end of each dowel rod is positioned within the first pour and the remainder of each dowel rod extends into a neighboring area where a second slab of concrete is to be poured. Thereafter, concrete is poured into such neighboring area and is permitted to set with the parallel aligned dowels extending thereinto. After the second pour has set, the slip dowels will be held firmly within the second slab but will be permitted to slide longitudinally within the drilled holes of the first slab thereby accomodating longitudinal expansion and contraction of the two slabs while at the same time preventing buckling or angular movement therebetween. Although the above described drilling method of placing slip dowels has become popular, it will be appreciated that such method is extremely labor intensive. In fact, it takes approximately ten minutes to drill a 1.54 cm (5/8 ) diameter by 0.305 m (12 ) long hole into the first pour and the drilling equipment, bits, accessories, and associated set up time tends to be very expensive. Moreover, the laborers who drill the holes and place the slip dowels must be adequately trained to insure that the dowels are arranged perpendicular to the joint but parallel to one another so as to permit the desired slippage during subsequent use. The second popular method of placing slip dowels involves the use of wax treated cardboard sleeves positioned over one end of each individual dowel. According to such method, a series of holes are drilled through one edge of a concrete form and smooth dowels are advanced through each such hole. Wax treated cardboard sleeves are placed over one end of each such dowel and the first pour is made within the form. After the first pour has set, the previously drilled form is stripped away leaving the individual dowels extending into a neighboring open space where the second pour is to be made. Subsequently, the second pour is made and permitted to cure. Thereafter, the slip dowels will be firmly held by the concrete of the second pour but will be permitted to longitudinally slide against the inner surfaces of the wax treated cardboard sleeves within the first pour. Thus, the waxed cardboard sleeves facilitate longitudinal slippage of the dowels, while at the same time holding the two concrete slabs in a common plane, and preventing undesirable buckling or angular movement thereof. This second method, while presently popular, is nonetheless associated with numerous deficiencies. For example, after the first pour has been made, the free ends of the dowels are likely to project as much as 10.46 m (18 ) through the forms and into the open space allowed for the second pour. Because the drilled section of form must be advanced over these exposed sections of dowel to accomplish stripping or removal of the form, it is not infrequent for the exposed portions of the dowels to become bent and, thus, nonparallel. Also, the drilled section of form may become damaged or broken during the removal process, thereby precluding its reuse. It is unfortunate that both of the above described popular methods of placing slip dowels often result in the dowels being finally positioned at various angles rather than in the desired parallel array. When such occurs, the necessary slippage of the dowels is impeded or prevented. In other applications wherein longitudinal slippage of the dowels is not desired, it is common to employ non-slip dowels or rebar disposed through two or more adjacent concrete pours. Because it is sometimes desirable to insert such non-slip dowels or rebar into a prepoured and set concrete slab, it is further desirable to provide apparatus to facilitate insertion and or grouting in place of such rod, without the need for drilling or cutting of the existing concrete slab. Concrete dowel placement apparatus has been proposed in EP-A-0 328 484 comprising a tubular dowel receiving sheath having an outer surface and a hollow interior compartment extending axially therein attached to a flat surface of a concrete form, said sheath having an open proximal end and an integrally formed closed distal end, and a flange at said open proximal end for mounting the apparatus to said concrete form, said flange being formed completely about and extending perpendicularly from said open proximal end and having a peripheral edge, an inner surface which is directed toward the closed distal end of the sheath, and an outer surface having a generally planar configuration for placement into abutting contact with the flat surface of the concrete form to prevent seepage of concrete into said interior compartment of said sheath. Whilst such an arrangement overcomes many of the deficiencies discussed above, there remains a need to provide reliable apparatus which is particularly strong and unlikely to become mis-shapen. In accordance with the present invention, there is provided concrete dowel placement apparatus generally of the type disclosed in EP-A-0 328 484, characterised in that said sheath is of generally rounded cylindrical configuration with a substantially constant wall thickness, and in that at least one strength imparting gusset is provided having a first side extending along the inner surface of the flange and terminating inwardly of the peripheral edge, a second side extending along a proximal portion of the outer surface of said sheath, and a third side extending between the first and second sides, said third side having a length substantially exceeding the length of the first side. Preferably, the flange at the open proximal end has a generally rectangular configuration and may be provided with apertures for receiving fasteners to facilitate attachment to a concrete form. These as well as other features of the present invention will become more apparent upon reference to the drawings wherein: Figure 1 is a perspective view of a dowel placement apparatus in the form of a sleeve, in accordance with the present invention. Figure 2 is a perspective view of three such sleeves nailed to a section of wooden concrete form. Figure 3 is a cutaway view of a poured concrete slab abutted by a section of wooden concrete form and having a plurality of such sleeves extending thereinto. Figure 4 is a cutaway perspective view of a poured concrete slab having a plurality of such sleeves remaining therein following stripping away of a portion of the attendant concrete form, and Figure 5 is a longitudinal sectional view of a cold joint formed between two poured concrete slabs with a slip dowel extending therethrough and positioned within such sleeve. The accompanying drawings are provided for purposes of illustrating a presently preferred embodiment of the invention and are not intended to limit the scope of the invention in any way. Referring now to the drawings, as shown in Figure 1, the slip dowel placement sleeve 10 comprises a generally rounded cylindrical dowel receiving sheath 12 of substantially constant wall thickness having a closed distal end 14 which is integrally formed, an open proximal end 16, and a hollow interior compartment formed therewithin. A generally rectangular flange 18 extends perpendicularly about the proximal end 16 of the sheath 12. A central aperture is formed in the flange 18 so as to permit passage of a dowel rod through the flange and into the open inner compartment of the sheath 12. Plural apertures 20, 22, 24, and 26 are formed near each corner of the flange 18 to permit nailing or stapling of the flange to the surface of a wooden concrete form or other surface. Referring also to Figure 5, the sleeve 10 is provided with gussets 60. These fins or gussets are of generally triangular configuration and extend between the proximal end 16 of the tubular sheath 12 and the inner surface of flange 18 so as to impart additional strength and rigidity to the apparatus. Preferably, the sleeve 10 is integrally formed of a plastic material fabricated by conventional molding techniques. The manner in which the basic slip dowel positioning sleeves 10 are employed is illustrated in Figures 2 through 5. As shown, a series of individual slip dowel placement sleeves 10A, 10B, 10C, and 10D are positioned and affixed in an array along the inner surface of a section of wooden concrete form 30 such that each individual sleeve 10A, 10B, 10C, 10D extends perpendicularly from the inner surface of the form 30 in substantially parallel disposition. The attachment of the dowel rod placement apparatus, 10A, 10B, 10C, 10D to form 30 is made by passing staples or small head nails through the apertures 20, 22, 24, 26 of flanges 18 A - D. Thereafter, the form 30 is held firmly in position by stakes 32, 34. A first concrete pour is made within the form 30 so as to form first concrete slab 36. After slab 36 has set, the form 30 is stripped away, separating the individual flanges, 18 A - D and their associated nail or staple fasteners from the inner surface of the form 30. Such stripping away of the form 30 leaves the individual dowel rod position sleeves 10A - D in a parallel array within the slab 36 while the proximal flanges 18 A - D thereof reside flush with the formed edge 38 of slab 36. Sections of smooth dowel 40, 41, 42 are then inserted through apertures located in flanges 18 A - D and advanced distally into the longitudinal inner cavities of the dowel receiving sheaths of sleeves 10 A - D. The portion of the dowel rods 40, 41, 42 advanced into the sleeves 10 A - D will remain slidably disposed therein while the remaining portion of dowel rods 40, 41, 42 extend outwardly into an adjacent space 46 wherein a second concrete pour is to be made. Thereafter, concrete is poured into space 46 in a conventional manner and allowed to set, thereby forming a second concrete slab 48. A cold joint or seam 50 extends between the first slab 36 and the second slab 48. Through use of the dowel rod positioning sleeves 10 A - D of the present invention, the dowel rods 40, 41, 42 remain parallel to one-another and longitudinally slidable within the first slab 36 while being firmly cured in place within second slab 48. By such arrangement, the individual first 36 and second 48 slabs are permitted to undergo longitudinal expansion and contraction along the dowels 40, 41 and 42 while at the same time being prevented from buckling or undergoing vertical or angular displacement at the cold joint 50. It will be appreciated that modifications and alterations of the basic invention described above are possible within the scope of the following claims.
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A concrete dowel placement apparatus of the type comprising a tubular dowel receiving sheath (12) having an outer surface and a hollow interior compartment extending axially therein attached to a flat surface of a concrete form (30), said sheath (12) having an open proximal end (16) and an integrally formed closed distal end (14), and a flange (18) at said open proximal end for mounting the apparatus to said concrete form, said flange (18) being formed completely about and extending perpendicularly from said open proximal end (16) and having a peripheral edge, an inner surface which is directed toward the closed distal end (14) of the sheath (12), and an outer surface having a generally planar configuration for placement into abutting contact with the flat surface of the concrete form (30) to prevent seepage of concrete into said interior compartment of said sheath (12); characterised in that said sheath (12) is of generally rounded cylindrical configuration with a substantially constant wall thickness, and in that at least one strength imparting gusset (60) is provided having a first side extending along the inner surface of the flange (18) and terminating inwardly of the peripheral edge, a second side extending along a proximal portion of the outer surface of said sheath (12), and a third side extending between the first and second sides, said third side having a length substantially exceeding the length of the first side. A concrete dowel placement apparatus according to Claim 1, characterised in that said flange (18) has a generally rectangular configuration/ A concrete dowel placement apparatus according to Claim 1 or 2, characterised in that a plurality of apertures (20, 22, 24, 26) are formed in said flange (18), said apertures being sized, configured and positioned to permit the passage of fasteners therethrough in such a manner as to facilitate the attachment of said flange (18) to said flat surface of said concrete form (30) such that the outer surface of the flange (18) is held in abutting contact with the flat surface of the form (30). A concrete dowel placement apparatus according to any one of Claims 1 to 3, characterised in that said interior compartment of said dowel receiving sheath (12) is sized and configured to permit a dowel rod (40) to be slidably inserted therein and to allow said dowel rod (40) to remain longitudinally slidable therewithin so long as said dowel rod (40) resides within said interior compartment. A concrete dowel placement apparatus according to any one of Claims 1 to 4, characterised in that said apparatus is formed of molded plastic.
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SHAW LEE A; SHAW LEROY E; SHAW RONALD D; SHAW, LEE A.; SHAW, LEROY E.; SHAW, RONALD D.
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SHAW LEE A; SHAW LEROY E; SHAW RONALD D; SHAW, LEE A.; SHAW, LEROY E.; SHAW, RONALD D.
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EP-0489989-B1
| 489,989 |
EP
|
B1
|
EN
| 19,960,124 | 1,992 | 20,100,220 |
new
|
H04L12
|
H04L12
|
H04L12, G01R31
|
H04L 12/26M, S01R31:02B
|
LAN measurement apparatus
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A LAN parameter-measuring instrument is provided for measuring at least one physical parameter of a wired, packet-based, baseband LAN. The instrument comprises input means (21) for providing a connection to the LAN transmission medium (10) to enable measurements to be made while the LAN is active, and voltage measuring means arranged to connect to the LAN transmission medium (10) through said input means (21) and operative to measure the voltage on the LAN transmission medium during inter-packet gaps. The voltage measuring means may, for example, be in the form of a peak detector or sample-and-hold circuit. The instrument can also be arranged to determine the resistance of the LAN transmission medium (10) by measuring the inter-packet voltage during the injection of a known current into the transmission medium.
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The present invention relates to apparatus for measuring at least one physical parameter of a wired, packet-based, baseband local area network (LAN) while the LAN is active. The term wired, packet-based, baseband LAN is intended to mean a LAN, or LAN segment, in which the LAN transmission medium (for example, twisted pair wiring, coaxial cable) is adapted to carry electrical signals and in which the data being transferred between stations is transmitted over the transmission medium in packets using baseband signalling techniques. Such wired, packet-based, baseband LANs are referred to below as LANs of the aforesaid type . LANs of the aforesaid type may use various media access control techniques including CSMA/CD, token passing and slotted ring but all have the general characteristic that signals are normally only present on the LAN when user data or control data is being transferred - that is, no signals are normally present in the gaps between packets ( inter-packet gaps). The majority of faults on LANs of the aforesaid type are very simple and are typically caused by the failure of a particular component such as a network node, spanning device (bridge), or the wires or cables (or their terminators) themselves. In diagnosing network faults, it is therefore useful to be able to make simple observations of the state of any particular segment of a LAN, as disclosed in general by documents EP-A-0 383 291 or GB-A-2 106 358. It is an object of the present invention to provide apparatus which by simple measurements, can substantially facilitate fault diagnosis on LANs of the aforesaid type. According to one aspect of the present invention, there is provided apparatus for measuring at least one physical parameter of a wired, packet-based, baseband LAN, characterized in that said apparatus comprises input means for providing a connection to the transmission medium of the LAN to enable measurements to be made while the LAN is active, and voltage measuring means arranged to connect to the LAN transmission medium through said input means and operative to pick out and provide a measure of the voltage that is present on the LAN transmission medium during inter-packet gaps. The voltage on the LAN during inter-packet gaps is a useful measurement as it permits the user to tell whether any of the stations connected to the LAN are malfunctioning by leaking current into the LAN. The ability to measure inter-packet voltage also permits the resistance of the transmission medium to be measured as will be explained below. The voltage measuring means may comprise packet-detecting means for detecting the presence of a packet on said LAN and sample-and-hold means controlled by said packet-detecting means to capture the voltage on the LAN transmission medium when a packet is not present. Advantageously, the sample-and-hold means samples the voltage on the LAN of a predetermined time interval after the end of the last preceding packet. Alternatively, for LANs in which the mean voltage on the LAN transmission medium during passage of a packet differs from that present between packets, the voltage measuring means may comprise a peak voltage detector operative to capture the peak voltage on the LAN transmission medium in a direction opposite to the direction of excursion of said mean voltage during passage of a packet relative to the mean voltage between packets. Where the voltage excursions on the LAN during passage of a packet are all in the same direction with respect to the voltage of the LAN between packets, then the peak voltage detector can simply measure instantaneous peak voltage. As already noted, the ability to measure the inter-packet voltage facilitates the measurement of the resistance of the LAN transmission medium. This is achieved by providing the apparatus with current injection means for injecting a known current into the transmission medium, and processor means connected to said voltage measuring means to determine from the inter-packet voltage measured thereby during injection of said known current by said current injection means, and from the magnitude of said known current, the resistance presented by the LAN transmission medium. Measurement of the resistance of the LAN transmission medium readily shows whether a terminator has been left off or whether the medium has been incorrectly terminated. For simplicity, the current injection means can be manually controlled to effect current insertion and the value of the injected current is pre-programmed into the processor means. Conveniently, the measuring apparatus is provided in hand-held form enabling a technician to move rapidly from one location to another to isolate a network fault. A hand-portable, LAN parameter-measuring instrument embodying the invention will now be particularly described, by way of non-limiting example, with reference to the accompanying diagrammatic drawings, in which: Figure 1 illustrates generally how the instrument is used to carry out measurements on a LAN; Figure 2 is a schematic diagram of a first form of measurement circuitry for the LAN instrument; and Figure 3 is a schematic diagram of a second form of measurement circuitry for the LAN instrument. Figure 1 illustrates a LAN segment the transmission medium of which is constituted by a coaxial cable 10. A number of computer workstations 11 are connected to the cable 10 via connectors 12. The ends of the cable 10 are terminated by terminators 13 which match the characteristic impedance of the cable 10. The illustrated LAN is, for example, a CSMA/CD LAN complying with the 10BASE5 variant of the IEEE 802.3 standard. In this case, the characteristic impedance of the coaxial cable 10 is 50 ohms and the terminators 13 can be simply constituted by 50 ohm resistors connected between the inner conductor and the outer shield of the cable. The signalling technique used is baseband with Manchester encoding and with a data rate of 10 megabits/second. In transmitting packets over the LAN cable, the stations output pulse signals which have negative voltage excursions relative to the voltage of the cable between the packets (in this case, zero volts); thus, the inter-packet voltage will be the peak positive voltage on the cable. The LAN segment may be connected to one or more other LAN segments 15 via connectors 12 and one or more appropriate spanning devices such as the bridge 14. Also illustrated in Figure 1 is the hand-portable LAN parameter-measuring instrument 20. This instrument is battery powered and is provided with a coaxial-cable connector 21 for connecting the instrument to the cable 10 through a T-junction cable connector 16. Such connectors are generally to be found throughout the length of the LAN segment cable 10 and can serve as the connectors 12. When not providing a connection to the cable 10, the connector 16 has its unconnected stub left disconnected. As can be seen in Figure 1, the instrument 20 includes a power on/off switch 22, a liquid crystal display (LCD) 23, and a push button switch 24. Two forms of the internal circuitry of the instrument 20 will now be described with reference to Figures 2 and 3. The first form of circuitry (Figure 2) utilizes a peak voltage detector to capture the inter-packet voltage of the LAN cable 10, this voltage then being displayed on the LCD 23. More particularly, connecting the instrument 20 to the LAN through the connectors 21 and 16, connects the inner conductor of the cable 10 to an input line 30 of the instrument circuitry. This line 30 is connected to the + input of a comparator 31 the output of which feeds, via a diode 32 and a resistor 33, a storage capacitor 34 intended to hold the peak positive voltage of the LAN cable. A resistor 59 permits slow decay of the voltage on the capacitor 34. The voltage held on the capacitor 34 is output via a voltage follower 35 with this output being fed back to the - input of the comparator 31. The output of the voltage follower 35 is fed through a scaling potentiometer 36 and a switch member 24A to a digital voltmeter 37 whose output is constituted by the LCD 23. The switch member 24A is part of the switch 24 and in its normal position connects the potentiometer 36 to the digital voltmeter 37. In operation, if the voltage on line 30 is more positive than the voltage stored on the capacitor 34, then the output of the comparator 31 will go high causing the capacitor 34 to charge up through the diode 32 and resistor 33. As the capacitor 34 charges, its voltage will rise to equal that of the line 30 and thereafter the output of the comparator 31 will go low causing charging of the capacitor 34 to cease. The diode 32 prevents the discharge of the capacitor 34 through the output stage of comparator 31. The output of the comparator 31 will remain low until the voltage on line 30 next exceeds the voltage on the capacitor 34. In this way, the Figure 2 circuitry acts to capture the peak positive voltage of the inner conductor of the LAN cable 10. As previously noted, data is transmitted over the cable 10 in the form of negative voltage excursions from the inter-packet voltage (that is, zero volts); by capturing the peak positive voltage the Figure 2 circuitry thus acts to measure the inter-packet voltage on the cable 10. The presence of the resistor 33 insures that some short term averaging takes place of the peak voltage. This is advantageous as it avoids spurious positive spikes from giving false positive peak readings. In addition, should the voltage pulses used to encode data have small positive excursions as well as their large negative excursions, then by appropriate choice of the value of the resistor 33, these positive excursions can be smoothed out, the mean voltage present during passage of a packet being negative. Of course, the value of the resistor 33 must be such that the voltage on the capacitor 34 tracks to the inter-packet voltage before the end of the minimum inter-packet gap. The resistor 33 can be omitted if no short term averaging is required. The measurement of the inter-packet voltage is useful in its own right since if this voltage is not zero, it can be concluded that one or more stations is leaking current onto the LAN cable. The instrument 20 can also be used to measure the resistance of the LAN cable by injecting a small predetermined current into the cable and observing the resultant inter-packet voltage. To this end, a current source 38 is provided which when energized by operation of the switch 24 to close a switch member 24B, injects a predetermined current via the line 30 into the LAN cable. The magnitude of this current is chosen such as not to disturb the normal operation of the LAN. The resultant inter-packet voltage measured by the peak-voltage detection circuitry of Figure 2 provides a measure of the LAN resistance. By feeding the output of the voltage follower 35 via a scaling potentiometer 39 to the digital voltmeter 37, a reading can be produced on the LCD which is a direct reading of the cable resistance. The scaling potentiometer 39 is selected by the operation of the switch 24 which not only closes the switch member 24B but also changes over the switch member 24A from its normal position. For a properly connected LAN cable, the measured resistance would be just in excess of 25 ohms (the cable terminators constituting two 50 ohm resistors in parallel and the cable itself adding a small amount of resistance). Measurement of the LAN cable resistance is useful since if a termination 13 is missing, this will be readily apparent from the measurement of the LAN cable resistance. Figure 3 shows a second form of circuitry for the instrument 20. The Figure 3 circuitry uses a sample-and-hold circuit to capture the inter-packet voltage. More particularly, an input line 40 of the circuitry feeds the voltage on the inner conductor of the cable 10 to the inverting input of a fast comparator 41, the non-inverting input of which is fed with a reference voltage VR provided through a chain of resistors 42, 43. The output of the comparator 41 is low when the voltage on line 40 exceeds the reference voltage VR but goes high when the voltage on line 40 falls below VR. Thus, in the absence of a packet on the LAN cable 10, the output of the comparator 41 remains low whereas during the passage of a packet each negative data pulse on the cable will cause the voltage of the line 40 to fall below VR resulting in the output of the comparator 41 going high for the duration of the pulse. The output of the comparator 41 is connected to a re-triggerable monostable 44 which is triggered off the positive going transitions of the output of the comparator 41 (that is, the monostable will be triggered in correspondence to the leading edge of each negative going data pulse of the cable 10). At each triggering, the monostable 44 starts the output of a positive pulse of a predetermined duration corresponding to three quarters of the minimum inter-packet gap (this minimum being specified in the LAN design specification); if the monostable 44 is re-triggered before the end of a current output pulse, then the pulse is extended by the same predetermined duration. The output of the monostable 44 is fed to a sample-and-hold circuit 45 and to the clocking input of a D-type flip-flop 51. This sample-and-hold circuit 45 comprises a high impedance input voltage follower 46 fed with the voltage on the line 40, an electronic switch 47, a storage capacitor 48, and an output voltage follower 49. The electronic switch 47 is controlled by the output of a NAND gate 50 such that the switch is closed when the NAND gate output is low and open (the hold state) when the NAND gate output is high. The inputs of the NAND gate 50 are connected to the output of the monostable 44 and to an output of the D-type flip-flop 57. The flip-flop 57 is clocked by the rising edge of the pulse generated at the output of the monostable 44, that is, in correspondence with the leading edge of a packet. The flip-flop 57 has its input connected to a pull-up resistor 56 and a switch 55 (not shown in Figure 1). When the switch 55 is open, the leading edge of a packet will cause the output of the flip-flop to be set high whereas with the switch closed, the leading edge of a packet will cause the output of the flip-flop to be set low. As a result, when the switch 55 is open, the NAND gate 50 will be enabled so that its output will be low when the monostable output is high and vice versa whereby the voltage on the capacitor 48 will follow the LAN voltage during a packet and for a predetermined time interval thereafter but will then hold the inter-packet voltage. However upon closure of the switch 55 by the user of the instrument, the gate 50 will be disabled, causing the output of the gate 50 to go high, and hold the switch 47 open, thereby holding the last-sampled inter-packet voltage on the capacitor 48. The voltage on the capacitor 48 is fed via the output voltage follower 49, a scaling potentiometer 51 and the switch member 24A, to a digital voltmeter 52 the output of which is constituted by the LCD display 23. The sample-and-hold circuitry of Figure 3 can be used in an equivalent manner to the peak voltage detector circuitry of Figure 2 for the purposes of measuring the resistance of the LAN. For this purpose, the Figure 3 circuitry is provided with a current source 53 energizable via a switch member 24B, and a scaling potentiometer 54 selectable by switch member 24A. Operation of the switch 24 serves to inject a current into the LAN and to display the resulting voltage as a resistance reading on the LCD display 23 in the same general manner as for the Figure 2 circuitry. It will be appreciated that a number of modifications to the illustrated embodiments are possible. For example, the instrument need not be a hand portable instrument but could be incorporated in a test card to be plugged into a LAN station 11 or a spanning device (bridge 40). It will also be appreciated that the LAN cable upon which measurements are made need not be a coaxial cable but could equally be twisted pair wiring or other transmission media adapted to carry electrical signals. Furthermore, the derivation of the resistance of the LAN cable can be effected in ways other than by the use of scaling resistors 39, 54; thus, for example, a digital calculation unit could be used which digitized the voltage measured on the LAN upon current injection and thereafter calculated the resistance of the LAN cable, the value of the injected current either being pre-programmed into the calculation device or being separately measured and supplied in digital form to the calculation device.
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Apparatus for measuring at least one physical parameter of a wired, packet-based, paseband LAN, said apparatus comprising input means (21) for providing a connection to said transmission medium (10) of the LAN to enable measurements to be made while the LAN is active, and voltage measuring means (31-37; 41-52) arranged to connect to the LAN transmission medium (10) through said input means (21) characterized in that said apparatus is operative to pick out and provide a measure of the voltage that is present on the LAN transmission medium during inter-packet gaps. Apparatus according to claim 1, wherein said voltage measuring means (41-52) comprises: packet-detecting means (41) for detecting the presence of a packet on said LAN; and sample-and-hold means (45) controlled by said packet-detecting means to capture the voltage on the LAN transmission medium (10) when a packet is not present. Apparatus according to claim 2, wherein said sample-and-hold means (45) is operative to sample the voltage on the LAN a predetermined time interval after the end of the last preceding packet detected by said packet-detecting means (41). Apparatus according to claim 1, for use with a LAN in which the mean voltage on the LAN transmission medium (10) during passage of a packet differs from that present between packets, said voltage measuring means (31-37) comprising a peak voltage detector (31-35) operative to capture the peak voltage on the LAN transmission medium in a direction opposite to the direction of excursion of said mean voltage during passage of a packet relative to the mean voltage between packets. Apparatus according to claim 4, wherein said peak voltage detector records the instantaneous peak voltage on the LAN. Apparatus according to claim 4, wherein said peak voltage detector records the peak voltage on the LAN integrated over a period sufficient to smooth out peaks during passage of a packet but short enough to permit tracking to the inter-packet voltage during the interval between packets. Apparatus according to any one of the preceding claims, further comprising current injection means (38; 53) for injecting a known current into the LAN transmission medium (10), and processor means (39, 54) connected to said voltage measuring means to determine in dependence on the inter-packet voltage measured thereby during injection of said known current by said current injection means (38; 53), and on the magnitude of said known current, the resistance presented by the LAN transmission medium (10). Apparatus according to claim 7, wherein said processor means is a scaling resistance (39; 54). Apparatus according to claim 1 in the form of a hand-held instrument.
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HEWLETT PACKARD CO; HEWLETT-PACKARD COMPANY
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I ANSON COLIN STEPHEN; PHAAL PETER; I'ANSON, COLIN STEPHEN; PHAAL, PETER
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EP-0489992-B1
| 489,992 |
EP
|
B1
|
EN
| 19,950,308 | 1,992 | 20,100,220 |
new
|
G01P15
| null |
A61N1, H01L29, G01P15
|
A61N 1/365B6, G01P 15/08A, H01R 23/72B, G01P 15/18
|
Multiaxial transducer interconnection apparatus
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An apparatus for use as a substrate assembly for providing electrical connections in a multiaxial transducer is disclosed. The multiaxial transducer includes transducer die elements, which are electrically connected to the substrate assembly. The transducer die elements each have a sensitivity axis and are mounted on the substrate such that their sensitivity axes are non-parallel. The substrate comprises at least two modules wherein each module is fabricated substantially identically to the other and further wherein each module is oriented along a different axis corresponding to the orientation of the sensitivity axes. A plurality of electrical pads are affixed to the substrate so as to allow for pad-to-pad connections from one module to the other and further provide a ratio of substrate module bonding pads to transducer die bonding. A multiaxial transducer interconnection apparatus. The apparatus comprises first, second and third substrate modules each having a plurality of electrical tracks thereon. A portion of the electrical tracks is structured and arranged to interconnect the substrate modules in an orthogonal relationship to each other. The plurality of tracks on each substrate module is further arranged to form a pattern identical to the plurality of tracks on the other substrate modules. The substrate modules each include a mounting region whereon transducer die elements are mounted. One alternate embodiment of the invention would include a base upon which the modules would mount. Another alternate invention of the invention employs a chip carrier to support the multiaxial transducer of the invention.
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BACKGROUND OF THE INVENTION I. Field of the Invention: The invention is directed generally to a multiaxial interconnection apparatus for transducers and, more particularly, to a multiaxial transducer interconnection apparatus for use in advanced rate adaptive cardiac pacemaker systems, defibrillators, cardioverters, heart monitors, metabolic need indicators and similar medical electronic devices. II. Discussion of the Prior Art:Heart and respiration activity generates mechanical energy. This energy propagates through the body and can be detected by appropriate transducers and may provide information useful for the control of organ functions such as heart rate pacing, for example. Current transducer technology does not address certain critical aspects of such medical electronics applications. Some prior approaches in the medical electronics art use active (piezoelectric) transducer elements which are well known such as Bruel & Kjaer Company's Type 4321 and Endevco Company's Model 2258-10/-100 devices. These devices are limited in their application, however, because they do not utilize the cost and size advantages of micromachining technology. Passive transducers are also known in the prior art. Passive transducers require excitation energy to operate. In the case of a multiaxial transducer, the number of supply lines is proportional to the number of uniaxial transducer components assembled together. The reduction in quantity of transducer terminals or wires is critical for many applications. A number of companies offer passive (piezoresistive) transducers such as IC Sensors, 1701 McCarthy Boulevard, Mulpitas, CA, for example. These devices are sensitive in one dimension only, but could be integrated into a multiaxial transducer. However, it is believed that the die substrates currently utilized in the industry, have no designed-in features to aid in substrate-to-substrate electrical connection. JP-A-63118667 discloses a three-dimensional acceleration sensor comprising a cubic block having a different acceleration sensor attached to each of the three of its faces which are mutually orthogonal. According to the present invention there is provided a multi-axial transducer interconnection apparatus comprising, either first and second, or first, second and third, substrate modules each having a plurality of electrical tracks thereon, the tracks on one module having an identical fabrication and identical pattern to the tracks on the other module or modules, the substrate modules being arranged in a mutually orthogonal relationship and being electrically interconnected, and the substrate modules each including a mounting region having a different transducer die element mounted thereon, each transducer die element being electrically connected with its respective substrate module. This invention provides a multiaxial transducer, useful for medical electronics applications, comprising transducer elements mounted on electrically interconnected modular substrates. The multiaxial transducer of the invention achieves a reduction in the quantity of terminals required for many applications as compared to other known devices. It is an object of the invention to provide a multiaxial transducer interconnection apparatus fabricated from identical substrate elements so as to allow use of identical masks for the basic substrate module fabrication. Other features, objects and advantages of the invention will become apparent to those skilled in the art through the description of the preferred embodiment, claims and drawings herein. BRIEF DESCRIPTION OF THE DRAWINGSIn the drawings like numerals refer to like elements. Figure 1 shows a plan view of one embodiment of a die substrate module according to the invention. Figure 2 shows a plan view of the interconnection scheme of one embodiment. Figure 3 shows a perspective view of one embodiment of a multiaxial transducer. Figure 4 is a diagram of the substrate module of the invention illustrating pad usage. Figure 5 shows a perspective view of an alternate embodiment of a multiaxial transducer including a base element for supporting the substrate modules. Figure 6 shows a perspective view of another alternative embodiment of a multiaxial transducer employing a chip carrier. DESCRIPTION OF THE PREFERRED EMBODIMENTReferring now to Figure 1, a plan view of one embodiment of a die substrate module according to the invention is shown. The die substrate module 100 comprises a substrate material upon which printed circuit tracks 102 for carrying electrical power or signals are deposited by means well known in the art. In one example, the substrate module 100 includes tracks 1, 2, 3 and 4. Track 1 is a negative voltage power line, track 4 is the positive voltage potential power line, 2 is the first signal line and 3 is a second signal line for carrying information from the transducer device to other electronics (not shown). A test pad, T, may advantageously be included. While the transducer to be used in connection with the invention is not shown in Figure 1, the mounting surface 106 for the transducer is shown as part of the substrate module adjacent to the tracks 102 and as bordered by the corner markings 110. Broken line 112 denotes a cutting line for removing excess material from some of the modules prior to assembly as appropriate as shown in Figure 3 and as described below in detail. The substrate module may be comprised of ceramic substrate material, for example, which may be cut by means of a laser or other cutting device well known in the art. Referring now to Figure 2, a plan view of an interconnection scheme of one embodiment of a substrate assembly including three die substrate modules is shown. Three substrate modules, 100A, 100B and 100C, are shown arranged for the purposes of illustrating the interconnections for this embodiment. Each of the modules 100A, 100B and 100C initially is fabricated identically as a die substrate module 100. Depending on where the module is to be used, certain modifications are made by the removal of unwanted material. Crossed-hatched areas 200A and 200C are advantageously removed prior to assembly of the three modules into a multiaxial transducer as shown in Figure 3 by means of laser trimming or micromachine milling, for example. Note that Figure 2 is intended to be used as an interconnection illustration only and is not representative of a manufacturing process step. Each of the substrates 100A, 100B and 100C includes a mounting surface area. These are denoted as 106A, 106B and 106C, respectively. Transducer die elements 300A, 300B and 300C as shown in Figure 3 are advantageously affixed to the mounting surfaces prior to assembly of the modules into the multiaxial transducer. Each of the modules 100A, 100B and 100C have power and signal lines as described hereinabove with reference to module 100 in Figure 1. Referring now to Figure 3, a perspective view of one embodiment of the multiaxial transducer of the invention is shown. With continuing reference to Figure 2, it can be seen that the three substrate modules 100A, 100B and 100C have now been connected together to form a multiaxial transducer 202. Transducer devices 300A, 300B and 300C have been mounted to mounting surfaces 106A, 106B and 106C, respectively. The removed material is shown for reference purposes as 200A and 200C. No material is removed from module 100B. Modules 100A, 100B and 100C are oriented such that the mounting surfaces 106A, 106B and 106C abut each other in an orthogonal relationship. The transducer devices 300A, 300B and 300C have sensitivity axes 302A, 302B and 302C oriented in a perpendicular relationship for sensing, in this example, energy propagated in the X, Y and Z directions. Such transducer devices are well known in the art and may be, for example, accelerometers of the type as sold by IC Sensors, as for example, its 3000 Series accelerometer. Referring now to Figure 4, a diagram of the substrate module 100 is shown wherein each of the pad areas are designated by a reference numeral for the purposes of further clarifying the interconnections for the substrate assembly and multiaxial transducer. Those skilled in the art will recognize that this example is given by way of illustration and not limitation of the invention to the configuration shown. The table below defines the pad designations and module interconnections in accordance with the reference numerals in Figures 2 and 4. The following table enumerates the pad usages and ratios for the example embodiment of the substrate module shown in Figure 4. Triaxial Transducer Pad Configuration Ratios for this example are: E / C = 2 (E + F) / C = 3 (D + E + F) / C = 4 The above ratios would be smaller if E were equal to zero thereby providing no substrate interconnections via specially designed pads. Note that by utilizing a single substrate module 100 and a transducer 300, a unidirectional assembly can be fabricated utilizing edge connectors 19-22. Referring now to Figure 5, an alternate embodiment of the multiaxial transducer is shown in perspective view. This embodiment includes transducers 300A, 300B and 300C mounted to modular substrates 220A, 220B and 220C and further mounted to base 250. Interconnections are made by means of wire conductors or tracks 252. Referring now to Figure 6, yet another alternate embodiment is shown including a multiaxial transducer assembly 260 having transducers 300A, 300B and 300C (not shown) mounted on an integrated circuit chip carrier 262. Other pins 264 are then brought out from the chip carrier 262 for interfacing with external electronics. It is believed that this alternate configuration would be useful for certain applications. Those skilled in the art will recognize that the applications of the invention are not limited by the medical industry examples cited herein, but also have application to other fields utilizing multidirectional sensing devices, such as the automotive and aerospace arts.
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A multi-axial transducer interconnection apparatus comprising, either first and second, or first, second and third, substrate modules (100A-C, 220A-C) each having a plurality of electrical tracks (1,2,3,4,252) thereon, the tracks on one module having an identical fabrication and identical pattern to the tracks on the other module or modules, the substrate modules (100A-C,220A-C) being arranged in a mutually orthogonal relationship and being electrically interconnected, and the substrate modules (100A-C,220A-C) each including a mounting region (106A-C) having a different transducer die element (300A-C) mounted thereon, each transducer die element (300A-C) being electrically connected with its respective substrate module (100A-C,220A-C). The apparatus according to Claim 1 wherein the electrical tracks (1,2,3,4,) electrically interconnect the modules (100A-C) The apparatus according to Claim 1 comprising a base (250,260) having orthogonal mounting surfaces, wherein each mounting surface has a different one of said modules (220A-C) mounted thereon. The mounting apparatus of Claim 3 which further comprises an IC chip carrier (262) upon which the base (260) is mounted. The apparatus of any preceding claim, wherein the transducer die elements (300A-C) each have a sensitivity axis (x,y,z) and are mounted so as to orientate the sensitivity axes (x,y,z) in a mutually orthogonal relationship The apparatus of Claim 5, wherein the transducer die elements (300A-C) are accelerometers. The apparatus according to claim 5 or 6, wherein the transducer die elements (300A-C) have bonding pads. The apparatus according to any preceding claim, wherein each module has a plurality of electrical pads (1-22,T). The apparatus of any preceding claim wherein the substrate modules (100A-C,220A-C) are fabricated from ceramic material. The apparatus of any preceding claim wherein the plurality of electrical tracks (1,2,3,4,252) of each module (100A-C,220A-C) comprise at least two tracks (1,4) for carrying electrical power and at least two tracks (2,3) for carrying an electrical signal.
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CARDIAC PACEMAKERS INC; CARDIAC PACEMAKERS, INC.
|
SILVERMINT EMANUEL H; SILVERMINT, EMANUEL H.
|
EP-0489993-B1
| 489,993 |
EP
|
B1
|
EN
| 19,950,816 | 1,992 | 20,100,220 |
new
|
H04Q7
|
H04B7
|
G06F11, H04W88, H04B7
|
H04Q 7/30C, H04W 88/18C, G06F 11/08
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Data throughput enhancement
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A method characterized by distributing channel coding on either side of a limited capacity communication path (102) by partially channel coding (400) a signal at a first processing point (100) and communicating the partially coded signal over the communication path (102) to a second processing point (105). The partially coded signal is characterized by at least some but not all of the necessary coded bits. The channel coding algorithm is completed at the second processing point (105) using the communicated partially coded signal (401) thereby increasing throughput over the limited capacity path (102) while minimizing added delays.
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TECHNICAL FIELD OF INVENTIONThis invention relates generally to communication systems and more particularly to digital communication systems that employ redundant coding. BACKGROUND OF THE INVENTIONIn communication systems employing information coding, such as forward error correction coding, the number of code bits are increased by adding redundancy to information bits, such as by convolution. Redundancy coding, as known in the art, provides more signal elements than necessary to represent the intrinsic information. Channel coding, a type of redundancy coding, is often employed at the expense of using more channel capacity than might otherwise be necessary, to permit improved information recovery over channels that exhibit impairments, such as mobile radio communication channels. Channel coding is well understood in digital communication theory and is used in digital speech radio communication systems, such as digital radio telephone cellular systems. An information signal, such as digital data or a low bit rate encoded speech signal, is processed into a coded digital signal by some predetermined algorithm, and is hereafter referred to as the processed signal. In a digital cellular system, a switch site must typically communicate multiple digital voice channels or digital data channels to a cell site over landline interconnections. The cell site in turn transmits these voice channels to mobile subscriber units via radio frequency (RF) channels. In an attempt to improve system performance over such heavily impaired mobile RF channels, the information signals typically undergo channel coding at either the cell site or the switch site (or someplace in between) before they are communicated over the RF channel. In such digital communication systems, the landline communication paths are expensive to install and maintain; consequently, efficient use of these paths is of utmost importance. However, the performance of the system must also be a consideration so that minimum degradation occurs. The location of where the speech compression and the channel coding are accomplished is an important consideration. For example, Fig. 1 shows a known method of channel coding speech blocks wherein the switch site (100), comprised of a mobile switching center (MSC) (101) communicates one non-processed 64 kilobit per second (kbps) digitized voice channel over a single 64 kbps channel of a 2.048 Mbps megastream interconnect to a cell site (105). At the cell site, the information on the voice channel is digitally compressed into low bit rate speech information bits by a speech transcoder (110), whose average output data rate is 13 kbps. Some of these speech information bits are then sequentially channel coded by the channel coder (115) resulting in a processed signal of 22.8 kbps per voice that is sent to an RF transmitter (120). This method is not cost effective, since each voice channel requires its own 64 kbps path between the switching center and the cell site. If, however, all the processing was completed at the switch site, a maximum number of two (22.8 kbps + 22.8 kbps = 45.6 kbps) integral processed voice channels could be multiplexed onto a single 64 kbps channel of the megastream interconnect. The improvement realized is a reduction by two in the amount of landline capacity required to carry the same number of voices. Excessive landline interconnect costs still exist since only two voices are carried per megastream subchannel. Fig. 2 depicts a known method for providing four voice channels over one 64 kbps landline megastream subchannel by moving the speech transcoder (110) to the switch site (100) and performing only the speech coding (13 kbps per channel) on all four channels before transmitting over the landline path whereafter the channel coding (processing) is provided at the cell site. Consequently, a 52 kbps (4 × 13 kbps = 52 kbps) speech coded data stream is communicated over the landline connection to the cell site (105) where each voice channel then undergoes channel coding via the channel coder (115) resulting in four 22.8 kbps processed signals. These digital signals are then communicated to the transmitter (120) and transmitted over RF channels. Unfortunately, this can produce a downlink bulk audio delay since a majority of each speech block (each speech block being 260 bits and representing 20 msec of speech) must be transferred to the cell site before the necessary processing may begin. This is because the channel coded bits generated may each be a function of many of the input information bits. The delay to transfer a block of information is about 17 msec (1040 or (260 × 4) bits of speech at 64 kbps) and is long enough in duration to be undesirable. Accordingly, there exists a need to maximize processed data throughput over a limited channel capacity communication path while minimizing delays. The article entitled The GSM Base Station System and the Related Equipment , by S. Hansen et al., published in 8th European Conference on Electrotechnonics , Stockholm, 13th-17th June 1988, pages 470-473, provides background to the present invention and describes the system architecture of the GSM communication system. SUMMARY OF THE INVENTION According to a first aspect of the present invention there is provided a method for facilitating throughput of a signal over a communication path of the type wherein at least a portion of a signal is communicated from a first processing point over a limited capacity communication path to at least a second processing point remotely located from the first processing point and the signal is processed at the at least second processing point, the method characterized by the steps of: (a) generating a partially processed signal (400) having redundant data by applying a first algorithm to at least a portion of a signal at the first processing point; and (b) continuing processing of the partially processed signal at the at least a second processing point by using a second algorithm whose functional purpose is substantially related to the first algorithm. In a second aspect of the present invention there is provided a transmitter for facilitating throughput of a signal over a limited capacity communication path having transmitting means for transmitting at least a portion of a signal over a limited capacity communication path to a processing point remotely located from the transmitter, the transmitter characterized by: generating means, operably coupled to the transmitting means, for generating a partially processed signal having redundant bits by applying a first algorithm to at least a portion of the signal, the generating means applying the first algorithm to at least a portion of the signal such that the partially processed signal is capable of being subjected to continuing processing at the processing point with a second algorithm whose functional purpose is substantially related to the first algorithm. In a further aspect of the present invention there is provided a receiver for facilitating throughput of a processed signal over a limited capacity communication path having receiving means for receiving a signal and processing means, operably coupled to the receiving means, for processing of the signal, the receiver characterized in that: the receiving means comprises: (a) means for receiving a partially processed signal having redundant bits from a remotely located transmitter, the partially processed signal being derived from the application of a first algorithm to a signal; and the processing means comprises: (b) means for continuing processing of the partially processed signal with a second algorithm whose functional purpose is substantially related to the first algorithm applied to the partially processed signal. By partially processing (such as by channel coding) at least a portion of a signal, such as a coded speech block, at a first processing point (e.g. a cellular switch site), and then communicating this partially processed signal over a limited capacity communication path to a second processing point (such as a cell site), at which point the signal undergoes continuing processing (such as completing the channel coding commenced at the first processing point) to produce a processed signal, the present invention advantageously provides an enhanced method of data throughput. In a preferred embodiment, the partially processed signal comprises at least a portion of processed bits, such as bits which have been error correction/detection coded, and optionally information bits such as compressed digitized speech. To minimize waiting delays at the at least a second processing point, at least some of the portion of the processed bits are those need first by the second point to continue the processing or to effectuate further data transfer from the second point, such as transmission over a radio channel. The continuing processing generates remaining processed bits a the second processing point using a substantially related algorithm as that used to generate the initial processed bits at the first processing points. The first processing point may partially process the signal up to a level not exceeding the capacity of the communication path. An exemplary embodiment of the present invention will now be described with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a block diagram generally depicting a prior art system for channel coding speech blocks in which a cellular switch site communicates one non-processed signal over a single, limited capacity communication path from a cellular switch site to a cell site. Fig. 2 is a block diagram generally depicting a prior art system in which four coded speech channels at the switch are communicated over a limited capacity communication path to the cell site where they are entirely processed (channel coded), resulting in a transmission path bulk delay. Fig. 3 is a flow chart depicting a preferred method for data throughput enhancement according to the present invention. Fig. 4 is a block diagram generally depicting three voice channels partially processed (channel coded) at the switch site and communicated over a limited capacity communication path to the cell site wherein the processing (channel coding) is completed resulting in no added transmission path bulk delay in accordance with the invention. PREFERRED EMBODIMENT OF THE INVENTIONThe disclosed invention of distributed coding may be readily applied to a transmitting system, receiving system or any communication system comprising redundant coding techniques. The preferred embodiment of the invention is a method comprising distributing systematic error correction channel coding on either side of a limited capacity communication path in order to maximize throughput over the path while reducing delays in providing the processed signal. This embodiment assumes only an integral number of voice channels are allowed over a single megastream 64 kbps subchannel due to the complexities associated with switching a non-integral number of user channels. However, it is understood that the utility of this invention is not limited by this assumption. Fig. 3 discloses the preferred method of enhancing data throughput comprising partially processing (coding up) (310) a signal of information bits (300) to an average rate equal to or not to exceed the average rate of the fully processed (coded up) signal, then communicating (320) the partially processed signal over a limited capacity communication path to a second processing point, and continuing processing the signal (340) at the second processing point. The partially processed signal may also be sent with a preferential bit ordering (330) to a time critical stage before the entire processing is completed to effectuate a priority based communication scheme. The partially processed signal or the completely processed signal is then communicated (350) over an impairing medium. Partially processing (310) comprises algorithmically performing systematic error correction channel coding, as understood in the art, on a signal such as a coded (compressed) speech block, at a first processing point, resulting in a partially processed signal. The partially processed signal therefore comprises at least some bits of the original information signal plus some (but not the complete set) of processed bits. The number of processed bits generated at the first processing point is a function of at least the capacity of the limited capacity communication path and the priority scheme associated with the second processing point. This allows a maximum amount of data (information bits and some redundant bits) to be communicated over the path (320) in a priority order (if necessary) to allow at least a second processing point to continue processing (340) the signal without waiting for a completely processed signal to first be communicated over the path. Consequently, a first needed partially processed signal may be communicated first to allow a time critical stage (330) to begin utilizing the partially processed signal, such as first transmitting the partially processed data to a subscriber radiotelephone, while a remaining portion of redundant bits is generated by continuing coding (340) of the information bits to facilitate the completion of channel coding. Continuing coding (340) comprises using the same algorithm as that used in partially coding (310) the signal to algorithmically generate a remaining portion of the needed redundant bits, thereby completing the coding initially started at the first processing point resulting in a completely channel coded signal at the second processing point. Although the same algorithm is used in the preferred embodiment, any substantially related algorithm may also be used to aid in providing the necessary unprocessed input information. For example, a substantially related algorithm may be a non-systematic channel coding algorithm, as understood in the art, the first processing point may algorithmically generate a portion of coded bits and communicate only a portion, if any, of the signal information bits and the coded bits to the second processing point where continuing processing comprises algorithmically deriving the remaining unknown information bits from the partially processed signal. This algorithm may be considered complementary to the algorithm used in partially processing as it completes processing by inferentially deriving information bits based on the subset of coded bits generated by the partially processing algorithm. As appreciated by those skilled in the art, any other suitable coding technique which generates coded bits may also be employed by the disclosed invention. Such techniques are hereby referred to as combinatorial processing techniques. In addition, the method of invention is not limited to one processing point on either side of the limited communication path, but consistently applies for N processing points on either side of the communication path. The method for data throughput enhancement can be described by applying it to the aforementioned submultiplexing digital cellular radio communication system. Fig. 4 depicts the invention as applied in a three to one (three voice channels to one 64 kbps path) submultiplexed system that uses systematic channel coding to provide redundant error correction/detection bits to a digital speech signal before the signal is transmitted over an RF channel. A transmitter, such as the switch site (100), comprises means for partially processing a signal such as three coded voice channels in its partial channel coder (400) up to a point not exceeding the limited capacity of a communication path (102) and communicates the partially processed speech signals over the limited capacity path (102) to a receiver, such as a cell site (105). The partially processed signal is comprised of portions of the original signal and a subset of the coded bits. Communication is facilitated via means for transmitting comprising interface transceivers as commonly known in the art. Three voices at 13 kbps coding requires 39 kbps (3*13) of the 64 kbps path. If all processing were performed at the switch site (100), 68.4 kbps would be required (3*22.8 after complete processing). Thus, of the total 29.4 kbps (68.4 kbps - 39 kbps) of overhead processing that is needed for the three voices, only an estimated 25 kbps (64 kbps - 39 kbps) of the 29.4 kbps can be sent (as understood in the art, some nominal framing bits or side information bits may also detract from the total available 64 kbps throughput) which translates to over 85% of the needed processing for each frame. Therefore, taking each speech coded frame to be 20 msec (260 bits = 13 kbps * 20 msec), the first 17 msec (0.85*20 msec) of each voice can be processed by the switch site channel coder (400) and communicated with the speech blocks at full rate over the 64 kbps path to the cell site (105). The total time to transmit the processed signal (over the RF medium) is actually 40 msec due to interleaving, as known in the art, therefore a 17 msec block actually accounts for 34 msec of real time. Consequently, the transmitter (120) has all the information needed to compute the unknown redundant bits 14 msec in advance of when they are needed and the cell site (105) continues the processing in its channel coder (401) and sends the completed processed signals to the transmitter (120) in the order they are needed thereby reducing idle time of the transmitter. Since error coding expends a minimal amount of digital signal processing time, the distributed coding (processing) substantially eliminates the bulk delay at a minimal expense. As a result, three voice channels may be communicated over one path with no appreciable delay. For purposes of optimizing the invention's performance, it is evident that considerable latitude is available in selecting what type of data and in what order the data may be communicated to the second unit. As a minimum, some but not all of the processed data (redundant data) is communicated. Communication of the original information is not necessary in all cases. Another embodiment provides a four to one submultiplex system reducing the traditional four to one submultiplexing (as depicted by Fig. 2.) delay by substantially reducing the 17 msec bulk audio delay to approximately 8 msec. Applying the same data rates as discussed above, four voices at 13 kbps requires 52 kbps (4*13 kbps) of the 64 kbps path. After complete channel coding, 91.2 kbps would be needed (4*22.8 kbps after channel coding). Thus, of the total 39.2 kbps (91.2 kbps - 52 kbps) of the necessary overhead processing for the four voices, only 12 kbps can be sent. This is over 30% of the needed redundant bits. This translates into 12 msec (.30*40 msec due to interleaving) of the 20 msec of redundant bit time associated with each voice block. Therefore, 8 msec of the complete processed signal is not yet available, and an 8 msec delay must be inserted before the transmission is allowed to begin. As is evident, this is less than half of the delay required compared to the conventional approach. Various other optimizations are also possible to reduce the incurred delay, for example, where all bits need not be present to begin channel coding at the second processing point. As appreciated by those ordinarily skilled in the art, the invention readily applies to communication systems comprising decoding of a channel coded signal, or any other coded signal, where decoding is distributed on either side of a limited capacity communication path. It will also be appreciated that the invention is not limited to error correction/detection coding algorithms but rather any kind of algorithm involving redundancy, such as information compression/expansion. For example, in a time critical compression/expansion system, a first processing point containing a compressed signal, may partially expand (adding a greater number of bits to the compressed signal) a portion of the compressed signal before communicating a portion of the compressed data along with some expanded data to a second communication unit. The second communication unit may then first use the already expanded portion while it continues to expand the received compressed data. It is further understood that this invention applies to any type of information signal and is not restricted to the voice example described.
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A method for facilitating throughput of a signal over a communication path (102) of the type wherein at least a portion of a signal is communicated from a first processing point (100) over a limited capacity communication path (102) to at least a second processing point (105) remotely located from the first processing point (100) and the signal is processed (401) at the at least second processing point (105), the method characterized by the steps of: (a) generating a partially processed signal (400) having redundant data by applying a first algorithm to at least a portion of a signal at the first processing point (100); and (b) continuing processing of the partially processed signal (401) at the at least a second processing point (105) by using a second algorithm whose functional purpose is substantially related to the first algorithm. The method of Claim 1, wherein each algorithm is a channel coding algorithm. The method of Claim 2, wherein each channel coding algorithm is a channel coding process selected from the group consisting of systematic linear block coding, nonsystematic linear block coding, systematic convolutional coding and nonsystematic convolutional coding. The method of Claim 1, 2 or 3, wherein the step of generating is characterized by expanding at least a portion of a compressed data signal. The method of any preceding Claim, wherein the step of continuing processing is characterized by expanding at least a portion of a compressed data signal. The method of any preceding Claim, wherein the step of communicating is characterized by communicating at least a portion of the partially processed signal in an order of priority based on a first-needed, first-sent basis to the at least second processing point (105). The method of any preceding Claim, wherein the partially processed signal is characterized by a portion of information bits and a portion of coded bits. The method of any preceding Claim, wherein the limited capacity communication path (102) operably couples at least two subsystems of a digital cellular communication infrastructure system. A transmitter for facilitating throughput of a signal over a limited capacity communication path (102) having transmitting means for transmitting at least a portion of a signal over a limited capacity communication path (102) to a processing point (105) remotely located from the transmitter, the transmitter characterized by: generating means (400), operably coupled to the transmitting means, for generating a partially processed signal having redundant bits by applying a first algorithm to at least a portion of the signal, the generating means applying the first algorithm to at least a portion of the signal such that the partially processed signal is capable of being subjected to continuing processing at the processing point (105) with a second algorithm whose functional purpose is substantially related to the first algorithm. A receiver for facilitating throughput of a processed signal over a limited capacity communication path (102) having receiving means for receiving a signal and processing means (401), operably coupled to the receiving means, for processing of the signal, the receiver characterized in that: the receiving means comprises: (a) means for receiving a partially processed signal having redundant bits from a remotely located transmitter, the partially processed signal being derived from the application of a first algorithm to a signal; and the processing means (401) comprises: (b) means for continuing processing of the partially processed signal with a second algorithm whose functional purpose is substantially related to the first algorithm applied to the partially processed signal.
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MOTOROLA INC; MOTOROLA, INC.
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KOTZIN MICHAEL D; KOTZIN, MICHAEL D.
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EP-0489994-B1
| 489,994 |
EP
|
B1
|
EN
| 19,940,921 | 1,992 | 20,100,220 |
new
|
E06B3
|
A47B96
|
E04C2, B44C5, B44C3, E06B3, A47B96
|
E06B 3/70A, B44C 3/08D, B44C 5/04L, E04C 2/30
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Door of concave surface
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A door includes a board (20) having opposed depressed portions (201) formed in major opposed side walls and two thermoplastics sheets (10, 30) respectively attached to the major side walls of the board and having depressed portions (101, 301 respectively) shaped or embossed with decorative designs, fitted in the depressed portions of the board.
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This invention relates to the structure of a door, and more particularly to a door with its board covered with thermoplastics sheets which are embossed with decorative patterns or figures within deformed depressions or cavities. Doors covered with plastics sheets which are embossed with decorative patterns or figures by means of thermoplastics deformation art for closing the entrance to a building, room, cupboard, etc. are well known in the prior art. Referring to Figure 2, a thermoplastics sheet 10 of a suitable thickness and about the size of a major side wall of a board of a door is used and then heated to the plastics deformable state by a heater or suitable number of infrared heaters located on the top and bottom of the sheet 10. The thermoplastics sheet 10 may be moved relative to the heaters or the heaters may be moved relative to the sheet 10 so as to evenly distribute the heating effect to the sheet 10 to achieve a uniform deformable plastic state. The thermoplastics sheet 10 is then placed between a male die 11 and a female die 12 and further sealed therebetween. The metal block of the male die 11 is cut with desired pattern or figure 111 and provided with a plurality of passages 110 extending downwardly to connect an air conduit 13 which is connected to a vacuum pump (not shown). The vacuum pump will create a vacuum in the chamber in top portion of the male die 11 to form desired pattern or figure 102 in the sheet 10 corresponding to the shapes cut in the male die 11 by creating an excess of pressure on the upper face of the sheet 10. After this is accomplished, the thermoplastics sheet 11 is then removed from the moulds 11 or 12 into the open air for air cooling. Two such thermoplastics sheets 10 both a size can be attached to major opposed sides of the board of the door by means of adhesives. It is found that the embossed patterns or figures of the thermoplastics sheets attached to doors are easily fractured in transport as doors generally stacked up in container or aboard. To alleviate this problem, sufficient packing arranged between doors is necessary to prevent the embossed patterns or figures from fracturing or undesired deformations caused by loading pressure, and that is obviously costly and labour consuming. An object of the present invention is to provide an improved door covered with thermoplastics sheets each of which has a concave surface shaped or embossed with decorative design such as pattern or figure. Another object of the present invention is to provide an improved door with its concave surface for securing designs shaped or embossed therein from being fractured. It is a further object of the present invention to provide an improved door with a concave surface which is easy to pack giving labour and space savings in packing. According to the invention there is provided a door of concave surface comprising; a door board having at least a major side wall formed with at least a depressed portion; at least a thermoplastics sheet attached to the major side wall of the door board and having a surface formed with at least a depressed portion to be fitted in the depressed portion of the major side wall of the door board; and at least a pattern shaped in the depressed portion of the thermoplastics sheet below a level with the surface of the thermoplastics sheet. The invention will now be further described, by way of example only, with reference to the accompanying drawings, in which:- Figure 1 is a perspective view showing a preferred embodiment of the present invention; Figure 2 is a cross-sectional view showing the moulding process of a thermoplastics sheet; Figure 3 is a side elevational view of two doors of the present invention in stacking condition; and Figure 4 is a perspective view showing another preferred embodiment of the present invention. Referring to figures 1 and 3 of the accompanying drawings, a door according to the present invention comprises a board 20 having an opposedly depressed portion 201 preferably formed in mid portion of its major opposed side walls and two thermoplastics sheets 10, 30 exactly and respectively attached to the major side walls of the board 20. Each of said sheets 10, 30 has a depressed portion 101 or 301 preferably corresponding to respective depressed portion 201 of the board 20 in dimension and within which is shaped or embossed with a decorative design such as a flower design 102. In attachment condition, the depressed portion 101, 301 fit in the depressed portion 201 of the board 20 wherein the shapes of bottoms of the depressed portions in the major opposed side walls of the board 20 can be flat or entirely mating with corresponding portions of the sheets 10, 30, as shown in Figure 3. The patterns 102 within each depressed portion 101 or 301 of the sheet 10 or 30 is shaped or embossed on or below a level with its surface so that there is no disturbance between stacked doors in package. The patterns or designs of the sheets of this invention are shaped or embossed through prior thermoplastics deformation art described above and shown in Figure 2 except that a depression or cavity corresponding to said depressed portion should be previously machined in the metal block of the male die 11, then cut desired pattern or figure within the depression or cavity. It should be noted that two or more depressions or cavities 501, 502 with individual patterns or figures 503, 504, as shown in Figure 4, can be formed in one major side of the door 5 according to user's choice.
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A door of concave surface comprising; a door board (20) having at least a major side wall formed with at least a depressed portion (201); at least a thermoplastics sheet (10, 30) attached to the major side wall of the door board and having a surface formed with at least a depressed portion (101, 301) to be fitted in the depressed portion of the major side wall of the door board; and at least a pattern (102) shaped in the depressed portion of the thermoplastics sheet below a level with the surface of the thermoplastics sheet. A door as claimed in claim 1 having two or more depressed portions formed in one major side of the door. A door as claimed in claim 1 or 2, wherein the pattern shaped in the depressed portion of the thermoplastics sheet is on or below a level with its surface.
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FANG HO TSUNG; FANG, HO-TSUNG
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FANG HO-TSUNG; FANG, HO-TSUNG
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EP-0489996-B1
| 489,996 |
EP
|
B1
|
EN
| 19,950,208 | 1,992 | 20,100,220 |
new
|
B60C27
| null |
B60C27
|
B60C 27/10
|
Anti-skid device for automobile tires
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An anti-skid device for automobile tires wherein mutually spaced tightening end portions of an anti-skid device body which are extended inwards along the side surfaces of a tire (1) when the device body (2) is set on the tire (1) are connected to each other by a length-variable fastener consisting of hooks (6) connected at one ends thereof to the opposed tightening end portions, and a plate (7) having holes in its base portion and pivotably supporting the other ends of the hooks (6) in different holes therein. A length (ℓo') between the opposite tightening end portions can be set smaller than the free length (ℓo) thereof by turning the plate (7).
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This invention relates to an anti-skid device for automobile tires. Description of the Prior Art:The conventional anti-skid devices for automobile tires which have mainly been used are the anti-skid devices disclosed in Japanese Patent Publication Nos. 13337/1983 and 49366/1983. In these examples, an inner rope C is fixed via inner metal members G or directly to the inner side surface of a tire skid preventing net body B as shown in Fig. 14, and the tire skid preventing net body B is put over a tire T with the inner rope C fixed to the tread thereof. Both ends of this net body B are then joined together by a suitable method so that the net body B extends annularly. The inner side surface portion of the net body B is then tightened with the rope C, and the outer side surface portion thereof with a setting strap D via outer metal members E to set the anti-skid device as shown in Fig. 15. However, according to this method, hooking the setting strap D on a plurality of outer metal members E one by one takes much time and labor. This setting strap D in use is designed so that it can be handled without much pulling force, taking a female user into consideration. Another reason why the setting strap D is made in the mentioned manner resides in that, if the strength of the setting strap D is set excessively high, the rope C used on the inner side surface of the net body B would be broken. It has been considered impossible for this reason as well that the strength of the setting strap D be set excessively high. Therefore, when a centrifugal force is applied to the tire skid preventing net body B while the vehicle travels, the setting strap D expands to cause the net body B to float and return and locally slip. Consequently, the net body B becomes rather loose with respect to the tire T, and variation of position of the net body and a locally concentrated load occur to cause the net body B to be locally broken or displaced, making such an anti-skid device unfit for use. Especially, in the case of a non-metallic net type anti-skid device which is in recent years growing to be a leading anti-skid device of this kind, the floating of a tire skid preventing net body B due to a centrifugal force from the tire T causes a decrease in the durability of the device, and the swelling of the net body B which brings the net body B into contact with the inner surface of the fender and results in the breakage of the net body B. These inconveniences suggest the important points of designing the anti-skid device. On the other hand, it is necessary that the level of the tightening force occurring in the setting strap D as a whole for the prevention of the floating of the net body B be increased. Under the circumstances, there is a limit to the tension of the setting strap D which can be hooked manually with ease on the outer metal members E, and the tension of such a single setting strap D cannot prevent the floating of the tire skid preventing net body B from the tire T which occurs due to the centrifugal force exerted on the net body B when the tire T is rotated. Therefore, two to three pieces of setting straps the tension of which is set to the very limit of the range of levels at which the setting straps D can be hooked manually on the outer metal members are generally used. Since the operation of hooking the increased number of setting straps D one by one on each of a plurality of outer metal members E sequentially causes an increase in the length of time and quantity of labor for carrying out the attaching and detaching of the anti-skid device to and from a tire, it hinders the further spreading of this kind of anti-skid device which has been reconsidered in view of the prospective total abolition of spike tires. The conventional tire skid preventing net body B shown in Fig. 15 is formed flat as shown in Fig. 14, and the tightening portions thereof which are to be applied to the inner side surface of a tire T are then set to a pitch ℓu' at which these tightening portions are held finally on the tire by using inner metal members G. Regarding the tightening portions of the net body B which are to be applied to the outer side surface of the tire T, the diameter of a circle connecting these tightening portions held on the outer side surface of the tire T by hooking the setting strap D on the outer metal members E and tightening the same is reduced so that the pitch ℓo of these tightening poritons of the net body B in a flat-extending state becomes ℓo'. Unless a sufficiently large pitch of the tightening portions of the tire skid prevening net body B which correspond to the outer sided surface of a tire is secured, the net body B cannot be set on the tire. Therefore, the net body B is set on the tire T with the outer tightening portions spaced with the same pitch ℓo as that when the tightening portions of the net body B is formed in a flat-extending state. Thus, a lot of energy is required to reduce the pitch of the tightening portions corresponding to the outer side of the tire to the level at which these tightening portions are finally held on the tire, and putting the net body over the tire and fixing the same thereto in this manner also causes the tightening portions to be swollen greatly by the centrifugal force. An anti-skid device which solves the above defects is disclosed in Japanese Patent Laid-Open No. 48204/1990 (corresponding to the preamble of claim 1). However, in said device, it is difficult to fasten to the tire and it requires much time and labour. An object of the present invention is to provide an anti-skid device for automobile tires which is free from the above-mentioned drawbacks. The anti-skid device for automobile tires according to the present invention consists of anti-skid device body comprising the features of claim 1. The above and other objects as well as characteristics of the present invention will become apparent from the following description of the preferred embodiments taken in conjunction with the drawings. Fig. 1 illustrates the anti-skid device in an assembled state for automobile tires according to the present invention; Fig. 2 is a plan view of an anti-skid device body of the anti-skid device for automobile tires according to the present invention; Fig. 3 illustrates parts of the anti-skid device body which are connected together by a first hook and bent; Fig. 4 illustrates a fastener in a released state in the anti-skid device for automobile tires according to the present invention; Fig. 5 is a plan view of a plate in the fastener; Fig. 6 illustrates a plate assembly in the fastener; Fig. 7 illustrates a special tool for turning and setting the fastener; Fig. 8 illustrates the fastener in a device body-setting state in the anti-skid device for automobile tires according to the present invention; Figs. 9(a) - 9(c) illustrate each part of a second hook for the fastener; Fig. 10 is a sectional view of the fastener in a device body-setting state; Figs. 11 and 12 illustrate a process for assembling the anti-skid device for automobile tires according to the present invention; Fig. 13 illustrates another example of the fastener; Fig. 14 is a plan view of an anti-skid device body in a conventional anti-skid device for automobile tires; and Fig. 15 illustrates the conventional anti-skid device in an assembled state for automobile tires. An embodiment of the present invention will now be described with reference to the drawings. The anti-skid device for automobile tires according to the present invention has a quartered non-metallic anti-skid device body 2 in which the four device body members are joined together by joint hooks 3, 3' in four positions on the outer circumferential portion of a tire as shown in Fig. 1. Both of the joint hooks 3' among these joint hooks in four positions can be attached to and detached from the device body members. As shown in Fig. 2, the anti-skid device body 2 has a plurality of mutually spaced tightening end portions which are to extend inward along the inner side surface of a tire when the device body 2 is set on the tire, and integrally formed connecting projections 4 extending toward each other from first and fourth tightening end portions among the tightening end portions spaced with a pitch of ℓo and applied to the outer side surface of a tire. The length of this connecting projection 4 is ℓo', and the free end of the connecting projection 4 is finally joined to the adjacent tightening end portion by a first hook 5, as shown in Fig. 3. The connecting projection 4 has two holes in its free end portion as shown in Figs. 2-4, and is joined at the hole therein which is closer to the adjacent tightening end portion to the same tightening end portion by the hook 5. The connected part thus formed constitutes a bendable joint. The anti-skid device for automobile tires according to the present invention further has fasteners each of which consists of second hooks 6 and a plate 7, and each of which is provided with a power doubler for reducing the length ℓo, which is in a largely free state when the anti-skid device body is put over a tire with the outer tightening end portions thereof on the outer side surface of the tire, to the length ℓo', a level required when these tightening end portions are finally set. The bendable joints referred to above are moved in conjunction with the turning of the plates 7. Each of the device body members of the quartered anti-skid device body 2 is formed flat as shown in Fig. 2. The pitch ℓo of the portion of the member of the device body 2 which is on the outer side of the tire and that ℓu of the portion of the member which is on the inner side of the tire are equal to each other. This member of the device body 2 is assembled so that it forms a three-dimensional curved structure when the connecting projections 4 and tightening end portions are joined together by using first connecting hooks 5 and fastening hooks 8 on the side of the inner surface of the tire as shown in Fig. 3. The length of the fastening hook 8 is set so that the pitches ℓo', ℓu' corresponding to those ℓo, ℓu become equal to each other when the member of the anti-skid device body 2 is put over the tire 1, i.e., in the condition shown in Fig. 3. In the anti-skid device for automobile tires according to the present invention, some of the fasteners used on the outer side surface of the tire is made in advance to a length required when the device body is finally set. Accordingly, some of the fasteners on the outer side surface of the tire are made so that they can be simply attached to and detached from the device body 2. In the power doubler-carrying fastener used in the present invention, one end portion of a second hook 6 is connected to an end portion of a connecting projection 4 on the outer side of the tire so that the hook 6 extends in the same direction as the connecting projection 4 as shown in Fig. 4. The other ends of the second hooks 6, extending toward each other are fixed in two holes, which are made in the base portions of the relative plate 7 so as to be spaced by a distance r, in such a manner that the hooks 6 can be turned. As shown in Fig. 5, the plate 7 is formed flat and provided with a plurality of holes. The plate 7 is combined unitarily with a resilient member 9 as shown in Fig. 6. The plate 7 is provided with a first hole 10 in the center of pivotal movement thereof, and symmetrically arranged second and third holes 11, 12 spaced from each other by a distance m, and adapted to be turned by a special plate turning jig 13 shown in Fig. 7 and having projections 10'-12' corresponding to these holes 10, 11, 12. The special jig 13 is provided with a plate turning handle of M in length formed thereon. When the handle of the special jig 13 is turned around the hole 10 with the projections 10'-12' thereof inserted into the three holes 10-12 in the plate 7 correspondingly, the force of the handle is amplified in the ratio of M/m around the first hole 10 and works in the direction in which a distance Lo shown in Fig. 4 is reduced. When the plate 7 is turned reversely at 180° to be put in the condition shown in Fig. 8, the distance Lo is reduced to ℓo'=Lo-2r . The connecting projections 5 and tightening end portions are joined together by first hooks 5 to form bendable joints. Therefore, the distance 2r reduced by the turning of the plate 7 is divided uniformly between the portions to be fastened of the device body. When the plate 7 is turned, the distance between the portions to be fastened of the device body decreases uniformly as an angle α between the first hook 5 and the relative tightening end portion decreases, and, in the condition shown in Fig. 8, the distance between the opposed portions to be fastened of the device body becomes equal to a final required level ℓo'. In the anti-skid device for automobile tires according to the present invention, the distance between the opposed portions to be fastened is set to Lo which is somewhat shorter than the pitch ℓo of the tightening end portions of the device body in a flat condition shown in Fig. 2 with the lengths of the hooks 5, 6 and the distance r between the outermost holes in an initial free state. Accordingly, even when the connecting projections are fixedly set to the length ℓo' at which the device body is finally fastened to a tire, the device body can be easily attached to and detached from a tire. When the plate 7 is turned, so that Lo becomes equal to ℓo', the device body is put in a tire-fastened state shown in Fig. 1, and the fastened portions of the device body are effected to form a closed loop of force, whereby the device body attains a stable fastened state. Since the first hooks 5 in this condition are directed toward the center of rotation of the tire, a tensile force toward this center is imparted to the tightening end portions to which the hooks 5 are fastened, whereby the anti-skid device body is stabilized. The sizes of various parts of the anti-skid device body will now be calculated taking a tire 165R13 of general sizes as an example. The outer diameter of a 165R13 tire is 596 mm, and the diameters of circles connecting the outer and inner portions to be fastened of an anti-skid device body to be put over this tire are set equal, i.e., they are set to 464 mm. When the length of each joint hooks 3, 3' for connecting the members of the anti-skid device body 2 is set to 30 mm, the length ℓo' in the device shown in Fig. 1 is: The length ℓo in the device body in a flat extending state shown in Fig. 2 is: Accordingly, the squeezing of ℓo - ℓo' = 35 mm of the device body per portion to be fastened thereof is required. The length of each connecting projection 4 is set from the beginning to ℓo' which is required for a final device body fastening operation. The first hook 5 by which a connecting projection 4 and a tightening end portion are connected together moves like a link. Therefore, when the first hook 5 forms an angle α as shown in Fig. 4, the size of the portion to be fastened of the connecting projection 4 increases by a distance S to become ℓo' + S. On the other hand, the size of the portion to be fastened of a plate 7 decreases by the distance S to become L=Lo-2S . Since the length of the first hook 5 is set so as to satisfy relation of ℓo' + S = L , the distances between three portions to be fastened are equal. Regarding the power doubler-carrying fastener, Lo is set to 189 mm as shown in Fig. 4, in such a manner that the fastener expands 43 mm more than ℓo=146 mm which is the length thereof in a free state, taking the necessity of attaching and detaching the fastener easily to and from the device body into consideration. Namely, a size difference Lo - ℓo' = 189 - 111 = 78 mm is distributed equally to three portions (78/3 = 26 mm each). Consequently, the distance between the portions to be fastened of opposed connecting projections becomes ℓo' + 26 = 137 mm, while the distance between the portions to be fastened of the plate 7 becomes L = Lo - 2S = 189 - 2 x 26 = 137 mm , so that ℓo' + S = L . Thus, when the plate 7 is turned to cause the distance Lo to be reduced to ℓo', the distances between the three portions to be fastened become equal, i.e., decrease to ℓo'. In order to squeeze the portions to be fastened of the device body from Lo=189 mm to ℓo'=111 mm by the power doubler-carrying fasteners, r may be set equal to (189-111)/2=39 mm. If the length M of the handle of a special plate-turning tool is set to M=160 mm, the rotary force applied around the center of rotation is amplified four times, i.e., it becomes The distances r=39 mm and M=160 mm can be secured without any dimensional troubles. If the distance m between the plate-turning holes is set to m=20 mm, the rotary force generated by the handle becomes so that a force the level of which is two times as high as the force imparted to the holes in which the second hooks 6 are supported pivotably on the plate 7 is imparted to the plate-turning holes 11, 12 and plate-turning projections on the handle. Accordingly, the strength of each part is sufficiently high. A final fastening force generated for forming fastened portions by utilizing rubber belts in regular cases is around 20 kg f. If this force is obtained by using the handle of the plate-turning tool, a four-time-increased force is obtained as mentioned above, so that the rotary force becomes 5 kg f. This level of rotary force can be generated comparatively easily in a usual case by a less powerful person including a woman in view of the nature of the work. The rotary force imparted in this operation to the plate-turning holes 11, 12 is 10 kg f, which this anti-skid device body can withstand sufficiently, and it does not give rise to any problems. The first hole 10 and projection 10' are provided correspondingly to the centers of rotation of the plate 7 and handle of the plate-turning tool 13. Since the handle is turned necessarily around the mentioned centers, the handle turning operation can be carried out smoothly, and the disengagement of the projections 11', 12' of the handle from the plate-turning holes 11, 12 can be prevented. Each second hook 6 has a shape shown in Figs. 9(a) - 9(c), and a sectional view of the power double-carrying fastener in a fastened state is shown in Fig. 10. As is clear from Fig. 8, locking projections 14 are formed on the plate 7 as a part of and integrally with the resilient member 9 so that, when the power doubler-carrying fastener is in a fastened state, the fulcrums B, C of the second hooks 6, which are supported pivotably on the plate 7, are locked and retained in such condition that these fulcrums B, C are offset each other in the device body fastening direction with respect to a line connecting the fulcrums A, D, which are on the end portions of the connecting projections 4, of the same hooks 6. Namely, since the points B, C are in the positions offsetting each other in the direction in which the device body is turned and fastened, a force for turning the fastener in the direction opposite to the fastener unlocking direction is applied to the points B, C when a force for increasing the device body fastening distance ℓo' is applied to the points A, D. As shown in Fig. 10, the portion of a second hook 6 which is between the fastening portions at both end thereof is engaged at the surface of the plate 7 which is on the opposite side of the tire surface with the locking projection 14. Accordingly, when a force for separating the anti-skid device as a whole from the tire surface occurs due to the centrifugal force generated as the tire rotates, the plate 7 the mass of which is larger than that of the second hook 6 lifts the hook 6. This can prevent the second hook 6 from disengaging the locking projection 14, and enables the second hook 6 to be locked reliably. In order that the second hook 6 runs over the locking projection 14 to be locked, the plate 7 is turned as it is pressed against the tire surface. Consequently, the free end of the fastening portion of the hook 6 is pressed against the tire surface, and the plate 7 as a whole including the locking projection 14 is pressed down to the tire surface due to the elasticity of the tire. Thus, the locking of the second hook can be done easily. The unlocking of the second hook 6 can also be done easily by turning the plate 7 in the unlocking direction while pressing the same against the tire surface. Regarding each hook used in the anti-skid device for automobile tires according to the present invention, each hook fastening hole portion of the anti-skid device body has a stepped portion which is spaced from the tire surface by a distance corresponding to the thickness of the hook as shown in Fig. 10. The surface which contacts the tire of the hook and the surface which contacts the tire of the anti-skid device body are thus set flush with each other for the purpose of preventing the tire surface pressing force based on the anti-skid device fastening force occurring when the anti-skid device is fitted firmly around the tire from being imparted to the tire in a concentrated manner due to the surface of a small curvature of the hook, i.e., for the purpose of preventing this tire surface pressing force from causing the hook and tire to contact each other, and the tire to be thereby damaged while the vehicle travels. A method of fixing the anti-skid device according to the present invention will now be described. First, the members of an anti-skid device body 2 are attached to a tire 1 tentatively as shown in Fig. 11. During this time, the four power doubler-carrying fasteners are all put in a free state in which the plates 7 are in the condition shown in Fig. 4. The plates 7 of the power doubler-carrying fasteners are then turned to positions shown in Fig. 8, and fixed in a fastened state. The turning of the plates 7 during the tentative device body attaching operation can be done easily by hand without using a special tool. During this operation, the center of curvature of each member of the device body 2 and the center of the tire 1 are aligned with each other. The tire 1 is then turned about 1/4. During this device body attaching operation, the turning and fixing of the plates 7 may be done satisfactorily in even only two positions spaced from each other in the rotational direction of the tire 1. In a conventional anti-skid device shown in Figs. 14 and 15, a single setting strap D is hooked tentatively on several outer metal members E, and a tire 1 is then turned 1/4. Since the diameter of the setting strap D in a free state is small, a tensile force is imparted to the outer fastening portion of a device body during a tentative device body setting strap hooking operation. Consequently, the balance between the tension of the outer fastening portions and that of the inner fastening portions is lost, and, moreover, the setting strap D is moved on the outer metal members E as the tire 1 is turned. Due to these problems, the deviation of an anti-skid net body B from the center of the tire 1 occurs as the tire is turned. This makes it difficult to carry out a subsequent setting strap hooking operation. In the device according to the present invention, the squeeze rates of the inner and outer portions to be fastened of the device body are equal. Accordingly, the length of these portions with the power doubler-carrying fasteners in four positions in a tightened state become equal. Therefore, the tension of these inner and outer portions is balanced well, and the displacement of the device body does not occur when the tire is turned. Arrangements are then made to start an operation of turning the tire 1/4 and then fastening the joint hooks 3' on the inner side of the tire so as to endlessly connect the inner portions to be fastened. During this time, the members of the anti-skid device body 2 are dropped onto the inner side surface of the tire so that the fastening of the joint hooks 3' can be done easily. If the power doubler-carrying fasteners are set in a free state again and two outer joint hook 3', opposed to the other are set free as shown in Fig. 12 in this operation, the endless connecting of the inner portions of the device body can be done satisfactorily. The setting of the length Lo and the setting of the length of the first hook 5, which forms a link mechanism with the relative connecting projection 4, described with reference to Fig. 4 are done so as to make easy this operation of dropping the members of the anti-skid device body 2 onto the inner side of the tire, and enable an operation of endlessly connecting the quartered tread-covering members of the device body on the outer side as well of the tire to be carried out smoothly by fastening the outer joint hooks 3', which will be described below, to the members of the anti-skid device body 2. After the inner joint hooks 3' are fastened to the members of the device body, the device body 2 is drawn out to the outer side of the tire. This joint hook drawing operation is carried out with the connecting projections 4 gripped by hand, to enable the operation to be practiced easily. The joint hooks 3' in two positions are then fastened to the members of the device body 2 so as to endlessly connect the quartered tread-covering device body on the outer side of the tire, and the power doubler-carrying fasteners in four positions are tightened in an arbitrary order to complete the operation. The outer fastened portions of the device body in this condition form a closed loop of force, and the fastened portions are fixed unitarily. Accordingly, even when the tire skids, the fastened portions of the device body 2 are not displaced, so that the displacement and separation of the device body from the tire 1 do not occur. Since the portions to be fastened on both the outer and inner sides of a tire are fixed using the same system, the tensions of the outer and inner portions of the device body are balanced. Since the expansion of the fastened portions hardly occurs, the resistance of the anti-skid device to the centrifugal force and the durability thereof are improved markedly as compared with those of an anti-skid device employing rubber straps. When the power doubler-carrying fasteners are in a fixed state, the squeeze distances thereof are constant in any cases. In order to offset difference in the diameter of the outer fastened portions, which is due to a difference in size of the tire or a slight displacement of the anti-skid device fixed on the tire, and generate tension, which is relatively and slightly higher than that of the inner fastened portions, in the outer fastened portions, it is preferable that the connecting projection 4 consists of a buffer structure using such a material or structure that generates elastic energy, and that they be formed to a length slightly smaller than ℓo'. This buffer structure in the anti-skid device body 2 in the present invention including the connecting projections 4 is formed integrally out of, for example, an elastic body of polyurethane elastomer. If the connecting projections 4 are formed to such cross-sectional dimensions that enable these projections to expand more than the inner fastened portions and tread-covering portion of the anti-skid device body, satisfactory buffering connecting projections 4 can be obtained. The connecting projections 4 may also be provided with lengthwise extending spring-like buffer members 4' at the intermediate portions thereof as shown in Fig. 13. As described above, the device according to the present invention has an excellent fixing capability, i.e., it can be fastened to a tire without requiring much time and labor. It can prevent the swelling of the fastened portions of the device body which would otherwise be caused by a centrifugal force, and which constitutes a drawback in a conventional device of this kind, improve the durability of the device and prevent the displacement and separation of the device body from the tire. Such advantages of the present invention may be itemized as follows. (1) While this anti-skid device is fastened tentatively to a tire and the tire is turned therefore, the displacement of the device does not occur, so that the concentricity of the portions to be fastened of the device with the tire can be obtained easily. (2) The time and labor required to fasten rubber strap to the outer metal member in a conventional anti-skid device can be omitted. (3) The tightening forces to the fastened portions of the device on the inner and outer sides of the tire are balanced well, so that the durability of the device is improved. (4) Since the fastened portions are fixed unitarily, the displacement and separation of the device body from the tire rarely occur. (5) Since hooks to which a rubber strap is secured are not provided, the anti-skid device body as a whole need not extend into radially inner portion of a tire. Accordingly, this device can be put over a low profile tire, in which the outer diameter of the tire and that of a wheel body do not differ much, in such a manner that the fastened portions do not contact the wheel body. This can prevent the wheel body from being damaged. In the above embodiment, a net type anti-skid device body is used. However, the present invention can also be applied to a chain type anti-skid device as disclosed in Japanese Utility Model Laid-Open No. 68,809/1985 and Patent Publication No. 178,909/1982, or a ladder type anti-skid device as disclosed in Japanese Utility Model Laid-Open No. 28,509/1988 or Patent Laid-Open No. 138,203/1979 wherein a plurality of elongated anti-skid plates extending in an axial direction of the tire are fixed to the tread of the tire by means of a fastening wire.
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An anti-skid device for automobile tires comprising an anti-skid device body (2), detachable joint hooks (3') for connecting both ends of the device body (2) together, and a length-variable fastener, the anti-skid device body (2) having a plurality of mutually spaced tightening end portions which are extended radially inward along the side surfaces of a tire (1) when the device body (2) is set on the tire (1), characterised in that the length-variable fastener consists of bendable joints (4) extending toward each other from the tightening end portions at both ends of the device body (2), first hooks (6) connected at first ends thereof to the ends of the bendable joints (4), a plate (7) having holes in its based portion and pivotably supporting the other ends of the first hooks (6) in different holes therein, the length between the opposed tightening end portions being reduced by turning said plate (7), and second hooks (5) each extending in the radial direction of the tire (1) along the side surface of the tire (1), and connecting between said end of the bendable joints (4) and the other tightening end portions. The anti-skid device for automobile tires according to Claim 1, wherein when the length between said tightening end portions connected through said fastener is reduced by the rotation of said plate (7) of the fastener, each of said tightening end portions is elongated resiliently. The anti-skid device for automobile tires according to Claim 1, wherein said length-variable fastener comprises a hole (10) formed at a centre of rotation of said plate (7), and holes (11, 12) formed at positions symmetrically separated from said centre of rotation of said plate (7). The anti-skid device for automobile tires according to Claim 1, wherein each of the hook fastening hole portions of said anti-skid device body (2) has a stepped portion which is spaced from the tire surface by a distance corresponding to the thickness of the hooks (5 - 8) so that each of hooks (5 - 8) is not brought into contact directly with the tire surface. The anti-skid device for automobile tires according to Claim 1, further comprising lock means consisting of the hook (6) pivotably inserted into said hole of said plate (7) and a projection (14) formed on said plate (7) for holding said plate (7) in the rotated state. The anti-skid device for automobile tires according to Claim 5, wherein said projection (14) is formed on the surface of the plate (7) which is on the opposite side of the tire surface so as to be brought into contact with said hook (6), so that the locking force of the locking means is increased by the centrifugal force generated as the tire rotates. An exclusive jig for fastening tightening end portion of an anti-skid device for automobile tires comprising three projections (10' - 12') corresponding to three holes (10 - 12) of a rotary plate (7) of a length-variable fastener to rotate said rotary plate (7).
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CARMATE KK; KABUSHIKI KAISHA CARMATE
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SAKUMA KIYOSHI; SAKUMA, KIYOSHI
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EP-0489997-B1
| 489,997 |
EP
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B1
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EN
| 19,951,115 | 1,992 | 20,100,220 |
new
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F04D29
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F04D29
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F04D29
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F04D 29/32K2, F04D 29/38C, F04D 29/38C2
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Improved axial flow impeller
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An axial flow air impeller for automotive radiator fan use and the like comprising a hub (10) carrying a plurality of integrally formed similar circumaxially spaced and generally radially outwardly projecting air moving blades (12). Each blade (12) has a root end portion (14) integral with the hub (10) and a radially outwardly disposed tip end portion (18) with smoothly curving leading and trailing edges (20, 22) extending therebetween. The leading edge (20) curves substantially forwardly while the trailing edge (22) extends substantially radially to provide for a blade (12) projected width at the tip end portion (18) approximately 4⊘% greater than at the root end portion (14). The thickness of each blade (12) varies from a maximum at the root end portion (14) to a minimum at the tip end portion (18) with the latter being at least three times the thickness at the blade edge. An integral orifice ring (26) circumscribes the plurality of blades (12) and has a bell mouth at its upstream or downstream end.
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A variety of axial flow air impeller or fan designs have been employed in cooling automotive radiators and in similar heat exchanger applications and, while certain designs have been generally satisfactory, no single impeller design has been completely satisfactory in all respects. The present invention particularly concerns an axial flow air impeller for automotive radiator, heat exchanger use and the like and of the kind comprising a hub adapted for rotation about an axis and carrying a plurality of integrally formed similar circumaxially spaced and generally radially outwardly projecting air moving blades, each of the blades having a root end portion integral with the hub and a radially outwardly disposed tip end portion with smoothly curving side edges therebetween, the air impeller being adapted for unidirectional rotation in a forward direction and the side edges comprising leading and trailing edges the former of which curves substantially forwardly when viewed from root end portion to tip end portion to provide a projected width of each blade which is at least 40% greater at the tip end portion than at the root end portion; each blade having a maximum thickness which varies from a maximum at the root end portion and the maximum thickness at the tip end portion being at least three times the thickness at the blade trailing edge, and wherein an orifice ring is integral with each blade tip end portion and circumscribes the plurality of blades, the orifice ring having upstream and downstream ends and having a flange at one end with a substantially smooth radius at the junction with the ring portion. An air impeller of the aforegoing kind specified is disclosed in Patent Specification U.S.-A-4,900,229. It is the general object of the present invention to provide an improved axial flow air impeller of the kind specified and which represents a judicious compromise of design objectives such as minimum noise generation, highly efficient aerodynamic operation and economy of material and manufacture. SUMMARY OF THE INVENTIONAccording to the present invention there is provided an axial flow air impeller of the kind specified above and which is characterised in that the thickness of each blade reduces as it progresses from its root end portion to a minimum thickness at its tip end portion and the reduction is determined so that the maximum blade thickness at any blade section is: Ts = Tmax (rs/rroot)x where Ts = blade thickness at the measured section, s Tmax= maximum blade thickness near the root tip end portion rs= radius ratio x at section s rroot = section radius at blade root end x = between 1.0 and 0.5 (value assigned so that minimum value of Ts will not be less than three times thickness at blade trailing edge). Preferably the tip end portion of each blade is approximately 40% to 80% wider than the root end portion thereof. The orifice ring may be formed to be approximately bell mouthed as illustrated at its upstream or downstream end. BRIEF DESCRIPTION OF THE DRAWINGSFigure 1 is a fragmentary rear view of an improved axial flow air impeller constructed in accordance with the present invention. Figure 2 is a fragmentary side view of the air impeller of Figure 1. DESCRIPTION OF PREFERRED EMBODIMENTReferring particularly to Fig. 1, it will be observed that a hub is partially shown and indicated generally by the reference numeral 1⊘. The hub 1⊘ may be rotated by on output shaft of an electric motor, a belt drive from an internal combustion engine etc., and serves to support and rotate a plurality of air moving blades. An air moving blade 12 is illustrated at 12 and a second air moving blade is partially illustrated at 12a. The air impeller shown is provided with nine (9) identical blades equally spaced circumaxially and each blade projects radially outwardly from the hub 1⊘. Preferably, the impeller is of molded plastic construction and the hub 1⊘ and blades 12 are formed integrally. That is, a root end portion of each blade 12 is formed integrally with the hub 1⊘ and the blade projects generally radially outwardly from the hub to its termination 18. A root end portion of the blade 12 is illustrated at 14 and, as best shown in Fig. 2, the root end portion 14 of the blade 12 is inclined or arranged at an angle of pitch relative to an axis of rotation 16. As will be apparent in Fig. 2, blade pitch decreases from the root end portion to the tip end portion 18 of the blade 12. The blade 12 has smoothly curved side edges extending between its root end portion 14 and its tip end portion 18 and, more particularly, the blade has a leading edge 2⊘ and a trailing edge 22. The air impeller of the present invention is unidirectional and rotates in a counterclockwise direction as illustrated in Fig. 1 by the directional arrow 24. In accordance with the present invention, the leading edge of each blade 12 of the impeller of the present invention is curved substantially forwardly when viewed from root end portion to tip end portion and the width of each blade is thus increased substantially in progression from the root end portion to the tip end portion. That is, the trailing edge of each blade 12 is preferably at least approximately radial as illustrated in Fig. 1 such that a substantial increase in blade width or chord occurs as a result of the forward sweep of the blade leading edge 2⊘. Preferably, at least a 4⊘% increase in blade projected width occurs throughout blade length and, as illustrated, the blade is substantially twice as wide at its tip end portion as at its root end portion thus showing a 1⊘⊘% increase in width. Further, the forward sweep of the leading edge of the blade preferably occurs at a radially outwardly disposed portion thereof. Thus, the major portion of the forward curve at the leading edge of each blade preferably occurs at the outer one-half of the blade length measured from the root end portion to the tip end portion and, more specifically, at the outer one-third of the blade length so measured. The forward sweep of the leading edge of each of the blades 12 substantially improves the time incidence differential for radial points along the outer portion of the blade leading edge. This results in a significant reduction in noise generation. In observation of Fig. 2, it will be observed that a significant variation in thickness occurs as the blade progresses from its root end portion 14 to its tip end portion 18, the thickness of the blade being substantially reduced. The thickness variation is designed to minimize stress in the blades and at the same time reduce to the extent possible the amount of material required to make the blade relative to a uniform thickness blade of the same strength. The maximum blade thickness Tmax near the root portion of the blade is judiciously selected as are various section thicknesses along the length of the blade from its root end portion to its tip end portion. That is, the blade thickness Ts at any blade section may be determined as follows, Ts = Tmax (rs/rroot)x where: Ts= blade thickness at the measured section, s Tmax= maximum blade thickness near the root tip end portion rs= radius ratio x at section s rroot= section radius at blade root end x= between 1.⊘ and ⊘.5 (value assigned so that minimum value of Ts will not be less than 3 times thickness at blade trailing edge). In order that the minimum value of blade thickness Ts will not be less than three times the thickness of the blade edge, the value of x is selected as above falling between 1.⊘ and ⊘.5 as indicated. The limit of three times the thickness of the blade edge is desirable but a limit of four times blade edge thickness is regarded as well within the scope of the invention. As will be apparent from the foregoing, the blade mid-chord points are gradually shifted forwardly in progression from the root end portion of the blade to the tip end portion by the forward sweep of the blade leading edge. Thus, the dimension x shown in Fig. 2 may represent an approximate overall forward shift of the blade mid-chord point from the root end portion of the blade to the tip end portion thereof. Finally, and further in accordance with the present invention, the improved air impeller is provided with an orifice ring partially shown at 26. The orifice ring 26 includes a flange at one end thereof which forms a smooth radius with the remaining part of the ring. The ring 26 is formed integrally with the outer end portion 18 of the blade 12 and is similarly formed with the remaining nine blades of the impeller so as to circumscribe the plurality of blades forming the impeller. As best illustrated in Fig. 2, the impeller has upstream and downstream edges or ends and the upstream or downstream edge or end thereof is at least approximately bell mouthed. This of course serves to provide for a smooth flow of air into or from the fan blades and tends to prevent blade to blade leakage of air around the tips of the blades. Obviously, the outer surface of the orifice ring may be contoured to match an associated housing or other opening in which the impeller is mounted. Clearance employed between the moving and stationary surfaces at the outer diameter of the ring can be provided at normal manufacturing tolerances found in high volume commercial applications. With this arrangement a better air seal is achieved than can be obtained using a conventional air impeller design without an orifice ring but employing very tight running tolerances. That is, a clearance of ⊘.1⊘ inches (0.254 cms) with the ring will match a clearance of ⊘.⊘⊘5 inches (0.013 cms) without a ring. As mentioned, the improved axial flow air impeller of the present invention provides for very low operating noise, maximum aerodynamic efficiency, improved mechanical strength and minimum material usage in manufacture. The thickness variation minimizes stress in the blades and at the same time reduces the amount of material required to make the blades. The addition of the orifice ring provides lateral stiffness to the impeller blades which accommodates the relatively thin blade sections, this in addition to the primary function of the orifice ring in reducing blade tip leakage. The reduction in blade tip leakage contributes directly to higher aerodynamic efficiency and the resulting decrease in flow disturbance around the blade tips serve still further to reduce noise generation.
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An axial flow air impeller for automotive radiator, heat exchanger use and the like comprising a hub (10) adapted for rotation about an axis (16) and carrying a plurality of integrally formed similar circumaxially spaced and generally radially outwardly projecting air moving blades (12, 12a), each of said blades having a root end portion (14) integral with the hub (10) and a radially outwardly disposed tip end portion (18) with smoothly curving side edges (20, 22) therebetween, said air impeller being adapted for unidirectional rotation in a forward direction (24) and said side edges comprising leading (20) and trailing (22) edges the former of which curves substantially forwardly when viewed from root end portion (14) to tip end portion (18) to provide a projected width of each blade which is at least 40% greater at the tip end portion (18) than at the root end portion (14); each blade having a maximum thickness which varies from a maximum at the root end portion (14) and the maximum thickness at the tip end portion (18) being at least three times the thickness at the blade trailing edge (22); an orifice ring (26) integral with each blade tip end portion (18) and circumscribing the plurality of blades (12, 12a), said ring (26) having upstream and downstream ends and having a flange at one end with a substantially smooth radius at the junction with the ring portion, CHARACTERISED IN THAT the thickness of each blade reduces as it progresses from its root end portion (14) to a minimum thickness at its tip end portion (18) and said reduction is determined so that the maximum blade thickness at any blade section is: Ts = Tmax (rs/rroot)x where Ts= blade thickness at the measured section, s Tmax= maximum blade thickness near the root tip end portion rs= radius ratio x at section s rroot= section radius at blade root end x= between 1.0 and 0.5 (value assigned so that minimum value of Ts will not be less than three times thickness at blade trailing edge). An axial flow air impeller as claimed in claim 1 wherein said blade trailing edges (22) extend at least approximately along radial lines so that blade mid-chord points are gradually shifted forwardly in progression from root end portion (14) to tip end portion (18) by the forward sweep of the blade leading edges (20). An axial flow air impeller as claimed in either claim 1 or claim 2 wherein the forward curve of each blade leading edge (20) is such that the blade width is approximately 40% to 80% greater at the tip end portion (18) than at the root end portion (14). An axial flow air impeller as claimed in any one of the preceding claims in which the root end portion (14) of each blade is arranged at an angle of pitch relative to the axis (16) and said angle of pitch decreases from the root end portion (14) to the tip end portion (18) of the blade. An axial flow air impeller as claimed in any one of the preceding claims wherein a major portion of the forward curve at the leading edge (20) of each blade occurs at the outer one-half of the blade measured from the root end portion (14) to the tip end portion (18). An axial flow air impeller as claimed in claim 5 wherein the major portion of the forward curve at the leading edge of each blade occurs at the outer one-third of the blade measured from the root end portion (14) to the tip end portion (18).
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TORRINGTON RES COMP; THE TORRINGTON RESEARCH COMPANY
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O'CONNOR JOHN F; O'CONNOR, JOHN F.
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EP-0489998-B1
| 489,998 |
EP
|
B1
|
EN
| 19,940,427 | 1,992 | 20,100,220 |
new
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C09D5
| null |
C09D5, C09D187, C09D123
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C09D 5/16H3K
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Antifouling paint
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An antifouling paint which can retain antifouling properties over a long period of time comprises (A) 100 parts by weight of a film-forming resin, and (B) 1-50 parts by weight of a chain organopolysiloxane containing oxyalkylene groups and having an HLB of 3-12.
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This invention concerns an antifouling paint for application to underwater or marine structures including fishing nets such as stationary nets and culture nets, ocean tanks and bridge beams, various types of marine equipment, and ships; and in particular concerns an antifouling paint suitable for application to fishing nets. Fishing nets and marine structures, marine equipment and ships are exposed to long periods of use in water and especially sea water. As a result of this, marine organisms tend to adhere to and proliferate on parts in contact with sea water, and the function of said fishing nets and other equipment may be impaired. Insofar as concerns fishing nets, stationary nets and culture nets are left in sea water for very long periods of time. Adhesion and proliferation of marine organisms on these nets is particularly serious, so the nets must be replaced frequently and high economic losses are sustained. It is therefore essential to paint these fishing nets with an antifouling paint which makes it difficult for marine organisms to adhere to them. The marine organisms referred to here which cause such a problem include animal species such as barnacles, hydrozoa, slimy sea squirts, sponges, small polyzoans, skeleton shrimps, hairy polyzoans, sea squirts, serpulas, sea anemones and oysters, and plant species such as sea lettuces, ceramium and green laver. It is also necessary to prevent the adhesion of organic waste or slime originating from the excreta or carcasses of these animal and plant species. Antifouling paints with addition of silicone oils have been used for this purpose, conventional examples of these silicone oils being dimethyl silicone oil and phenylmodified silicone oil which has improved compatibility with the resin component and chemical components of the paint. However, although these conventional silicone oils conferred satisfactory water repellent peoperties on the paint, their antifouling properties were not so good, and an effective antifouling paint could not therefore be obtained. In conventional antifouling paints, moreover, it was unclear what kind of structure and properties the added silicone oil should have in order to confer good antifouling properties on the resin, and in particular acrylic resin, which is the main component of the paint film. A satisfactory antifouling paint therefore had still not been proposed. The inventors of the present invention carried out an extensive investigation of the factors affecting the performance of antifouling paints with added silicone oil, and made the following observations: (1) An organopolysiloxane with suitable coordination power to support the acrylic or other film-forming resin is required. (2) An organopolysiloxane with intermediate hydrophilic properties with respect to the film-forming resin is most desirable. (3) If a film-forming resin and liquid resin are used in conjuction, it is desirable that this organopolysiloxane has no interaction with the groups responsible for the cohesive force of the resins. The inventor of this invention then found that excellent results were obtained by the addition of polyether modified silicone oils with a specific hydrophilic lipophilic balance (HLB). One object of this invention is therefore to provide an antifouling paint with added silicone oil which retains high antifouling properties over a long period of time. A further object of this invention is to provide an antifouling paint which is particularly effective when applied to fishing nets. The above objects are attained by an antifouling paint comprising: (A) 100 parts by weight of a film-forming resin, and (B) 1-50 parts by weight of a chain organopolysiloxane containing oxyalkylene groups and having an HLB of 3-12. The antifouling paint of this invention exhibits equivalent or better antifouling properties than conventional antifouling paints even if the blending proportion of antifouling agent is greatly reduced, and also retains these properties over a long period of time. It is therefore an effective paint for underwater marine uses, and particularly for application to fishing nets. The above mentioned film-forming resin which is component (A) of this invention may be an insoluble matrix type resin or an ordinary organic polymer resin for use in antifouling paint. Examples of such insoluble matrix type resins are styrene-butadiene or vinyl chloride resins. Examples of organic polymer resins are polymers and copolymers of acrylic or methacrylic esters, styrene, vinyl acetate, monoethylene type unsaturated compounds such as ethylene and propylene, polyurethane, polyester and epoxy resins, urea resins, alkyd resins, and derivatives of these resins. There is no particular restriction on the molecular weight of the resin provided that it is high enough to effectively maintain strength. Of these resins, acrylic resins are particularly effective as component (A). The before mentioned chain organopolysiloxane with oxyalkylene groups which is component (B) of this invention is normally a polyether modified silicone oil, but it must in particular have a hydrophilic lipophilic balance (referred to hereafter as HLB) in the range 3-12. This component (B ) may typically be an organopolysiloxane represented by the following general formula: M₂-D₄-C₃H₆-O-(C₂H₄O)₉-Hin which M is a monofunctional siloxane unit wherein one oxygen atom is bonded to a silicon atom, and is preferably represented by the general formula: where R¹, R² and R³ are alkyl groups, and usually methyl groups, and D is a bifunctional siloxane unit wherein 2 oxygen atoms are bonded to a silicon atom, and is represented by the general formula: where R⁴ and R⁵ are alkyl, alkenyl or aryl groups, and are usually chosen from methyl, vinyl and phenyl. As described above, HLB is the hydrophilic lipophilic balance. The HLB of high molecular weight compounds is generally given by the following formula: HLB = Weight % of polyoxyethylene in high molecular weight compound5The hydrophilic properties of the compound are therefore greater for higher values of HLB. As stated, the HLB of component (B) in this invention must lie within the range 3-12, but preferably within the range 4-11, and more preferably within the range 9-11. If HLB is less than 3, antifouling properties deteriorate, while if it is greater than 12, hydrophilic properties are too marked and the antifouling effect cannot be retained over a long period of time. In addition to said components (A) and (B) of the antifouling paint of this invention, a liquid resin such as polybutene resin may also be included as a component (C), which confers adhesive properties on the paint (referred to hereafter as adhesive resin), and also functions to increase the pliancy of the film. Component (C) may for example be a random copolymer obtained by reacting, at low temperature in the presence of a catalyst, the isobutylene and normal butylene in the butane-butylene distillate produced by decomposition of naphtha. The blending proportion of component (C) may be adjusted suitably in order to provide film strength and retention of antifouling properties. In particular, if the antifouling paint of this invention is used on underwater structures to prevent adhesion and proliferation of marine organisms, it is desirable that in addition to components (A), (B) and (C), it also contains an antifouling agent (D). This antifouling agent may be a disinfectant or a repellent. Said antifouling agent may be for example be an organotin compound, organozinc compound, halogenated aromatic compound, sulfamide type compound, or flakes or a fine powder of uptic or cuprous oxide. A photosynthesis inhibitor such as a triazine type compound may also be blended with the antifouling paint of this invention as a further component (E). Conventional plasticizers, anti-drip agents, coloring pigments or body pigments known in the prior art may also be blended with the antifouling paint of this invention. When incorporating (A), (B) and other components of this invention into the paint, they may first be diluted with an organic solvent such as toluene or xylene. EXAMPLESWe shall explain this invention in more detail with reference to specific Examples, but it should be understood that the invention is in no way limited by them. The figures for blending proportions given in the tables are proportions by weight. EXAMPLES 1-5Antifouling paints were prepared by blending and thoroughly dispersing the specified components by means of a Labo Mixer so as to obtain the compositions shown in Table 1. The paints so prepared were applied to 35 cm × 45 cm fishing nets (Taito SeiKo K.K. Hizex (trade name), 400 denier, 60 strand, 60 mm mesh). After allowing the paint to harden, the nets were suspended off the coast of Shimonoseki, Yamaguchi Prefecture at an underwater depth of 2 m, and the adhesion of marine organisms and plants was observed so as to evaluate the antifouling performance of the paint. Table 3 shows the results. COMPARATIVE EXAMPLES 1-5Components were blended so as to obtain the compositions shown in Table 2. Antifouling paints were prepared and their antifouling performance was evaluated in the same way as in Example 1-5. Table 3 shows the results. The results of Table 3 show that antifouling paint of this invention is effective for marine applications, and in particular remarkably inhibits the adhesion of marine organisms to underwater structures.
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An antifouling paint comprising a film-forming resin and a silicone oil, characterised in that the paint comprises: (A) 100 parts by weight of a film-forming resin, and (B) 1-50 parts by weight of a chain organopolysiloxane containing oxyalkylene groups and having an HLB of 3-12. A paint as claimed in claim 1, wherein the film-forming resin (A) is an acrylic resin. A paint as claimed in claim 1 or 2, wherein the chain organopolysiloxane (B) is represented by the following general formula: M₂-D₄-C₃H₆-O-(C₂H₄O)₉-H in which M is a monofunctional siloxane unit containing one oxygen atom which is bonded to a silicon atom, and D is a bifunctional siloxane unit containing two oxygen atoms which are bonded to a silicon atom. A paint as claimed in claim 3, wherein the unit M is represented by the following general formula: in which R¹, R² and R³ are each an alkyl group. A paint as claimed in claim 4, wherein one or more of R¹, R² and R³ are methyl groups. A paint as claimed in claim 3 or 4, wherein the unit D is represented by the following general formula: in which R⁴ and R⁵ are each an alkyl, alkenyl or aryl group. A paint as claimed in claim 6, wherein R⁴ and R⁵ are selected from methyl, vinyl and phenyl groups. A paint as claimed in any preceding claim, wherein the HLB lies within the range 4-11. A paint as claimed in claim 8, wherein the HLB lies within the range 9-11. A paint as claimed in any preceding claim, and further containing one or more components selected from adhesive resins, disinfectant anti-fouling agents, repellent anti-fouling agents, photosynthesis inhibitors, anti-drip agents, coloring pigments and body pigments.
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HAYASHIKANE PAINT CO LTD; HAYASHIKANE PAINT CO., LTD.
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NAKAI YOSHITO HAYASHIKANE PAIN; NAKAI, YOSHITO, HAYASHIKANE PAINT CO. LTD.
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EP-0490001-B1
| 490,001 |
EP
|
B1
|
EN
| 19,960,710 | 1,992 | 20,100,220 |
new
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G06F3
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G06F3
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G06F3
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G06F 3/048A3G
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Coordinate processor for a computer system having a pointing device
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A coordinate processor for a computer system having an absolute position pointing device (10) such as a touch sensitive display screen comprises stimulus detection means (200) for detecting a tactile stimulus of an absolute position pointing device (10) directed to a point within a data display area (610) of a computer system. The processor further comprises coordinate locking means (210-320) for locking a current cursor position to the point within the display area corresponding to the tactile stimulus in response to said stimulus exceeding a predetermined threshold value. The processor permits the computer system to distinguish a stimulus of the pointing device (10) for repositioning the cursor within the data display area (610) from a stimulus of the pointing device (10) for issuing a button click command to the computer system. The processor may be embodied in an electronic logic circuit within a pointing device adapter portion of the computer system. Equally, the coordinate processor may be in the form of a central processing unit operating under the control of a computer program.
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The present invention generally relates to a coordinate processor for a computer system having a pointing device such as a touch sensitive display screen. Many widely available computer systems such as the IBM PS/2 Model 70 (IBM and PS/2 are trademarks of IBM Corporation) are capable of receiving and processing data generated by a pointing device such as a mouse, tracker ball or touch sensitive display screen. The pointing device enables a user of the computer system to move, with a simple hand movement, a cursor between points within a data display area of a visual display unit. A relative displacement pointing device such as a mouse or tracker ball provides the computer system with a vector which identifies the location within the data display area to which the cursor is to be moved relative to the current location of the cursor. The vector is generated by manipulating of the pointing device to achieve a desired cursor movement. An absolute position pointing device such as a touch sensitive display screen provides the computer system with two dimensional coordinates identifying a point within the data display area to which the cursor is to be moved. In a touch sensitive display screen, the coordinates are generated by touching the screen at the point to which the cursor is to be moved. In general, relative displacement pointing devices are also provided with at least one manually operable push button. The button can be operated by the user in a number of different modes and the computer system can be configured to respond differently to each mode of operation of the button. For example, the computer system may be configured to manipulate a window of displayed data within the data display area when the button is depressed as the pointing device is moved. Equally, the computer system may be programmed to perform another task when the cursor is placed on an icon representing the task within the display area and the button is depressed and released in rapid succession or clicked . The computer system may also be configured to perform yet another task when the cursor is placed on an icon and the button is clicked twice or double-clicked . Touch screens are not generally provided with a manually operable push button. A button click command may however be issued via a touch screen by applying a corresponding sequence of touch stimuli to the touch screen within a predetermined time period. An example of a virtual push-button system is described in US Patent No 4,914,624. However, it will be appreciated that if each stimulus in the sequence is applied to a different point within a target area of the screen, then the computer system may fail to distinguish the button click command from a request to move the cursor from one point to another. In general therefore, absolute position pointing devices have been thought of as unsuitable for issuing button click commands. Many commercially available application software packages have therefore been written with relative displacement pointing devices in mind. Such packages can therefore be wholly, or at least partially, incompatible with computer systems having absolute position pointing devices. An aim of the present invention is therefore to provide a coordinate processor which enables a computer system comprising an absolute position pointing device to operate in the same manner as a computer system having a relative displacement pointing device. In accordance with the present invention, there is now provided a coordinate processor comprising: stimulus detection means for detecting a tactile stimulus of an absolute position pointing device directed to a point within a data display area of a computer system; characterised in that the processor further comprises command distinguishing means responsive to the stimulus detection means to distinguish a stimulus of the pointing device for repositioning a cursor within the data display area from a stimulus of the pointing device for issuing a button click command to the computer system, and including coordinate locking means for locking a current cursor position to the point within the display area corresponding to the tactile stimulus in response to said stimulus exceeding a predetermined threshold value. This advantageously enables the computer system to distinguish between cursor movement commands and button click commands issued via an absolute position pointing device without requiring a separate, manually operable push button. An operator of such a computer system can therefore fully exploit application software packages designed for operation with relative displacement pointing device without any perceptible degradation in performance of the computer system. Specifically, the coordinate processor enables the computer system to lock the position of the cursor onto a particular coordinate when a stimulus which may signal a button click command is detected. If however, a button click command is not subsequently detected, the cursor is automatically unlocked. Preferably, the coordinate locking means further comprises first reset means for releasing the cursor for movement within the data display area upon detection of a predetermined button click command. The coordinate locking means of a preferred embodiment of the present invention further comprises second reset means for releasing the cursor for movement within the data display area upon expiry of a predetermined timeout period. In addition, the coordinate locking means preferably further comprises third reset means for releasing the cursor for movement within the data display area upon detection of a subsequent tactile stimulus of the pointing device directed to a point outside a predetermined subarea of the data display area. Preferably, the subarea is predetermined by the computer system to be commensurate in size with an graphical icon generated within the display area by the computer system. Viewing the present invention from a second aspect, there is now provided a coordinate processor comprising: stimulus detection means for detecting a stimulus applied to an absolute position pointing device and directed to a point within a data display area defined by a computer system; characterised in that the processor further comprises: command distinguishing means responsive to the stimulus detection means to distinguish a stimulus of the pointing device for repositioning a cursor within the data display area from a stimulus of the pointing device for issuing a button click command to the computer system. Preferably, the command distinguishing means can be manually preset to identify either a tactile stimulus of the pointing device for issuing a single button click command to the computer system, or a tactile stimulus of the pointing device for issuing a multiple button click command to the computer system. In a preferred embodiment of the present invention to be described later, there is provided a coordinate processor comprising: first receiver means for receiving from an absolute position pointing device an input two dimensional coordinate data value corresponding to a point within a data display area of a computer system and generated by the pointing device in response to a stimulus manually applied to the pointing device; second receiver means for receiving from the pointing device a force data value corresponding to the input coordinate value and generated by the pointing device in response to the stimulus; characterised in that the processor further comprises: coordinate locking means for setting a lock coordinate data value to the input coordinate data value in response to the force data value exceeding a predetermined threshold value; coordinate setting means for setting one or more further input coordinate force data values to the lock coordinate data value in response to any one of the further input coordinate data values falling within a predetermined range of coordinate data values during a predetermined time period; first reset means for resetting the lock coordinate data value in response to at least one discrete stimulus of the pointing device generating a force data value greater than the predetermined threshold value. A preferred embodiment of the present invention will now be described, by way of example only with reference to the accompanying drawings in which: Figure 1 is a block diagram of a computer system comprising an absolute position pointing device in the form of a touch-sensitive visual display screen. Figure 2 is a block diagram of a coordinate processor of the present invention in the form of a flow chart. Figure 3 is a front view of a touch sensitive display screen displaying an icon within a data display area. Figure 4 is a waveform diagram corresponding to tactile stimuli representative of a double click command. Figure 5 is a waveform diagram corresponding to a tactile stimulus representative of a single click command. Figure 1 illustrates an example of a computer system for processing input data from an absolute position pointing device. The system comprises a central processing unit (CPU) 20 for executing programmed instructions involving the input data. A bus architecture 30 communicates data between the CPU and other components of the computer system. A read only memory (ROS) 40 provides secure data storage. A random access system memory 50 provides temporary data storage. Data communication with other computer systems (not shown) is provided by a communications (COMM) adapter 60. An input/output (I/O) adapter 70 permits data communication between the bus architecture and a peripheral device such as a hard disk file 80. A visual output from the computer system in the form of a data display area is generated on a display device 110 by a display adapter 120. A user can operate the computer system using a keyboard 90 linked to the bus architecture via a keyboard adapter 100. By way of alternative to keyboard 90, an absolute position pointing device in the form of a touch sensitive display screen 10 is superimposed on display device 110. The touch screen 10 is responsive to a touch stimulus 130 applied by the user to issue a command to the computer system. The command may instruct the computer system to move a cursor between points within the data display area. Alternatively, the touch screen may be employed to issue a button click command instructing the computer system, to an operation corresponding to the current position of the cursor in the display area. The touch screen 10 is resolved by digitising circuitry (not shown) in a pointing device adapter 140 into a two dimensional array of discrete coordinate points. A touch stimulus applied to any one of the coordinate points is detected by a sensor array (not shown) in the touch screen 10. The sensor array generates an analog signal proportional to the force imparted to the touch screen by the stimulus. The signal is digitised by a sampling analogue to digital convertor (ADC) circuit (not shown) in the touch screen 10 to produce a input data value. The input data value, together with the coordinates to which it relates, are transmitted from the touch screen to the pointing device adapter 140. The input data value corresponding to each set of coordinates is typically refreshed by the ADC circuit sixty times a second. The pointing device adapter 140 connected to the bus architecture 30 passes each set of coordinates and the corresponding input data value to the bus architecture 30. Referring now to Figure 2, a coordinate processor of the present invention distinguishes stimuli applied to the touch screen 10 to issue button click commands from stimuli to move the cursor within the display area. It will be appreciated that the coordinate processor of the present invention may be embodied in a hardwired electronic logic circuit within the pointing device adapter 140 or the touch screen 10. However, it will also be appreciated that, in other preferred embodiments of the present invention, the coordinate processor may be in the form of a processing unit such as CPU 20 operating under the control of a computer program. The coordinate processor comprises an input stage 200. The input stage 200 sequentially reads the sampled input data value corresponding to each set of coordinates (x,y) of the touch screen 10 in turn. The coordinate processor increments a running total of button clicks BCNT each time a button click is detected. Initially BCNT is zero. A count detect stage 210 checks BCNT for each input data value (x,y)n received from input stage 200. If BCNT corresponding to coordinates (x,y) is zero, then a depress detect stage 280 determines whether or not the corresponding input data value has increased above a predetermined button threshold value, THOLD. If no such increase is detected, coordinates (x,y) are passed from coordinate processor to the computer system to control the positioning of the cursor within the display area. The next input data value is then received by input stage 200. If, however, the input data value has increased over and above THOLD, then a timer stage 290 sets a timeout period, TIMEOUT which is equal to a current system clock value plus a predetermined value. In a preferred embodiment of the present invention, the timeout period can be manually adjusted about a nominal preset centre value of 500ms. Another count detect stage 300 then determines again whether or not BCNT is zero. If BCNT is zero, then a coordinate locking stage 310 sets a pair of lock coordinates (xL,yL) to coordinates (x,y). If BCNT is not zero, the lock coordinates (xL,yL) retain their existing values. In either case, coordinates (x,y) are then passed to the computer system to control cursor positioning. A counter 320 then increments BCNT and the next input data value (x',y')n corresponding to coordinates (x',y') is received by input stage 200. If count detect stage 210 determines that BCNT is greater than zero for input data value (x',y')n, timer stage 220 indicates whether or not the timeout period has been exceeded. If the timeout period has been exceeded, then a reset stage 270 resets BCNT to zero before (x',y')n is passed to depress detect stage 280. If the timeout period has not been exceeded, then an location check stage 230 determines whether or not coordinates (x',y') are outside a predetermined coordinate locking area, AREA, of the data display area. If coordinates (x',y') are outside AREA, then reset stage 270 resets BCNT before the (x',y')n is passed to depress detect stage 280. If coordinates (x',y') are within AREA, then a lock stage 240 replaces coordinates (x'y') corresponding to input data value (x',y')n with the lock coordinates (xL,yL). Release detect stage 250 then detects whether or not input data value (x',y')n has decreased to below THOLD. If no such decrease is detected, then input data value (x',y')n, now corresponding to lock coordinates (xL,yL), is passed to depress detect stage 280. The cursor position is now locked to the lock coordinates (xL,yL). If input data value (x'y')n has decreased over and below THOLD, then count detect stage 260 determines whether or not BCNT is equal to a predetermined click value, NCLICK. In a particularly preferred embodiment of the present invention, NCLICK can be manually selected by the operator to detect different button click commands. For example, setting NCLICK to two configures the coordinate processor to detect both double and single click commands. Alternatively, setting NCLICK to one configures the cooordinate processor to detect only single click commands. If BCNT is equal to NCLICK, the button click command has been detected. BCNT is therefore reset to zero and input data value (x',y')n is passed to depress detect stage 280. The next input data value, (x'',y'')n corresponding to coordinates (x'',y''), is then received by input stage 200. In a preferred embodiment of the present invention, predetermined values TIMEOUT, AREA, THOLD, and NCLICK are supplied to the coordinate processor by CPU 20 under the control of an application software program. In particular, with reference to Figure 3, AREA is preferably selected to represent an area 600 of size and location commensurate with an icon 620 representing graphically, within the data display area 610, a push button or the like. Preferably, the computer system is configured by the software so that the operator can select a particular program option by issuing a click command via touch screen 10 at the position of the icon within the display area.. Referring now to Figure 4, a double click command can be represented in the form of a curve 400 of tactile force applied to touch screen 10 with respect to time. Button threshold THOLD is represented by reference line 420. Initially, BCNT is set to zero, NCLICK is set to 2, and TIMEOUT, AREA, and THOLD are set to appropriate values by the application software. Initial tactile contact with touch screen 10 is made at time t0 where curve 400 is coincident with reference line 410. At time t1, input data value (x,y)1 at coordinates (x,y) is lower than THOLD. However, at time t2, input data value (x,y)2 at coordinates (x,y) is greater than THOLD. Depress detect stage 280 therefore indicates that the button is being depressed, and the timeout period is initialised by timer stage 290. Lock coordinates (xL,yL) are now set to coordinates (x,y). BCNT is incremented to indicate that the position of the cursor within the display area are now locked to the lock coordinates (xL,yL). Therefore, if the next force data values (x',y')3 at time t3 and (x'',y'')4 at time t4, correspond to coordinates (x',y') and (x'',y'') within the confines of AREA, then coordinates (x'y') and (x'',y'') are both replaced by lock coordinates (xL,yL). It will be appreciated that if either (x',y') or (x'',y'') fall outside AREA then BCNT would reset to zero thereby unlocking the cursor position. At time t5, input data value (x,y)5 is just greater than THOLD. However, at time t6, input data value (x,y)6 is lower than THOLD. Release detect stage 260 therefore indicates that the button is being released. However, BCNT does not equal NCLICK. BCNT is therefore not reset to zero. Therefore coordinates (x',y') corresponding to input data value (x',y')7 at time t7 are also replaced by lock coordinates (xL,yL). The cursor position is therefore still locked. At time t8, input data value (x',y')8 is greater than THOLD. The timeout period is therefore initialised again by time stage 290. BCNT is incremented to indicate that a second button click has been detected. Lock coordinates (xL,yL) remain set to coordinates (x,y) originally corresponding to input data value (x,y)2. The cursor therefore remains locked to (x,y) within the display area. At time t9, input data value (x,y)9 is lower than THOLD. Therefore release detect stage 250 indicates that the button is being released. BCNT is now equal to NCLICK indicating that a double click command has been detected. BCNT is now reset to zero to unlock the cursor position. The next touch stimulus producing a input data value greater than THOLD will therefore refresh lock coordinates (xL,yL). It will be appreciated that BCNT will also be reset to zero if it is maintained at a value greater than zero for a period greater than the timeout period. Similarly, BCNT will be be reset to zero if any input stimulus is applied at a coordinate outside AREA. A coordinate processor of the present invention therefore permits the operator to issue a double click command to a computer system via a touch sensitive display screen by locking the cursor position to a position within the display area at which an applied touch stimulus is of a magnitude exceeding a threshold value. The cursor position is unlocked when the prescribed number of clicks identifying the command is detected. Alternatively, the cursor position is unlocked if a subsequent stimulus is applied to the touch screen outside a predetermined area of the touch screen. Furthermore, the cursor position is also unlocked if the delivery of the command extends beyond a predetermined timeout period. It will therefore be appreciated that the coordinate processor of the present invention provides the operator of the computer system with freedom at all times to move the cursor to any point within the display area. Simultaneously however, the coordinate processor of the present invention enables the operator to issue via the touch screen a button click command to the computer system which is independent of any cursor movement command. Referring now to Figure 5, a single click command can be represented in the form of a curve 500 of tactile force applied to the touch screen 10 with respect to time. Button threshold THOLD is represented by reference line 420. Initially, BCNT is set to zero and NCLICK is set to 1. TIMEOUT, AREA, and THOLD are set to appropriate values by an application software program. Initial tactile contact is made with the touch screen 10 at time t0 where curve 500 is coincident with reference line 410. At time t1, input data value (x,y)1 corresponding to coordinates (x,y) is lower than THOLD. At time t2 however, input data value (x,y)2 corresponding to coordinates (x,y) is greater than THOLD. Depress detect stage 280 therefore indicates that the button is being depressed and the timeout period is initialised by timer stage 290. Lock coordinates (xL,yL) are now set to coordinates (x,y) and BCNT is incremented. The cursor position is now locked to coordinates (x,y). If coordinates (x',y') and (x'',y''), corresponding to force data values (x',y')3 at time t3 and (x'',y'')4 at time t4, are within the confines of AREA, then (x',y') and (x'',y'') are both replaced by lock coordinates (xL,yL). The cursor position is therefore locked at coordinates (x,y). If either (x',y') or (x'',y'') are outside AREA then BCNT will be reset to zero and the next input data value to exceed THOLD will refresh lock coordinates (xL,yL) and relock the cursor position. values. At time t5, input data value (x,y)5 is lower than THOLD. Therefore, release detect stage 260 indicates that the button is being released. BCNT now equals NCLICK indicating that the single click command has been detected. BCNT is now reset to zero. Therefore, the next input data value to exceed THOLD will refresh lock coordinates (xL,yL) It will now be appreciated that a coordinate processor of the present invention also enables the operator of the computer system to issue a single click command to the a computer system via a touch sensitive display screen. In addition however, a coordinate processor of the present invention also enables the operator to issue cursor movement command to the computer system through the touch screen independently of button click commands. Specifically, the coordinate processor of the present invention locks the cursor position to a point on the touch screen at which an applied touch stimulus has a magnitude exceeding a threshold value. The cursor position is unlocked when the button click command is detected, or if a subsequent stimulus is outside a predetermined area of the touch screen. The cursor position is also unlocked if the delivery of the command extends beyond a predetermined timeout period. It will therefore be appreciated that the cursor may be freely moved to any point within the display area depending on whether or not the operator wishes to complete delivery of the button click command. Curve 510 illustrates a continuous tactile stimulus of the touch screen applied initially at time t0. BCNT is initially set to zero. At time t1, input data value (x,y)1 corresponding to coordinates (x,y) is lower than THOLD. However, at t2, input data value (x,y)2 corresponding to coordinates (x,y) is greater than THOLD. Therefore, depress detect stage 280 indicates that the button is being depressed and the timeout period is initialised. Lock coordinates (xL,yL) are now set to coordinates (x,y) and BCNT is incremented. The cursor position is now locked to (x,y). At time t5, input data value (x,y)5 is not below THOLD. Therefore, if no stimulus has been applied to the touch screen outside AREA at time t5, BCNT is not reset. The cursor position remains locked to coordinates (x,y). At time t5' however, the timeout period expires. BCNT is therefore reset to zero. The cursor position is therefore unlocked. The next touch stimulus exceeding THOLD will thus refresh lock coordinates (xL,yL). A coordinate processor for a computer system having touch sensitive display screen has now been described by way of example of the present invention. It will however be appreciated that the present invention is equally applicable to other absolute position pointing devices such as, for example, tablets.
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A coordinate processor comprising: stimulus detection means (200) for detecting a tactile stimulus of an absolute position pointing device (10) directed to a point within a data display area (610) of a computer system; characterised in that the processor further comprises command distinguishing means responsive to the stimulus detection means to distinguish a stimulus of the pointing device for repositioning a cursor within the data display area from a stimulus of the pointing device for issuing a button click command to the computer system, and including coordinate locking means (210-320) for locking a current cursor position to the point within the display area corresponding to the tactile stimulus in response to said stimulus exceeding a predetermined threshold value. A processor as claimed in claim 1 wherein the coordinate locking means (210-320) further comprises first reset means (260, 270) for releasing the cursor for movement within the data display area (610) upon detection of a predetermined button click command. A processor as claimed in claim 1 or claim 2 wherein the coordinate locking means (210-320) further comprises second reset means (290, 220, 270) for releasing the cursor movement within the data display area (610) upon expiry of a predetermined timeout period. A processor as claimed in any preceding claim wherein the coordinate locking means (210-320) further comprises third reset means (230, 270) for releasing the cursor for movement within the data display area (610) upon detection of a subsequent tactile stimulus of the pointing device (10) directed to a point outside a predetermined subarea (600) of the data display area (610). A processor as claimed in claim 4 wherein the subarea (600) is predetermined by the computer system to be commensurate in size with a graphical icon (620) generated within the display area (610) by the computer system. A processor as claimed in any preceding claim, wherein the coordinate locking means (210-320) can be manually preset to identify a tactile stimulus of the pointing device (10) for issuing a single button click command to the computer system. coordinate processor as claimed in any of claims 1 to 5 wherein the coordinate locking means (210-320) can be manually preset to identify a tactile stimulus of the pointing device (10) for issuing a multiple button click command to the computer system. A processor as claimed in any preceding claim wherein the coordinate locking means (210-320) is responsive to a digital input value corresponding to the force of the tactile stimulus. A processor as claimed in any preceding claim wherein the absolute pointing device (10) is a touch sensitive display screen (10). A computer system comprising a processor as claimed in any preceding claim.
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IBM; INTERNATIONAL BUSINESS MACHINES CORPORATION
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BEARDALL GAVIN DAVID; CALDER GARY JAMES; BEARDALL, GAVIN DAVID; CALDER, GARY JAMES
|
EP-0490002-B1
| 490,002 |
EP
|
B1
|
EN
| 19,960,327 | 1,992 | 20,100,220 |
new
|
H04L29
| null |
H04L29
|
T04L29:08A2, H04L 29/06
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A flag counter circuit
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The circuit counts pre-amble and post-amble synchronisation characters in a serial bit stream transmitted from one computer to another in a local area network and comprises: a detector circuit (2) for detecting the synchronisation characters of a serial bit stream and generating a synchronous output pulse for each synchronisation character detected; a counter circuit (3) for counting the number of output pulses generated by the detector circuit (2) and generating a terminal count output signal when a predetermined number of output pulses have been counted; and an interrupter circuit (4) for generating an interrupt request signal for the computer transmitting or receiving the serial bit stream on receipt of the terminal count output signal.
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This invention relates to a flag counter circuit for counting pre-amble and post-amble synchronisation characters in a serial bit stream transmitted from one computer to another in a local area network (LAN) Whenever a serial bit stream is to be transmitted along a network bus from one computer to another, all computers connected to the bus must receive a synchronisation character before the remainder of the serial bit stream can be transmitted. For this reason, the synchronisation field of the serial bit stream may comprise 40-60 characters and thus last several milliseconds so as to ensure that all computers on the network are synchronised. The more computers on the network or the longer the bus between them, the greater the number of synchronisation characters that must be provided to ensure that all parts of the network are synchronised before the remainder of the serial bit stream is transmitted. In practice, the duration of the synchronisation field is arranged to be at least twice as long as the round trip delay of the network bus. In the past, local area networks between two or more computers using carrier sense multiple access/collision detection (CSMA/CD) protocols, or other high level data link control (HDLC) protocols have performed the task of waiting for transport layer synchronisation character periods to complete by using a central processor unit (CPU) of the computer transmitting or receiving a serial bit stream signal to poll cable status registers when the signal is being received or to time transmission periods when the signal is being transmitted. An alternative technique, during transmit operations, has been to use dedicated hardware timer peripheral circuit to generate an interrupt request a pre-determined time after the start of the signal to allow an approximate number of synchronisation characters to be generated. Thus, in a transmission operation, the following steps occur: (1) the transmitter waits for the bus to become free (2) the transmitter then starts a continuous transmission of synchronisation characters (3) a timer circuit is programmed to time a given period t = number of synchronisation characters to be transmitted x the time duration of one synchronisation character (4) after time t has elapsed, an interrupt request signal is generated by the timer circuit (5) in response to the interrupt request signal, the transmitter ceases transmission of synchronisation characters and begins the transmission of packet data. Against a background of increasing demands on CPU bandwidth, particularly in single CPU systems such as personal computers (PCs), these known techniques have resulted in high usage of CPU time and resulted in inaccurate numbers of synchronisation characters being generated or detected. Such inaccuracy is inherent in systems that time periods rather than count the number of synchronisation characters due to rounding errors and the accuracy of the clock signal used. The rounding error may, for instance, be plus or minus one within a count of 20 or 30 and the clock signal may be innacurate to 1-2%. According to the present invention, there is provided a flag counter circuit for counting pre-amble and post-amble synchronisation characters in a serial bit stream transmitted from one computer to another in a local area network, the circuit comprising: detector means for detecting the synchronisation characters of a serial bit stream and generating a synchronous output pulse for each synchronisation character detected; counter means for counting the number of output pulses generated by the detector means and generating a terminal count output signal when a predetermined number of output pulses have been counted; and interrupter means for generating an interrupt request signal for the computer transmitting or receiving the serial bit stream on receipt of the terminal count output signal. Preferred features of the invention will be apparent from the following description and the subsidiary claims of the specification. The invention will now be further described, merely by way of examples, with reference to the accompanying drawings, in which:- Figure 1 is a block level schematic diagram of a CSMA/CD LAN interface incorporating a flag counter circuit according to an embodiment of the invention; and Figures 2, 3 and 4 are more detailed schematic diagrams of the three main functional units of the flag counter circuit shown in Figure 1, namely a synchronisation character detection circuit, a programmable counter circuit and an interrupt request generator circuit. The flag counter circuit 1 illustrated in the drawings detects and counts a programmable number of CSMA/CD pre-amble and post-amble synchronisation characters and then generates a system level interrupt request. It thus counts the LAN synchronisation characters without involving the CPU of the computer receiving or transmitting the signal in this overhead task. The flag counter circuit therefore removes from the CPU the overhead task of waiting for synchronisation characters to complete by using hardware to detect and count the synchronisation characters and generate a real time interrupt request when a predetermined number of characters have been detected. This is done for both the transmission and reception of synchronisation characters. Thus, during a transmission operation the steps (1) and (2) described above occur, then the steps: (3) a count value for the number of synchronisation characters to be generated is programmed (4) when the set number of synchronisation characters have been generated, an interrupt request signal is generated. Step (5) then occurs as described above. The three main functional units of the flag counter circuit 1 are shown within dashed lines in Figure 1. The circuit comprises a synchronisation character detection circuit 2, a programmable counter circuit 3 and an interrupt request circuit 4. The flag counter circuit 1 is connected to a cable transceiver 5, a CSMA/CD LAN controller 6 and a host computer interface/bus 7 as shown in Figure 1. The CSMA/CD controller 6, programmable counter circuit 3, interrupt request circuit 4 and the interface/bus 7 are linked by a data and control bus 8. The host computer 9 is also shown in Figure 1. The synchronisation character detection circuit 2 is connected to the cable transceiver 5 to receive serial bit streams which are to be transmitted from or received by the host computer 8. It is also connected to receive a clock signal from the CSMA/CD LAN controller 6. The function of the synchronisation character detection circuit 2 is to generate a synchronous output pulse for each synchronisation character detected in the serial bit stream. The programmable counter circuit 3 is connected to receive the output pulses from the synchronisation character detection circuit 2 and is also connected to the data and control bus 8. The function of the programmable counter circuit 3 is to count the number of output pulses generated by the synchronisation character detection circuit 2 and to generate a terminal count output signal when a predetermined number of output pulses has been counted. The interrupt request circuit 4 is connected to receive output signals from the programmable counter circuit 3 and is connected to the data and control bus 8. The function of the interrupt request circuit 4 is to generate an interrupt request signal for the computer which is to transmit or receive the serial bit stream on receipt of a terminal count output signal from the programmable counter circuit 3. The use of a counter circuit rather than a timer circuit, helps reduce the CPU overhead time by eliminating the inaccuracies referred to above which are inherent in a system which times periods. The provision of a counter circuit is usually also more convenient, simpler and less expensive than a timer circuit particularly as counters tend to be provided in blocks of four. The counter circuit may, for example, be conveniently incorporated into a gate array used for other purposes. Details of preferred forms of the synchronisation character detection circuit 2, programmable counter circuit 3 and interrupt request circuit 4 will now be given with reference to Figures 2, 3 and 4, respectively. As shown in Figure 2, the synchronisation character detection circuit 2 comprises a start bit detector circuit 10 connected to receive the serial bit stream from the cable transceiver 5 and a clock signal from the CSMA/CD LAN controller 6. The start bit receiver circuit 10 detects the start bit of a series of synchronisation characters in the serial bit stream. When a start bit has been detected, a character assembler circuit 11 assembles the synchronisation characters received and passes this to a comparator circuit 12. The comparator circuit 12 compares the synchronisation character received from the character assembler circuit 11 with synchronisation characters stored in a memory 13. If the synchronisation character received from the character assemble circuit 11 matches one of those stored in the memory 13, the comparator circuit 12 generates a synchronous output pulse which is passed to the programmable counter circuit 11. The implementation of the synchronisation character detection circuit 3 depends upon the protocol and the specific synchronisation characters used by that protocol. This circuit may be conveniently implemented in a standard serial data link control (SDLC) controller peripheral integrated circuit (IC), such as a Z-8530 serial communication controller (SCC). As shown in Figure 3, the programmable counter circuit 3 may be implemented as a synchronous down-counter, without reload or wrap-around on reaching the terminal count. The circuit comprises a programmable counter 14 connected to the host computer interface/bus 7, to receive a clock signal and to receive the output pulse from the synchronisation character detection circuit 2 via an AND gate 15. The other input of the AND gate 15 is connected to the output of the programmable counter 14 via a NOR gate 16. The programmable counter 14 is loadable with a count value under the control of the CPU of the host computer 9, the count value determining the number of synchronisation characters that will be counted before the terminal count output signal is generated. The programmable counter circuit 3 is conveniently implemented in discrete logic or as part of a user specified integrated circuit (USIC). As shown in Figure 4, the interrupt request circuit 4 comprises a transition detector and latch circuit 17 connected to receive the terminal count output signal from the programmable counter circuit 3, an interrupt control logic circuit 18 connected to the host computer interface/bus 7 and an AND gate 19 connected to outputs of these circuits 17 and 18. When the terminal count output signal is received, the transition detector and latch circuit 17 asserts an interrupt request signal which is latched active. The signal is gated by the interrupt control logic circuit 18. In response to the interupt request signal, the CPU is made available to receive or transmit the serial bit stream. When the request signal has been serviced, a service register bit is asserted by the logic circuit 18 to clear the detector and latch circuit 17. The precise manner in which the interrupt circuit 4 is arranged to function will depend on whether the circuit is to be used in an edge sensitive or level sensitive interrupt request environment. Either may be used. The interrupt request circuit 4 is again conveniently implemented in discrete logic or as part of a USIC. The type of flag counter circuit described above is applicable to micro, mini and mainframe computer networks using HDLC protocols such as CSMA/CD and CSMA/CA. The main improvements over past techniques are: Reduced CPU overhead in the task of detecting or generating synchronisation fields in CSMA/CD LAN interfaces Potentially reduced LAN cable occupation period by increased accuracy and determinancy of synchronisation field duration. Potentially reduced LAN cable occupation period by improved precision in the number of synchronisation characters generated.
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A flag counter circuit for counting pre-amble and post-amble synchronisation characters in a serial bit stream transmitted from one computer to another in a local area network, the circuit comprising: detector means (2) for detecting the synchronisation characters of a serial bit stream and generating a synchronous output pulse for each synchronisation character detected; counter means (3) for counting the number of output pulses generated by the detector means (2) and generating a terminal count output signal when a predetermined number of output pulses have been counted; and interrupter means (4) for generating an interrupt request signal for the computer transmitting or receiving the serial bit stream on receipt of the terminal count output signal. A flag counter circuit as claimed in claim 1 for use with a local area network using a carrier sense multiple access/collision detection (CSMA/CD) protocol. A flag counter circuit as claimed in claim 1 and 2 in which the detector means (2) comprises a start bit detector (10) for detecting the start bit of a synchronisation character, a character assembler (11) for regenerating the synchronisation character detected and comparator means (12) for comparing the regenerated synchronisation character with synchronisation character patterns held in memory (13) and providing the synchronous output pulse if this matches one of these patterns. A flag counter circuit as claimed in claims 1, 2 and 3 in which the counter means (3) comprises a programmable, synchronous down-counter (14) arranged to generate the terminal count output signal when it has counted down from the predetermined number to zero. A flag counter circuit as claimed in any preceding claim in which the interrupter means (4) comprises a transition detector and latch (17) arranged to assert an interrupt request signal on receipt of the terminal count output signal.
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RESEARCH MACHINES PLC
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DAVIDSON DOUGLAS STUART; DAVIDSON, DOUGLAS STUART
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EP-0490004-B1
| 490,004 |
EP
|
B1
|
EN
| 19,960,327 | 1,992 | 20,100,220 |
new
|
H01J29
| null |
H04N9, H01J29
|
H01J 29/70B
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Field harmonic enhancer in a deflection yoke
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In a deflection yoke (55) mounted on a cathode ray tube (90), a pair of field harmonic enhancers (8a,8b) made of high permeability soft magnetic material are placed over rear portions of horizontal deflection coils (10a,10b) of a saddle coil type near an electron beam entrance region of the coils such that portions of the saddle coils are interposed between the field harmonic enhancers and a neck portion (33) of the cathode ray tube. The field harmonic enhancers (8a,8b) reduce horizontal coma error by making the horizontal deflection field in the rear portion of the saddle coils (10a,10b) more pincushion shaped.
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The invention relates to a display apparatus with a deflection yoke corrector that provides, for example, raster coma error correction. In deflection yokes for cathode ray tubes (CRT) having three horizontal in-line electron beams R, G and B, the red, green and blue beams are required to substantially converge on the CRT display screen. A deflection yoke which does not require dynamic convergence circuitry is referred to as self-converging yoke. In the self converging yoke, the field Intensity or flux lines produced by the horizontal deflection winding or coil are nonuniform and made generally pincushion-shaped at a portion of the yoke, referred to as the main deflection region, that is closer to the screen than to the gun. Consequently, at a given deflection current, the magnetic field in the main deflection region of the yoke is stronger at, for example, the right-center edge of the screen, referred to as the 3 o'clock hour point than at the center of the screen. Such field nonuniformity is known to reduce misconvergence at, for example, the 3 o'clock hour point. Typically, the horizontal deflection coil is constructed as a pair of saddle coils. An upper one of the pair of saddle coils is placed around an upper half of an envelope of the CRT, above a horizontal plane. The horizontal plane intersects with the screen of the CRT along a horizontal axis X of the CRT. The other one of the saddle coils is placed around a lower half of the envelope of the CRT, below the horizontal plane. A cone shaped insulator or plastic liner has an inner surface placed around and close to the saddle coils so as to surround them. The plastic liner has an outer surface that is, in turn, surrounded by a toroidal vertical deflection coll wound around a magnetic core. Thus, the toroidal vertical deflection coil surrounds at least a substantial portion of the plastic liner that, in turn, surrounds at least a substantial portion of the saddle coils. The pincushion shaped horizontal deflection field in the main deflection region of each of the saddle coils has a flux density in the vicinity of the red and blue electron beams, when the electron beams form beam spots along horizontal axis X of the CRT, that is stronger than in the vicinity of the green electron beam. Therefore, the pincushion shaped horizontal deflection field in the main deflection region of the saddle coils tends to reduce a width, in the horizontal direction, of a raster produced by the green electron beam relative to a width of a raster produced by the red or by the blue electron beam. Such convergence error is referred to as horizontal coma (hcoma). Hcoma is typically reduced by utilizing a winding distribution in a rear portion of each of the saddle coils, near an electron beam entrance region, that produces a barrel shaped horizontal deflection field in the rear portion of the saddle coils. For a given winding distribution of the saddle coils, one type of hcoma correction requires a horizontal deflection field in the rear portion of the saddle coils that is more pincushion shaped. In US-A-4 524 340 a saddle type deflection unit is described on which the first part of claim 1 is based which uses two U-shaped members of soft magnetic material near the tube neck in order to correct vertical coma error by providing a pincushion field at the entrance end of the vertical deflection winding. The invention provides a display appparatus as characterized in Claim 1. The dependent claims describe particular embodiments of the invention. In accordance with an aspect of the invention, a pair of arcuate, first and second field harmonic enhancers made of, for example, silicon steel of high permeability are placed, each, near the rear portions of the saddle coils that are near the electron beams entrance region of the saddle coils. The rear portions of the saddle coils are interposed between the field harmonic enhancers and a neck portion of the CRT. One end of each field harmonic enhancer, in a direction of its length dimension, is located above the horizontal plane: the other end is located, illustratively, symmetrically, below the horizontal plane. Thus, each field harmonic enhancer surrounds a corresponding portion of each of the upper and lower saddle coils in the vicinity of the beam entrance region. The first field harmonic enhancer is located closer to the red electron beam than to the green electron beam. The second field harmonic enhancer is located symmetrically relative to axis Y of the CRT and closer to the blue electron beam than to the green electron beam. The high permeability of the first field harmonic enhancer enhances the horizontal deflection field in the rear portion of the saddle coils near the red electron beam relative to that near the green electron beam. Similarly, the second field harmonic enhancer enhances the horizontal deflection field in the rear portion of the saddle coils near the blue electron beam relative to that near the green electron beam. The result is that the horizontal deflection field in the rear portion of the saddle coils is made more pincushion shaped than what it would have been without the field harmonic enhancers. In this way, closer to optimal hcoma correction may be obtained. A deflection apparatus embodying an aspect of the invention includes a cathode ray tube of an in-line system including an evacuated glass envelope. A display screen is disposed at one end of the envelope. An electron gun assembly is disposed at a second end of the envelope. The electron gun assembly produces a plurality of electron beams that form corresponding rasters on the screen upon deflection. A deflection yoke is mounted around the envelope and includes a vertical deflection coil for producing a vertical deflection field in the cathode ray tube. First and second horizontal deflection coils each of a saddle type are disposed diametrically opposite with respect to each other for producing a horizontal deflection field in the cathode ray tube. Each of the first and second horizontal deflection coils includes a plurality of conductors forming corresponding first and second lateral winding packets extending in a longitudinal direction of the cathode ray tube. A core made of magnetically permeable material is magnetically coupled to the vertical and horizontal deflection coils. A field former member is disposed in the vicinity of an outer surface of a portion of the first lateral winding packet of the first horizontal deflection coil that is in the vicinity of the beam entrance end of the horizontal deflection coils near the gun assembly. The winding packet portion is interposed between the neck of the envelope and the field former member. The field former member varies a strength of a Fourier coefficient of the horizontal deflection field in the vicinity of the beam entrance end to correct a beam landing error associated with the horizontal deflection coils. FIGURE 1 illustrates a deflection system including a deflection yoke, embodying an aspect of the invention; FIGURE 2 illustrates a cross sectional view in a plane perpendicular to axis Z at a rear portion of a pair of saddle coils of the yoke of FIGURE 1 and a pair of field harmonic enhancers, embodying an aspect of the invention that provide horizontal coma correction; FIGURE 3 illustrates a side view of the yoke of FIGURE 1; FIGURE 4 illustrates a partially exploded side view of the yoke of FIGURE 3; FIGURE 5 illustrates a field distribution function of the yoke of FIGURE 1 when the field harmonic enhancers of FIGURE 2 are not employed; FIGURE 6 illustrates a field distribution function of the yoke of FIGURE 1 when the field harmonic enhancers of FIGURE 2 are employed; and FIGURES 7 and 8 illustrate top and side views of one of the field harmonic enhancers of FIGURE 2. FIGURE 1 illustrates a longitudinal sectional view in diagrammatic form through an in-line, color television display tube assembly whose longitudinal axis is indicated by Z. An in-line display tube, CRT 90, has a at the conical front of the tube. CRT 90 is, for example, of the type GE A48ATA26X having a deflection angle 90° and a 48 cm (19 inches) viewable screen size. It should be understood that a CRT with a different deflection angle may also be used, instead. A neck end 33 remote from display screen 22 contains three in-line electron guns 44 situated in plane X-Z The longitudinal axis Z lies on that plane with the central electron gun centered on axis Z. Guns 44 produce the three horizontal electron beams R, G and B, that are the red, green and blue beams, respectively. The green electron beam G is the inner electron beam and the blue and red electron beams are the outer electron beams in the three of in-line electron beams. The electron beams are required to substantially converge on the CRT display screen 22. A self converging deflection yoke 55, embodying an aspect of the invention, is mounted on CRT 90 such that it surrounds a portion of neck 33 and a portion of a conical or flared part of CRT 90. Deflection yoke 55 includes a line deflection coil assembly 77 formed by a pair of saddle coils 10. An upper saddle coil 10a of the pair of saddle coils 10 is placed around an upper half of an envelope of CRT 90, above a horizontal plane X-Z formed by axes X and Z of CRT 90. Horizontal plane X-Z intersects with screen 22 of the CRT along horizontal axis X of CRT 90 at the vertical center of screen 22 of CRT 90. The other one of the saddle coils, a coil 10b, is placed around a lower half of the envelope of CRT 90, below horizontal plane X-Z and symmetrically opposite with respect to coil 10a. A support of insulating material such as plastic whose shape is substantially that of a frustum, referred to as a plastic liner 11, has an inner surface 11a surrounding an upper surface of saddle coils 10. Plastic liner 11 has an outer surface 11b that is surrounded by a field deflection coil assembly 88 formed by a pair of toroidal coils 99, including coils 99a and 99b. Coils 99a and 99b are wound on a pair of upper and lower core portions 66a and 66b, respectively, of a core 66 made of soft magnetic material. Coils 10 are driven by a horizontal deflection circuit 178 and coils 99 are driven by a vertical deflection circuit 177 of a television receiver. Each of saddle coils 10 has a bent, rear end turn portion 9 adjacent electron guns 44, referred to as the gun end. This end turn portion is bent away from the neck of CRT 90 in a direction generally transverse to axis Z. A second, front end turn portion 19 of each of saddle coils 10 is located adjacent display screen 22, referred to as the screen end, and is also bent away from axis Z in a direction generally transversed to axis Z. FIGURE 2 illustrates a cross section of yoke 55 in a plane x-y that is perpendicular to axis Z having the coordinate Z=Z1. Axes x and y of FIGURE 2 are in parallel with axes X and Y of CRT 90 of FIGURE 1, respectively. Similar numbers and symbols in FIGURES 1 and 2 indicate similar items or functions. A first lateral winding packet 10a1 and a second lateral winding packet 10a2 of FIGURE 2 that extend in a direction of axis Z, in a manner not shown in FIGURE 2, define a winding window W of coil 10a with a portion of coil 10a that is not shown in FIGURE 2. Similarly, lateral winding packets 10b1 and 10b2 define a corresponding winding window of coil 10b. Coils 10a and 10b are disposed diametrically opposite with respect to axis x of plane x-y. The field intensity or flux lines produced by coils 10 of FIGURE 1 are nonuniform and made generally pincushion-shaped at a portion of the yoke, referred to as the main deflection region, that is closer to screen 22 than to guns 44. Consequently, the horizontal deflection field in the main deflection region of the yoke is stronger at, for example, the right-enter edge of the screen, referred to as the 3 o'clock hour point than at the center of the screen. Such field nonuniformity is known to reduce misconvergence at, for example, the 3 o'clock hour point. Hcoma is reduced, in part, by employing a predetermined winding distribution in a rear portion of each of saddle coils 10 near an electron beam entrance region in the vicinity of a coordinate Z=Z1 such that a barrel shaped horizontal deflection field is produced in the rear portion of horizontal deflection saddle coils 10. Convergence errors are corrected in the main deflection region of yoke 55, between the beam exit and entrance regions of yoke 55. Geometry errors at the extreme edges of the display screen are corrected in the exit region. The winding distribution in coils 10, established for correcting various beam landing errors, may not by itself provide sufficient pincushion shaped field nonuniformity for obtaining optimal hcoma correction. In accordance with an aspect of the invention, a pair of arcuate field formers or field harmonic enhancers 8a and 8b of FIGURE 2 made, for example, entirely of silicon steel having high permeability are placed, each, on outer surface 11b of plastic liner 11. Surface 11b is located between vertical deflection coil 99 and an outer surface of coils 10. An inner surface of coil 10a is located closer to neck 33 of CRT 90 than the outer surface of coil 10a. Field harmonic enhancer 8a overlaps and bridges portions of lateral winding packets 10a1 and 10b1 of coils 10a and 10b, respectively. Each of the portion of packets 10a1 and 10b1 that is overlapped by field harmonic enhancer 8a is closer to electron beams R, G and B than field harmonic enhancer 8a. Similarly, field harmonic enhancer 8b overlaps and bridges portions of packets 10a2 and 10b2. A midpoint of a width dimension of each of field harmonic enhancers 8a and 8b of FIGURE 1 is shown illustratively as being located at coordinate Z=Z1. Field harmonic enhancers 8a and 8b are placed in the vicinity of the beam paths where the three beams are not yet deflected significantly. The rear portions of saddle coils 10a and 10b are interposed between field harmonic enhancer 8a or 8b and neck portion 33 of CRT 90. Field harmonic enhancers 8a and 8b are located symmetrically relative to axis y of FIGURE 2. Upper half portion 8b1 and lower half portion 8b2 of field harmonic enhancer 8b are located symmetrically relative to axis x. Similarly, upper half portion 8a1 and lower half portion 8a2 of field harmonic enhancer 8a are located symmetrically relative to axis x. Each of field harmonic enhancers 8a and 8b that is arcuate surrounds a corresponding arcuate portion formed by each of rear end portions or sections of saddle coils 10a and 10b in the vicinity of the beam entrance region at, for example, coordinate Z=Z1. Field harmonic enhancer 8a, for example, is placed between angle ₁ = +30° and ₁ = 30° of FIGURE 2. An angle ₂, between axis x and the side of window W of coil 10a, is larger than angle ₁. Field harmonic enhancer 8a is located closer to the red electron beam R than to the green electron beam G. Field harmonic enhancer 8b is located closer to the blue electron beam B than to the green electron beam G. Field harmonic enhancer 8a enhances the strength of the horizontal deflection field in the rear portion of saddle coils 10 in the vicinity of coordinate Z=Z1 near the red electron beam R relative to that near the green electron beam G. Field harmonic enhancer 8b enhances the strength of the horizontal deflection field in the rear portion of coils 10 in the vicinity of coordinate Z=Z1, near the blue electron beam B relative to that near the green electron beam G. The result is that the horizontal deflection field in the rear portion of the saddle coils is made more pincushion shaped than what it would have been without field harmonic enhancers 8a and 8b. Consequently, field harmonic enhancers 8a and 8b cause the width of the rasters formed by red electron beam R and blue electron beam B to increase relative to that formed by the green electron beam G. In this way, closer to optimal hcoma correction may be obtained. FIGURE 3 illustrates a side view and FIGURE 4 illustrates an exploded side view with a partial cutout of yoke 55 of FIGURE 1. Similar symbols and numerals in FIGURES 1-4 indicate similar items or functions. In FIGURE 3, core 66 is shown as being formed by upper core portion 66a and by lower core portion 66b that are joined by a pair of resilient clips 222. Upper toroidal coil 99a of vertical deflection coil 99 is wound around core portion 66a and lower toroidal coil 99b of vertical deflection coil 99 is wound around core portion 66b. An arrangement 223, not shown in detail, that includes a permeable material collects flux of a vertical deflection field and channels the collected flux to a region of neck 33 of CRT 90 in the vicinity of a coordinate Z=Z2, in the rear of yoke 55 that is further away from screen 22 than coordinate Z=Z1. Arrangement 223 forms a quadrupole field, not shown, at a vertical rate in a plane that is parallel with plane X-Z at coordinate Z=Z2 that corrects vertical coma, in a well known manner. In FIGURE 4, for explanation purposes, a portion of outer surface 11b of plastic liner 11 is shown exposed and core portion 66a and coil 99a that is wound thereon are shown lifted up. Also, a cutout in plastic liner 11 exposes, for explanation purposes, a packet of conductor wires that extend in a direction of axis Z that form a portion of upper saddle coil 10a. As can be seen, coil 10a extends toward the rear of yoke 55 to a coordinate Z=Z4 that is further from screen 22 of CRT 90 of FIGURE 1 than the rearmost portion of vertical deflection coils 99 and of core 66 at a coordinate Z=Z3. For explanation purposes, upper half portion 8b1 of field harmonic enhancer 8b that abuts upper surface 11b of plastic liner 11 is also shown exposed, when core portion 66a is lifted up. Field harmonic enhancer 8b of FIGURE 4 includes a portion in the direction of axis Z between coordinates Z=Z3 and Z=Z4 that overlaps portions of both coils 10a and 10b but that does not overlap core 66 since it extends further from the screen side of yoke 55 than the rearmost or end portion of core 66 at coordinate Z=Z3. The strength or intensity of the magnetic field produced by saddle coils 10 can be measured with a suitable probe. Such measurement can be performed for a given coordinate Y=O and Z=Z1 of FIGURE 1 and for a given coordinate X=X1, where coordinate X1 varies in a direction parallel to axis X, the horizontal deflection direction. The plane X-Z in which coordinate X=X1 varies separates saddle coils 10. The results of measuring the strength of the magnetic field as a function of coordinate X, for a constant coordinate Z=Z1 and for a coordinate Y=O, can be used for computing in a well known manner field distribution functions or Fourier coefficients H0(Z1), H2(Z1) and H4(Z1) of a power series H(X) = H0(Z1) + H2(Z1)X2 + H4(Z1)X4. The term H(X) represents the strength of the magnetic field as a function of the X coordinate, at the coordinates Z=Z1, Y=O. The coefficients H0(Z), H2(Z) and H4(Z) can then be computed for different values of the coordinate Z. A graph can then be plotted depicting the variation of each of coefficients H0(Z), H2(Z) and H4(Z) as a function of the coordinate Z. Field distribution function H2 is determined significantly by the third harmonic of the winding distribution in the saddle coil. The magnitude of the third harmonic is computed using the Fourier analysis technique. FIGURE 5 illustrates a graph depicting the variations of coefficients H0(Z), H2(Z) and H4(Z) for yoke 55 of FIGURE 1 when field harmonic enhancers 8a and 8b are not utilized. FIGURE 6 illustrates a graph depicting the variations of the coefficients when field harmonic enhancers 8a and 8b are utilized. The field harmonic enhancers 8a and 8b enhance coefficient H2 in the rear portion of saddle coils 10. The positive increase in coefficient H2 indicates that the horizontal deflection field in the rear portion of coils 10 becomes more pincushion shaped when field harmonic enhancers 8a and 8b are used than without them. Because the beams are not yet significantly deflected in the rear portion of coils 10, the enhanced pincushion shaped horizontal deflection field causes the red beam R and the blue beam B to be deflected more than the green beam G. Thus, the type of hcoma error of the arrangement of FIGURE 1 is corrected. It should be understood that in a different deflection system in which correction of hcoma requires the red beam R and the blue beam B to be deflected more than the green beam G, field formers would be placed between different angles in a manner to produce a negative increase in coefficient H2 for correcting hcoma. Negative increase in coefficient H2 may be produced by utilizing for example, four field formers, symmetrically, to axes x and y of FIGURE 2. Thus, for example, in a first quadrant of axes x and y of FIGURE 2 a field former 8' may be placed between angle ₁ = 30° and ₁ = 60°, as shown in broken lines. Field harmonic enhancers 8a and 8b of FIGURE 1 may have a tendency to increase positive overconvergence at 6 and 12 o'clock hour points of screen 22 of CRT 90 of FIGURE 1. They also may have a tendency to increase negative overconvergence at the 3 and 9 o'clock hour points, hence a more positive horizontal trap error could result. Such overconvergence and trap error can be reduced by varying other parameters such as by varying the winding distribution of coils 10. After such overconvergence and trap error are reduced, the hcoma error is maintained, advantageously, smaller than if field harmonic enhancers 8a and 8b were not utilized. Field harmonic enhancers 8a and 8b do not produce a significant effect on north-south geometry pincushion distortion after the aforementioned overconvergence is readjusted. FIGURES 7 and 8 illustrate top and side views of field harmonic enhancer 8a or 8b of FIGURE 1. Similar symbols and numerals in FIGURES 1-8 indicate similar items or functions. Field harmonic enhancer 8a or 8b of FIGURE 7 includes a notch 250 that mates with a corresponding rib in liner 11 for mechanically fixing the position of the field harmonic enhancer on liner 11 relative to saddle coils 10. The width dimension of field harmonic enhancer 8a or 8b of FIGURE 7 that is in the direction of axis Z is selected to obtain the required effect on hcoma. The length dimension of field harmonic enhancer 8a or 8b or the angle, that is equal to twice the angle ₁ in plane x-y is also selected to obtain the required effect on hcoma. A smaller length reduces the effect of the field harmonic enhancer on hcoma and causes an increase in the variations of coefficient H4(Z) of FIGURE 5 or 6. Whereas, an increase in the length of field harmonic enhancer 8a or 8b of FIGURE 7 or 8 increases its effect on hcoma and decreases the variations of coefficient H4(Z) of FIGURE 5 or 6. Thus, the length of the field harmonic enhancer is selected to provide an optimized trade-off between its effect on hcoma and on other parameters of the yoke.
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A display apparatus, comprising: a cathode ray tube (90) of an in-line system including an evacuated glass envelope, a display screen (22) disposed at one end of said envelope, an electron gun assembly (44) disposed at a second end of said envelope, said electron gun assembly producing a plurality of electron beams (R,G,B) that form corresponding rasters on said screen upon deflection; a deflection yoke (55) mounted around said envelope including, a vertical deflection coil (99a,99b) for producing a vertical deflection field in said cathode ray tube; first and second horizontal deflection coils (10a, 10b) each of a saddle type disposed diametrically opposite with respect to each other for producing a horizontal deflection field in said cathode ray tube, each of said first and second horizontal deflection coils including a plurality of conductors forming corresponding first and second lateral winding packets (10a1, 10a2; 10b1, 10b2) extending in a longitudinal direction of said cathode ray tube; a core (66) made of magnetically permeable material magnetically coupled to said vertical and horizontal deflection coils; characterized bya pair of field former members (8a, 8b) each disposed in the vicinity of both an outer surface of a portion of said first lateral winding packet (10a1) of a respective first horizontal deflection coil (10a) and an outer surface of a portion of said first lateral winding packet (10b1) of a respective second horizontal deflection coil (10b), both lateral winding portions being in the vicinity of the beam entrance end (ENTRANCE REGION) of said horizontal deflection coils near said gun assembly (44), in a manner to bridge said portion of said first lateral winding packet of said first packet of said first horizontal deflection coil and said portion of said first lateral winding packet of said second horizontal deflection coil, said portion of said first lateral winding packet of said first horizontal deflection coil and said portion of said first lateral winding packet of said second horizontal deflection coil being disposed adjacent each other such that each of said portion of said first lateral winding packet of said first horizontal deflection coil and said portion of said first lateral winding packet of said second horizontal deflection coil is interposed between the neck of said envelope and said field former member, said field former member varying the field strength distribution as described by a Fourier coefficient (H2(Z)) of said horizontal deflection field that is produced in said vicinity of said beam entrance end in a manner to correct for a beam landing coma error. An apparatus according to Claim 1, characterized in that each of said horizontal deflection coils (10a,10b) forms first and second winding windows (W-front, W-back), respectively, and wherein each of said field former members (8a,8b) is disposed entirely outside each of said winding windows. An apparatus according to Claim 1, characterized in that said first and second lateral winding packet of said first horizontal deflection coil form a winding window (W1) therebetween, and wherein each of said field former members is disposed entirely outside said winding window. An apparatus according to Claim 1, characterized in that said field former members (8a,8b) enhance the strength of said horizontal deflection field in the vicinity of each of a pair of outer electron beams (R,B) of said electron beams relative to the strength of said horizontal deflection field in the vicinity of an inner electron beam (G) of said electron beams. An apparatus according to Claim 1, characterized in that said field former members (8a,8b) make said horizontal deflection field more pincushion shaped in the vicinity of the beam entrance end of said horizontal deflection coils (10a, 10b) near said gun assembly (44) than what it would have been without said field former members. An apparatus according to Claim 1, characterized in that said field former members (8a,8b) reduce horizontal coma error. An apparatus according to Claim 1, characterized by an insulator (11 ) for mounting said horizontal deflection coils (10a, 10b) on an inner surface thereof and said vertical deflection coil (99a,99b) on an outer surface thereof, and wherein said first field former member (8a) is disposed on said outer surface of said insulator. An apparatus according to Claim 7 characterized in that each of said first field former members (8a, 8b) includes a notch (250) for mating with a rib of said insulator (11) to establish a position of said field former member relative to said horizontal deflection coils (10a, 10b). An apparatus according to Claim 1, characterized in that said field former members (8a, 8b) are composed of a soft magnetic material having a high permeability. An apparatus according to Claim 9, characterized in that said field former members (8a, 8b) are composed of silicon steel. An apparatus according to Claim 1, characterized in that said core (66) surrounds a corresponding portion (Z3 - edge of 8a closer to screen) of each of said horizontal deflection coils (10a, 10b) and wherein at least a first portion (Z1 - Z4) of said field former members (8a, 8b) extends outside the portions of said horizontal deflection coils that are surrounded by said core. An apparatus according to Claim 11, characterized in that a second portion of said field former members (Z3 - edge of 8a closer to screen) is interposed between said core (66) and said neck of said cathode ray tube (90). An apparatus according to Claim 1, characterized in that said first lateral winding packet (10a1) of said first horizontal deflection coil (10a) and said first lateral winding packet (10b1) of said second horizontal deflection coil (10b) are disposed in one side of a Y-Z plane of said cathode ray tube (90) and wherein said second lateral winding packet (10a2) of said first horizontal deflection coil (10a) and said second lateral winding packet (10b2) of said second horizontal deflection coil (10b) are disposed in the other side of said Y-Z plane of said cathode ray tube. An apparatus according to Claim 1, characterized in that said first lateral winding packet (10a1) of said first horizontal deflection coil (10a) and said second lateral winding packet (10a2) of said first horizontal deflection coil are disposed in one side of an X-Z plane of said cathode ray tube (90) and wherein said first lateral winding packet (10b1) of said second horizontal deflection coil (10b) and said second lateral winding packet (10b2) of said second horizontal deflection coil are disposed in the other side of said X-Z plane of said cathode ray tube.
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VIDEOCOLOR SA; VIDEOCOLOR S.A.
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MAILLOT ANDRE; MILILI MARC; MAILLOT, ANDRE; MILILI, MARC; Maillot, André
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EP-0490006-B1
| 490,006 |
EP
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B1
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EN
| 19,940,622 | 1,992 | 20,100,220 |
new
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A61K37
| null |
A61P37, A61K38
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A61K 38/20D
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Pharmaceutical compositions for the treatment of B-cell malignancies
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The present invention concerns pharmaceutical compositions for treating B-cell malignancies in a mammal afflicted with B-cell malignancies. More precisely, according to the invention, these pharmaceutical compositions comprise IL-4 as an active ingredient. The present invention is also directed to a method of treating B-cell malignancies, or inhibiting the proliferation or growth of malignant B-cell by administering IL-4 into mammals afflicted with B-cell malignancies.
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The invention relates to the use of IL-4 in the manufacture of medicaments for treating non-Hodgkin's malignant lymphomas in mammals. Interleukin-4 [hereinafter IL-4 but also known as B-Cell Stimulatory Factor 1, (BSF-1)] was originally described by M. Howard et al. in J.Exp. Med. (1982), Vol. 155, pp. 914-23 as a T cell-derived growth factor, distinct from IL-2, which permitted long-term tissue culture of normal mouse B lymphocytes and which interacted with activated B lymphocytes to maintain the proliferation thereof for as long as 4 months. Although mixed B lymphocyte explants have been used to initiate cultures, it appears that B lymphocytes with immature phenotype are specifically enhanced by IL-4 in tissue culture. See for example C. Peschel et al., J. Immunol. (1989), Vol. 142, 1558-1568. In addition, G. Trenn et al. J. Immunol. (1988) Vol. 140, 1101-1106 discloses that IL-4 stimulates the development of cytotoxic T cells from the Lyt-2+ subpopulation of resting murine T lymphocytes. The mouse IL-4 gene was cloned and expressed in COS-7 cells [See T. Otsuka et al., Nuc. Acids Res. (1987), Vol. 15,333-334]. The cloned factor had all the activities in tissue culture seen for the factor purified from T cell culture supernatants. Cloning and expression of the human IL-4 gene have been described by N. Arai et a]., J. Immunol. (1989, Vol. 142, 274-282 and T. Yokota et al., Proc. Natl. Acad. Sci. (1986), Vol. 83, 5844-5848 with the factor produced in COS-7 cells having similar activities to the native molecule as studied in tissue culture. As IL-4 was studied both in human and murine cell systems, additional in-vitro activities were attributed to the molecule: (i) IL-4 played an important role in the induction and regulation of IgE synthesis, a process occuring as B lymphocyte subpopulations were induced into proliferation [See Pene, J., Proc. Natl. Acad. Sci (1988), Vol 85, 6880-6884]; (ii) IL-4 induced low affinity FcΣ receptors (CD23) on normal human B lymphocytes in tissue culture [See T. DeFrance et al., J. Exp. Med. (1987), Vol. 165, 1459-1457]; (iii) IL-4 interacted in an extremely precise way with other lymphokines, notably interferon-γ [See R.L. Coffman et al. Immunol. Res. (1988), Vol. 102, 5-27 and Pene et al., supra] and T cells [See R.L. Coffman et al. supra, Pene et al. supra, and M.D. Widmer et al., Nature, (1987), Vol. 326, 795-98] to bring about B cell proliferation and alteration; and (iv) IL-4 increased MHC class II antigen expression on resting B cells (R Noelle et al., PNAS 81. 6149-6153, 1984). T.R. Mosmann et al. in J. Immuno., Vol. 138, 1813-1816 disclosed that human and murine IL-4 which are 50% homologous at amino acid sequence 1-90 and 129-149 were species specific. Studies in humans showed that IL-4 has an effect on monoclonal B cell tumors. S. Karray et al. in J. Exp. Med. (1988), Vol. 168, 85-94, disclose that human IL-4 suppresses the IL-2-dependent proliferation of B-type chronic lymphocytic leukemia (B-CLL) in vitro. T. DeFrance et al. J. Exp. Med. (1988), Vol 168, 1321 disclose that IL-4 inhibits the in vitro proliferation but not the differentiation of activated human cells in response to IL-2. See also D.F. Jelinek et al. J. Immunol. (1988), Vol 141; 164. C.M. Higuchi et al. in Can. Res. (1989), Vol. 49, 6487-6492, disclose that in human peripheral blood lymphocytes preactivated by IL-2, IL-4 induces lymphokine-activated killer activity (LAK). J.J. Mule et al. in J. Exp. Med. (1987), Vol. 166; 792-797, disclose that in the murine system, resting splenocytes treated with murine IL-4 alone or in combination with IL-2 generate LAK activity against fresh syngenic tumor cells in vitro. G. Forni et al. in Int. J. Can. Sup. (1989), Vol. 4; 62-65, disclose that antitumor activity can be induced by injecting murine IL-4 around the tumor draining lymph node and that when IL-4 is used in combination with a nonapeptide from human IL-1β, very active lymphokine-activated tumor inhibition (LATI) is observed. J.J. Mule et al. in J. Immuno. (1989), Vol. 142; 726-733 disclose that the major phenotype of the cells induced by murine IL-4 is surface expression of asialo-GM₁, Thy⁺, Lyt²⁺, T³⁺ and that in LAK cells generated by a combination of IL-2 plus IL-4, there is an increase in granule-associated serine esterase. D.J. Peace et al. in J. Immuno. (1988), Vol. 140, 3679-3685 disclose that IL-4 induced LAK activity is associated with two different cell types, one NK-like (NK1.1⁺, Lyt²⁻) and the other T cells like (NK 1.1⁻, Lyt²⁺). R.I. Tepper et al. in Cell (1989), Vol. 57; 503-512 disclose that murine tumor cell lines transfected with murine IL-4 are inhibited from growing in vivo but that IL-4 transfected tumor cells mixed with nontransfected tumor cells resulted in the inhibition of the nontransfected tumor growth in vivo when the two tumor cell types were colocalized. R.I. Tepper et al. also disclose that when the nontransfected tumor was at a distal site from the IL-4-transfected tumor, inhibition was not observed. R.I. Tepper further disclose that parenteral administration of a cytokine, e.g. IL-2 or IL-4 to a tumor-bearing animal is compromised by the short half life of the factor (as is the case for IL-2) and the need to obtain the cytokine in quantities sufficient to achieve effective dose levels. G. D'Orazi et al. in Proceedings of the American Association for Cancer Research, (March 1990), Vol. 31, p. 252, Abstract N° 1490 disclose that IL-4 induced an antitumor response in a nude mouse model. A method of treating solid tumors in mammals afflicted with solid tumors by systemically administering IL-4 to said mammals is disclosed in WO-A-9114450. The potential of inhibiting the growth of a variety of lymphoid neoplasms including B-Cell neoplasms is disclosed by Taylor and al. in BLOOD, vol. 75, N° 5 March 1990, pages 1114-1118. But, accordingly to these document, not all kinds of B-cell lymphomas are susceptible to inhibition by IL-4. Surprisingly, we have found that non-Hodgkin's malignant lymphomas may be treated and the growth thereof inhibited by administering an effective amount of IL-4 into mammals, such as human beings, afflicted with such B-cell malignancies. Accordingly, the present invention has for object the use of IL-4 for the manufacture of a pharmaceutical composition for treating non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies. The present invention also has for object the use of IL-4 for the manufacture of a pharmaceutical composition for inhibiting the growth of non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies. The present invention still further has for object the use of IL-4 in the manufacture of a pharmaceutical composition for inhibiting the proliferation of non-Hodgkin's malignant lymphomas in mammals afflicted with such malignancies. Another object of the invention is the use of IL-4 in the manufacture of a medicament for inducing an effective immune response to inhibit non-Hodgkin's malignant lymphomas growth or to effect non-Hodgkin's malignant lymphomas regression. Still another object of the invention is the use of IL-4 in the manufacture of a pharmaceutical composition for augmenting an effective immune response to effect inhibition or regression of non-Hodgkin's malignant lymphomas in mammals afflicted with such malignancies. The use of E-Coli derived recombinant human IL-4 in the manufacture of the above cited pharmaceutical composition is also an object of the invention. Furthermore, a possible application of the invention is to provide a method of treating non-Hodgkin's malignant lymphomas in a mamal afflicted with such malignancies which comprises administering to said mammal an amount of IL-4 effective for such treating. Another possible application of the invention is to provide a method of inhibiting the growth of non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies which comprises administering to said mammals an amount of IL-4 effective for such inhibiting. It is also a possible application of the invention to provide a method of inhibiting the proliferation of non-Hodgkin's malignant lymphomas in mammals afflicted with such malignancies which comprises administering said mammals an amount of IL-4 effective for such inhibiting. It is still further a possible application of the invention to provide a method for inducing an effective immune response to inhibit non-Hodgkin's malignant lymphomas growth or to effect non-Hodgkin's malignant lymphomas regression which comprises administering to said mammals an amount of IL-4 effective for such inhibitings. A method for augmenting an effective immune response to effect inhibition or regression of malignant non-hodgkin's malignant lymphomas in mammals afflicted with such malignancies is a possible application of the invention. Figure 1 illustrates the dose-response curve of the growth-inhibitory effect in-vitro of IL-4 in accordance with this invention on the IL-2 driven proliferation of malignant B-cells from lymph nodes. Figure 2 illustrates the dose-response curve of the growth-inhibitory effect of IL-4 in accordance with this invention on the anti-IgM-induced proliferation of, malignant B-celles from lymph nodes. The term B-cell malignancy and the term malignant B-cell as used herein refer to non-Hodgkin malignant lymphoma (hereinafter NHML ) B-cells. In an in vitro study, we demonstrated that IL-4 inhibited the in vitro proliferative response of freshly-isolated non-Hodgkin malignant lymphoma (hereinafter NHML ) B-cells. For this in vitro antiproliferation assay, the leukemic NHML B cells were activated with insolubilized anti-IgM antibodies or Staphylococcus Aureus Strain Cowan 1 (hereinafter SAC ). For 8 of the 9 leukemic NHML B cells, IL-2 was the sole cytokin/B cell tropic factor which significantly and reproducibly stimulated DNA synthesis in these NHML B-cells activated through their surface Igs. IL-4 strongly suppressed the proliferative signals delivered to the NHML B cells either by anti-Ig reagents alone or by the combination of IL-2 and anti-Ig reagents. These in vitro data suggest that IL-4 essentially provides growth inhibitory signals to NHML B-cells where said B-cells are activated through their surface Ig receptors. It is expected based on these invitro results that IL-4 would be useful in clinical treatment of mature B-cell malignancies. The phrase treating a B-cell malignancy as used herein means a broad range of anti-B cell responses resulting from administration of IL-4 in accordance with this invention including: (1) effecting B-cell malignancy regression; (2) inhibiting malignant B-cell growth; (3) inhibiting the proliferation of malignant B-cells; (4) inducing an effective immune response to inhibit malignant B-cell growth or effect malignant B-cell regression; and (5) augmenting an effective immune response to effect inhibition or regression of malignant B-cell growth in mammals. The immune response of some mammals in the absence of IL-4 may not be strong enough or fast enough to effect malignant B-cell growth inhibition or malignant B-cell regression but we have found effective methods which comprise administering to malignant B-cell bearing mammals an amount of IL-4, preferably recombinant IL-4, effective for each of such purposes. Any suitable IL-4 may be employed in the present invention. Complementary DNAs (cDNAs) for IL-4 have recently been cloned and sequenced by a number of laboratories, e.g. Yokota et al., Proc. Natl. Acad. Sci.USA. (1986), Vol. 83; 5894-5898 (human); Lee et al., Proc. Natl. Acad. Sci. USA (1986), Vol. 83; 2061-2065 (mouse); Noma et al., Nature (1986), Vol. 319; 640-646 (mouse); and Genzyme Corporation, Boston, Massachusetts (human and mouse). Moreover, non-recombinant IL-4 has been purified from various culture supernatants, e.g.; Grabstein et al., J. Exp. Med. (1985), Vol. 163; 1405-1413 (mouse); and Ohara et al., J. Immunol. (1985), Vol. 135; 2518-2523 (mouse BSF-1). Preferably, the IL-4 used in the present invention is human IL-4, and most preferably it is the human version with the sequence described in Yokota et al., Proc.Natl. Acad. Sci. USA (1986), Vol. 83; 5894-5898 and PCT Patent Application N° 87/02990 published May 21, 1987 that is expressed in and isolated from E. Coli (U.S. Patent Application N° 079,666, filed July 29, 1987 and U.S. Patent Application N° 194,799, filed July 12, 1988). The production of IL-4 from CHO cells is described in commonly-owned U.S. Patent Application SN 386,937, filed July 28, 1989. The production of IL-4 from E. coli is described in commonly-owned U.S. Patent Application SN 429,588, filed October 31, 1989. According to this invention, mammals are administered an effective amount of an IL-4 to inhibit malignant B-cell growth, to effect malignant B-cell regression, to induce an effective immune response, to inhibit malignant B-cell growth or to effect malignant B-cell regression or to augment an effective immune response to effect solid tumor growth inhibition or solid tumor regression. From about 0.25 to about 15 micrograms of IL-4, preferably human IL-4 ( hIL-4 ) recombinantly produced from E. coli or CHO cells, more preferably E.coli-derived recombinant hIL-4, per kilogram of body weight per day is preferably administered. More preferably, mammals are administered about 5 to about 15 micrograms of recombinant hIL-4 per kilogram of body weight per day, and most preferably mammals are administered about 5 to about 10 micrograms of recombinant hIL-4 per kilogram of body weight per day in single or divided doses. The amount, frequency and period of administration will vary depending upon factors such as the level of the neutrophil and monocyte count (e.g., the severity of the monocytopenia or granulocytopenia), age of the patient, nutrition, etc. Usually, the administration of IL-4 will be daily initially and it may continue periodically during the patient's lifetime. Dosage amount and frequency may be determined during initial screenings of neutrophil count and the magnitude of the effect of IL-4 upon the increase in antibody levels. Administration of the dose can be intravenous, parenteral, subcutaneous, intramuscular, or any other acceptable systemic method. The IL-4 can be administered in any number of conventional dosage forms. Parenteral preparations include sterile solutions or suspensions. Dosages of more than about 10 to about 15 micrograms of recombinant IL-4 per kilogram of body weight are preferably intravenously or subcutaneously (e.g. by bolus s.c.) administered to human beings. The formulations of pharmaceutical compositions contemplated by the above dosage forms can be prepared with conventional pharmaceutically acceptable excipients and additives, using conventional techniques. Presently, the IL-4 is preferably administered systemically via injection, preferably via subcutaneous bolus or intraperitoneal injection or even intravenous injection. The solutions to be administered may be reconstituted lyophilized powders and they may additionally contain preservatives, buffers, dispersants, etc. Preferably, IL-4 is reconstituted with 10 millimolar citrate buffer and preservative-free sterile water with the maximum concentration not to exceed 100 micrograms per milliliter and administered systemically via subcutaneous injection, intraperitoneal injection or via continuous intravenous infusion or by intravenous injection. For continuous infusion, the daily dose can be added to 5 ml of normal saline and the solution infused by mechanical pump or by gravity. The effect of IL-4 on B-cell malignancies can be determined inter alia by shrinkage of lymph nodes and spleen, a fall in the circulatory malignant B-cells as well as by the reduction in tumor volume (which can be measured using standard techniques such as caliper measurements, X-ray and MRI) as well as by increased life span or survival of such mammals by the following test protocol. MATERIALS AND METHODSIsolation and purification of malignant (leukemic) B cellsPathological samples were provided by Pr. Sotto (Hospital Albert Michallon, Grenoble, France), Dr. J.F. Rossi (Hospital Val d'Aurelle, Montpellier, France) and Dr. J.P. Magaud (Hospital Edouard Herriot, Lyon, France). Nine patients with the diagnosis of low grade non Hodgkin, non Burkitt, malignant lymphoma (NHML) B-cells according to the Kiel classification, who have not received chemotherapy for the last four months preceding surgery were selected for this study. The available specimens included 5 lymph nodes (EMZ, GAN, PP, MAI, PRO) and 4 spleens (BOU, DEL, BRE, THE). Mononuclear cells were obtained after dilaceration of the organs on a steel mesh and centrifugation of the cell suspension over Ficoll/Hypaque gradient. For B-cell purification, mononuclear cells were first submitted to E rosetting with sheep red blood cells. The non-rosetting cells (E⁻ fraction) were subsequently incubated with a cocktail of anti-T cells (anti-CD3, anti-CD2) and anti-monocytes (anti-CD14) monoclonal antibodies. Residual non-B cells were next removed from the E⁻ population after incubation with magnetic beads (Dynabeads, Dynal, Oslo, Norway) coated with anti-mouse IgG. ReagentsInsolubilized anti-IgM antibodies were purchased from BioRad Laboratories (Richmond, CA) and were used at the final concentration of 10 µg/mL. Formalinized particles of Staphylococcus Aureus Strain Cowan I (SAC) were purchased as Pansorbin from Calbiochem-Behring Corporation (La Jolla, CA). SAC was used at 0.005% final concentration (w/v). CytokinesPurified recombinant IL-2 (3 x 10⁶ U/ml) was purchased from Amgen Biologicals (Thousand Oaks, CA) and used at the final concentration of 20 U/mL which was determined to be optimal for the growth of normal B cells co-stimulated with insolubilized anti-IgM antibodies. Purified recombinant human IL-4 (derived from E. coli, 1 x 10⁷ U/mg) was provided by Drs. P. Trotta and T.L. Nagabhushan (Schering-Plough Research, Bloomfield, NJ). In the experiments, IL-4 was used at the final concentration of 500 U/ml which concentration provides maximal stimulation of B cell growth, as estimated on normal B cells activated with insolubilized anti-IgM antibodies. CulturesThe nine purified leukemic NHML B cells were cultured in Iscove's medium (Flow Laboratories, Irvine, CA) enriched with 50 µg/mL of human transferrin, (Sigma Chemical Co., St Louis, MO), 0.5% bovine serum albumin (Sigma), 5 µg/mL of bovine insulin (Sigma), 5% selected heat inactivated fetal calf serum, 100 U/ml of penicillin, 100 µg/ml of Streptomycin (all from Flow Laboratories) and 10⁻⁵M of β mercaptoethanol (Sigma). For proliferation assays, 1 x 10⁵ of leukemic B-cells were plated in 100 µL of culture medium in round-bottom microwells and incubated in a 5% CO₂ humidified atmosphere at 37°C for five days in the presence of Polyclonal B cell activators PBA-SAC, or insolubilized anti-IgM antibodies and/or factors IL-4 (500 U/ml) and/or IL-2 (20 U/mL) which were added at the onset of the culture. DNA synthesis was determined by pulsing cells with (3H)thymidine (hereinafter (3H)TdR ) for the final 16h of the culture period. Due to the heterogeneity of the responses of leukemic B cell samples, DNA synthesis was assessed at four different time intervals (on days 3, 4, 5 and 6) after onset of the culture. The results presented in Table I correspond to the time point which provided the maximal stimulation indices. Counts per minute of (3H)TdR incorporation (cpm X10⁻³) are expressed as means of triplicate determinations. Standard deviation never exceeded 10% of the mean value. The results are listed in Table I. IL-4 was assayed for its capacity to antagonize the proliferative response of NHML B-cells to IL-2. Each of the 9 specimens of NHML B-cells was therefore co-cultured with IL-2 (20 U/ml) and IL-4 (500 U/ml) in the presence of the anti-Ig reagent previously defined as being optimal for activation. Since the leukemic samples also differed from one to another in terms of time kinetics of the response to the growth-promoting effect of IL-2, DNA synthesis was measured 4, 5, 6 and 7 days after onset of the culture. Data displayed in Table I represent, for each clone, the levels of (3H)TdR incorporation obtained at the time point corresponding to the peak of the proliferative response to IL-2. One clone (MAI) did not display significant growth response to IL-2 or IL-4 in both activation systems and therefore is not included in Table I. In 7 out 8 cases, IL-4 failed to synergize with anti-Ig reagents to support DNA synthesis from NHML B-cells. However, one clone (BRE) exhibited the opposite pattern of response and proliferated upon culturing with IL-4 and anti-IgM antibodies. With the exception of clone BRE, all NHML B-cells samples displayed a growth response to IL-2. For all IL-2 responsive clones, IL-4 was found to significantly inhibit the IL-2 driven proliferation of the cells. The titration of the growth-inhibitory effect of IL-4 on the IL-2 induced response of 1 x 10⁵ cells of the leukemic clone GAN co-stimulated with 0.005% of SAC and 10 U/mL of IL-2 in the absence or in the presence of serial dilutions of IL-A. The incorporation of (3H)TdR was assessed on day 4. Figure 1 is dose-response curve which is representative of three experiments and graphically shows that complete inhibition of the response to IL-2 is already achieved for concentrations of IL-4 as low as 16 U/mL. Figure 2 is a dose response curve which graphically summarizes four experiments and shows the growth inhibiting effect of IL-4 on the anti-Ig M-induced proliferation of clone PRO. These leukemic B-cells (1 x 10⁵ of PRO) were stimulated with insolubilized anti-Ig M antibodies (10 µg/mL), in the absence or in the presence of serial dilutions of IL-4. The (3H)TdR was added during the last 16h of a 4 day culture period. The (3H)TdR incorporation is unstimulated cultures was 346 ± 28 cpm. Moreover, IL-4 also inhibited the growth of the three other NHML B-cells specimens (BOU, EMZ, PRO) which already exhibited a significant proliferative response upon ligation of their surface Igs with SAC or anti-IgM antibodies (Table I, Fig. 2). In the present study, we show that, in their great majority, NHML B-cells activated through their surface Ig receptors can be stimulated for DNA synthesis by IL-2. In some tumor specimens (3 out of 9), a proliferative response could also be induced by the sole ligation of the surface Igs in the absence of exogenous growth factors. IL-4 significantly suppressed not only the growth response of these cells to IL-2 but also to the anti-Ig reagent by itself.
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Use of IL-4 for the manufacture of a medicament for treating non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies. Use of IL-4 for the manufacture of a medicament for inhibiting the growth of non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies. Use of IL-4 in the manufacture of a medicament for inhibiting the proliferation of non-Hodgkin's malignant lymphomas in a mammal afflicted with such malignancies. Use of IL-4 in the manufacture of a medicament for inducing an effective immune response to inhibit the growth of non-Hodgkin's malignant lymphomas or to effect non-Hodgkin's malignant lymphomas regression. Use of IL-4 in the manufacture of a medicament for augmenting an effective immune response to effect inhibition or regression of non-Hodgkin's malignant lymphomas in mammals afflicted with such malignancies. The use according to one of the claims 1 to 5 wherein said medicament is in the form adapted to be intraveneously or intraperitonealy or subcutaneously administered. The use according to claims 1 to 5 wherein said medicament comprises an amount of IL-4 in the range of about 0.25 to about 15 micrograms per kilogram of body weight for a daily administration. The use according to one of the claims 1 to 7 wherein IL-4 is a E.Coli derived recombinant human IL-4.
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SCHERING PLOUGH CORP; SCHERING-PLOUGH
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BANCHEREAU JACQUES; DE FRANCE THIERRY CHARRIERE BL; BANCHEREAU, JACQUES; DE FRANCE, THIERRY, CHARRIERE BLANCHE
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EP-0490011-B1
| 490,011 |
EP
|
B1
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EN
| 19,940,907 | 1,992 | 20,100,220 |
new
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C01B33
| null |
C01B39, B01F5, B01F3
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C01B 33/28B2B
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A process to obtain zeolite 4A starting from bauxite
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The invention purpose is a process to obtain a gel to elaborate Zeolite 4A, to be used in detergents due to its capaticy for calcium retaining; the process lies in the obtention of an alkaline aluminum solution starting from bauxite provided by tank 3 which is attacked in digester 1 with sodium hydroxide provided by tank 4, with a concentration of 11% (preferably between 11 and 15%), with a filtration of the reacting mass and a purification 13 before the gel formation step in whose reactor 14 is also introduced an alkaline solution of SiO2 to obatin by shaking and temperature a gel which is treated in a crystallizier, cooling and concentrating the crystallizied mass in 16, filtrated in 17, and passed to a drier 20 from where the raw material 21 pass to consumption. Bauxite residues are attacked with boiling sulphuric acid in reactor 9, filetring the resulting mass to recycle the silica and to use the metal sulphates in solution.
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PURPOSE OF THE INVENTIONThe purpose of the invention is a process to obtain Zeolite 4A starting from bauxite or from any other aluminium mineral suitable to be attacked by NaOH at atmospheric pressure. According to the invention, the obtained Zeolite has a particle size between 1 and 10 microns (Coulter counter), an absorption capacity of calcium higher than 330 mg CaCO3 per gram of anhydrous product and whiteness not less than 99.0 (Hunter lab), and consequently is specially recommended for detergent manufacturing. This process is cheaper than others due to the use of a cheaper aluminium raw material and because it requires a minimum energy supply. Besides, it does not generate any residues, neither solids nor liquids that could affect the ecological environment. BACKGROUND OF THE INVENTIONThe processes known until now to obtain Zeolite 4A do not mention the bauxite as an aluminium source. The manufacture of Zeolite 4A starting from bauxite has several inconveniences in the crystallization step and in the color and purity of the final product, and also in the generation of contaminant residues. With the technology described in this invention, all these inconveniences are avoided, obtaining an optimum product for the manufacture of detergents. Moreover, the substitution of alumina trihydrate by bauxite, which is cheaper, and the possibility of its digestion at atmospheric pressure, notably reduces the manufacturing costs of Zeolite 4A. STATE OF THE ARTIn the existing bibliography there are no references starting from bauxite to obtain Zeolite A. The references to US 3310373, BE 840315 and IT 19617A/79 are mentioned only as an information source of the previous art known by the inventors, and that is the why and wherefore they have researched the possibility to make a suitable, profitable and non-contaminating industrial process to obtain Zeolite A starting from a cheap raw material, abundant and rich in A12O3, such as the bauxite. DESCRIPTION OF THE INVENTIONAccording to the invention, it is started from bauxite, but any other aluminium mineral could be used which is capable of being attacked by sodium hydroxide at atmospheric pressure. Digestion of bauxite is performed in a rotative disolver with a solution of sodium hydroxide at a temperature below 100ºC, preferably between 90 and 100ºC. The aluminium alkaline solution is filtered to separate it from the insoluble residues. The filtrate is purified by absorption of the organic material in resins of hydrophobic interaction. The purified aluminium solution (without organic material) is driven to a reactor provided with a strong agitation where it is mixed at 65-70ºC with an alkaline solution of SiO2 obtained by digestion of silica with NaOH, forming a stable gel of sodium silicoaluminate. Crystallyzation is made in a conventional way; the mother liquor and washing waters, after their purification, are used again recycling them respectively to the bauxite and SiO2 digestors. Bauxite muds are subjected to a digestion with 30% sulphuric acid which disolves all the cations but keeps up the SiO2 insoluble. The acid solution is filtered and the residue (SiO2) is sent to the digestor of SiO2, being recovered for the process. The filtrate, mainly formed by A12 (SO4)3 is adjusted in concentration and acidity, resulting suitable to be used in residual water treatment. EXAMPLESExample 1A rotative reactor is continuously fed with 100Kg/h of an alkaline solution at 12% in NaOH and a temperature of 95ºC together with 10Kg/h of natural guyana bauxite having the following composition: A12O3-55.4% SiO2-6.2% Fe2O3-2.0% TiO2-4.6% CaO-0.15% MgO-0.12% Na2O-1.13% H2O-30.1% Organic material: 0.3%The effluent suspension is filtered in a pressure filter; the clear liquid is cooled to 40ºC and is passed through a bed of resins of hydrophobic interaction, which retains the organic material. The fluid is heated to 70ºC and is fed continuously to a reactor provided with a strong agitation, together with an alkaline solution of SiO2 of molar ratio SiO2/Na2O=2.0 preheated to 70ºC in such a way that the reacting molar composition results in:94% H2O; SiO2/Na2O=0.47;A12O3/Na2O=0.26 The obtained gel is transferred to a crystallizer and agitated, while its temperature is raised to 98±2ºC in 50 minutes. The crystallization is completed after 60 minutes, being the slurry fast cooled to 75ºC, filtered, washed and dried. The dry product has a Ca absorption of 345mg CaCO3 per gram of anhydrous Zeolite, an average size of 4.0 microns with a modulation of (particles between 3 and 8 microns) of 87% and a whiteness L=99.3. Example 2The muds produced in Example 1 during one hour of continuous attack of the bauxite are treated with 12Kg of 30% H2SO4 at 100ºC, during 1h, in a glass reactor provided with agitation. The resulting solution is filtered and the residue is disolved in an alkaline solution in such a way that the molar ratio SiO2/Na2O is 2.0. This solution is used in the obtention of the gel of Example 1 with the result there mentioned. DESCRIPTION OF THE DRAWINGSIn order to illustrate what has been said, there is attached a sheet of drawings with a diagram of the process integrated in an industrial facility to produce Zeolite 4A. Taking this diagram as a reference, it could be observed how to the aluminium digestor 1 arrives from tank 3 bauxite and from tank 4 sodium hydroxide. Natural silica coming from tank 6 and sodium hydroxide from tank 4 go to reactor 5. The reaction mixture of digestor 1 of aluminium mineral passes through a heat exchanger 7 where gets a temperature between 90 and 100ºC to a filtration step 8. When the process is started from bauxite, unattacked residues formed by oxides and silicates of iron and aluminium are obtained which are treated with boiling sulphuric acid forming soluble sulphates of iron and aluminium; sulphuric acid comes from tank 23. Iron and aluminium are dissolved and the insoluble silica is used again. In filtration step 8 a residues drain to the acid reactor 9 is prepared which is at the same time fed with sulphuric acid from tank 23. The acid reaction product passes to a filtration step 11 where the resulting solid silica is recovered passing to the silica digestor 5 and the metal sulphates solution 12 can be used for water treatment. The filtrate coming from filtration step 8 passes to a purification step 13 where the organic material is removed by means of a treatment with hydrophobic interaction resins. From digestor 5 and from purification step 13 the reacting products pass to the gel reactor 14 where with agitation and at temperature of 60-65ºC the gel is obtained and passed to the crystallization step in the crystallizer 15 where, with adjustable temperature and agitation, it is achieved a crystallinity of 98%, passing afterwards to a cooling and concentration step 16 which cools the mass to a temperature below 75ºC in order to optimize the absorption of calcium of the Zeolite. Filtration and washing with de-ionized water in a vacuum filter 17 removes the excess alkalinity. The filtration 17 resulting mass is treated in dryer 20, and the resulting product, Zeolite 4A, with a particle size between 1 and 10 microns passes to the storage 21. The water coming from 16 passes to the tank 22; the mother liquor from filtration 17 through the exchanger 7 returns to the digestor 1. The washing waters of filter 17 are purified in 18 with silica alkaline solution provided by the digestor 5 and after filtration 19 pass to the SiO2 reactor 5 returning them to the process. The cake passes to reactor 1.
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A process for preparing a gel usable for obtaining zeolites characterized by preparing an alkaline aluminium solution starting from bauxite, attacking said bauxite in a reactor at atmospheric pressure with a solution of NaOH of 11 wt% minimum, purifying the resulting solution with resins and passing the purified product to a gel preparing step together with an alkaline solution of SiO2 with a molar ratio SiO2/Na2O between 2.0 and 2.5. A process according to Claim 1 where the solution of the bauxite is made in a rotative reactor. A process according to Claim 1 characterized because the bauxite residues (muds) are treated with boiling sulphuric acid, separating the sulphates as by-products and the SiO2 resulting from the acid attack is recycled as raw material to the SiO2 reactor. A process according to Claim 1 characterized by the purification of the alkaline aluminium solution, resulting from the digestion of the bauxite with NaOH, with hydrophobic interaction resins. A process according to Claim 1 where the NaOH solution has a concentration between 11 and 15 wt%.
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FORET SA; FORET, S.A.
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ARTIGAS PUERTO RAMON; FORNER BENITO JUAN; ARTIGAS PUERTO, RAMON; FORNER BENITO, JUAN
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